Spectroscopic Properties of Inorganic and Organometallic Compounds: v. 9: A Review of Chemical Literature (Specialist Periodical Reports)

A Specialist Periodical Report

Spectroscopic Properties of Inorganic and Organometallic Compounds Volume 9

A Review of the Literature Published during 1975

Senior Reporter N. N. Greenwood, School of Chemistry, University of Leeds Reporters D. M. Adams, University of Leicester J. H. Carpenter, University of Newcastle upon Tyne G. Davidson, University of Nottingham P. Gans, University of Leeds M. Goldstein, Shemeld City Polytechnic R. Greatrex, University of Leeds B. E. Mann, University of Shefield

@ Copyright 1976

The Chemical Society Burlington House, London,

WIV OBN

ISBN: 0 85186 083 4

ISS N : 0584-8555 Library of Congress Catalog Card No. 74-6662

Organic formulae composed by Wright’s Symbolset method

Printed in Great Britain by John Wright and Sons Ltd. at The Stonebridge Press, Bristol BS4 SNU

Foreword

Spectroscopic Properties of Inorganic and Organometallic Compounds was one of the first two Specialist Periodical Reports to be published by the Chemical Society in 1968, and it has appeared annually since that time. Now, after nine years, the Senior Reporter believes that the series should develop under the guidance of a new co-ordinator, and it is therefore a convenient time to review the achievements in this first formative stage. As mentioned in the Foreword to Volume 1 our aim has been not only to record results, but also to indicate the wide variety of ways in which spectroscopic information is used. Over the years the Report has indicated the pattern of development of the methods reviewed and has served as a useful source of ideas for further work. Some measure of the extensive use of spectroscopic techniques in the development of inorganic and organometallic chemistry can be gauged from the following paragraphs. During the past 20 years n.m.r. spectroscopy has grown from a specialist technique to a basic prerequisite for work in most areas of the subject. In Volume 1 the n.m.r. chapter cited 608 references and this number rapidly grew to 2272 references in Volume 5 . Further expansion of the chapter was moderated first by the appearance of a new SPR title devoted entirely to n.m.r. and later by the need to economize on space in order to achieve a realistic publication price. Nevertheless, the n.m.r. content of over 14 000 papers has been reviewed in this chapter during the past 9 years. Chapters on electron spin resonance and electronic spectra were included in the first three volumes but these topics were transferred in later years to a separate SPR entitled Electronic Structure and Magnetism of Inorganic Compounds. This enabled them to be treated more fully and made more space available for the remaining techniques. The use of n.q.r. and microwave techniques to study inorganic and organometallic compounds has also expanded substantially over the past decade. Both techniques give extremely valuable information on selected areas, but they are considerably more restricted in their applications than other spectroscopic techniques, and this is reflected in the fact that fewer than 100 papers on inorganictype compounds appear annually on each. Infrared and Raman spectra have been in the forefront of the development of inorganic chemistry for several decades and the recent burgeoning of interest in the laser Raman and matrix isolation techniques testifies to the continuing value of vibrational spectroscopic information. Inorganic chemists are particularly well served with bibliographic data in this area and there is a virtually complete inventory available. For work published before 1967 when the first SPR appeared there is an alphabetical listing of all compounds studied in the threevolume Index of Vibrational Spectra of Inorganic and Organometallic Compounds by N. N. Greenwood, E. J. F. Ross (and B. P. Straughan for Vol. 1). These volumes, published by Butterworths in 1972, 1975, and 1976, illustrate the

iv Foreword dramatic increase in t h e use of vibrational spectroscopy during the past two decades. By the beginning of 1950 fewer than a total of 1000 papers had been published, ever, on the i.r. and Raman spectra of inorganic compounds. Even in 1953 only 80 papers appeared and it was not until 1954 (140 publications) that the number started to increase rapidly. By the end of 1957, 2000 papers had been published in all, and the total passed 3000 in 1960 (the year in which the annual publication rate exceeded 400 for the first time). The annual rate exceeded 1000 in 1963 and was nearly 1500 in 1966, the last year covered by the Index. The present title began the following year, and it is salutory to note that, whereas a total of 9600 papers containing vibrational spectroscopic data on inorganic and organometallic compounds had been published up to the end of 1966 no fewer than 16 250 have been reviewed in the appropriate SPR chapters during the past 9 years. Mossbauer spectroscopy has likewise found extensive inorganic applications and the great variety of information obtainable for many elements by this technique is now widely appreciated. The number of papers on this technique reviewed annually in these volumes has trebled from 344 in 1967 to over 900 in the present volume, the total number of publications cited during the 9 years being nearly 5000. Whilst it is true that work on iron compounds still predominates, the results for many other elements are now appearing more extensively, notably tin, antimony, tellurium, and iodine in the main groups, ruthenium, osmium, iridium, platinum, and gold among the transition elements, and europium and several other lanthanide and actinide elements. Over the years the Senior Reporter has been most ably and energetically supported by a team of skilful and dedicated reporters. At various times a total of eighteen reporters have been involved in locating, selecting, and abstracting the vast domains of inorganic spectroscopic literature. That they have been able to compress their 39 OOO chosen publications into the confines of the nine reports at an average rate of 7.4 references per page, whilst still maintaining a readable style that is both reliable and informative, testifies to their enthusiasm, resourcefulness, and skill, The Chemical Society, and indeed the whole international community of chemists, is considerably in their debt. One feature that none can welcome is the continued trend to higher prices. Volumes 1 and 2 cost f 5 each, and Volumes, 3, 4, and 5 were priced at €10, but the next three volumes cost E l l , f24, and E25 respectively. It is true that there was a 40% increase in size between Volumes 1 and 8, but it would be wrong to disguise the fact that general inflation has more than trebled the ‘price per reference cited’ from 0 . 1 8 ~to 0 . 5 7 ~ . Indeed, it is a measure of the individual Reporters’ dedication to their work that the only thing that has not markedly increased for many years is their remuneration for an increasingly arduous job. ‘Spectroscopic Properties’, under the guidance of a new Senior Reporter, will continue to appear annually. Its place is assured as the primary source of spectroscopic information on inorganic and organometallic compounds being published each year, though it is no longer possible, or even desirable, to give a truly comprehensive coverage. Despite this, readers can be assured that all significant advances, and all interesting new applications and developments will be recorded, together with the important archival listings of data on which the possibilities of further advances depend. May 1976 N. N. G.

Contents

Chapter 1 Nuclear Magnetic Resonance Spectroscopy By B. E. Mann 1 Introduction 2 Stereochemistry Complexes of Complexes of Complexes of Complexes of Complexes of Complexes of Complexes of Complexes of Complexes of

1

1

Group I and Group I1 Elements Y,U, Ti, Zr, and Hf Cr, Mo and W Mn and Re Fe, Ru, and 0 s Co, Rh, and Ir Ni, Pd, and Pt Cu, Ag, and Au Zn, Cd, and Hg

3 Dynamic Systems F1uxional Molecules Li and Be Ti, Zr, and Hf V, Nb, and Ta Cr, Mo, and W Mn, Tc, and Re Fe, Ru, and 0 s Co, Rh, and Ir Ni, Pd, and Pt Cu, Ag, and Au Hg B, Al, and T1 Si, Ge, and Sn P, As, and Sb S, Se, and Te Equilibria Solvation Studies of Ions Ionic Equilibria Equilibria among Uncharged Species Course of Reactions Li and Mg Ti, Zr, Nb, Ta, Mo, W, Mn, and Re Fe, Ru, and 0 s

5 6

7 9 15 17 25 30 38 38

43 43 43 44 45 45 46 47 53 55 58 58 59 60 62 63 64 64 70 78 85 85 85 86

vi

Contents

co Rh and Ir Ni Pd, Pt, and Au Hg B and A1 Si, Ge, Sn, and Pb P

4 Paramagnetic Complexes Compounds of d-Block Transition Elements Compounds of the Lanthanides and Actinides 5 Solid-state N.M.R. Spectroscopy Motions in Solids Structure of Solids Molecules Sorbed onto Solids Water Sorbed onto Solids Other Molecules Sorbed onto Solids

86 86 87 87

88 89 90 91

91 92 100 103 105 110

119 119 121

6 Group III Compounds Boron Hydrides and Carbaboranes Other Compounds of Boron Complexes of other Group 111 Elements

124 124 129 133

7 Compounds of Silicon, Germanium, Tin, and Lead

134

8 Compounds of Group V Elements

145

9 Compounds of Groups VI, VII, and Xenon

161

10 Appendix

Chapter 2 Nuclear Quadrupole Resonance Spectroscopy By J. H. Carpenter 1 Introduction 2 Main-group Elements Deuterium Group I (Sodium-23) Group I1 (Magnesium-25) Group 111 (Gallium-69, Gallium-71, and Indium-1 15) Group V (Nitrogen-14, Arsenic-75, Antimony-121, Antimony-123, and Bismuth-209) Group VII (Chlorine-35, Chlorine-37, Bromine-79, Bromine-8 I , and Iodine-1 27)

163

167 167 167 167 168 168 168 169 171

vii

Contents

3 Transition Metals Manganese-55 Cobal t-59 Copper-63 and Copper-65 Rhenium-1 85 and Rhenium-1 87

Chapter 3 Microwave Spectroscopy By J. H. Carpenter

177 177 177 178 179

180

1 Introduction

180

2 Diatomic Molecules

180

3 Triatomic Molecules

182

4 Tetra-atomic Molecules

184

5 Inorganic and Organometallic Molecules containing Five or more Atoms

186

Chapter 4 Vibrational Spectra of Small Symmetric Species and of Single Crystals By D. M.Adams and P. Gans

190

1 General Introduction

190

2 Spectra of Small Symmetric Species Diatomic Species Tr i a t omic Species Tetra-atomic Species Penta-atomic Species Hexa-atomic Species Hepta-atomic Species

191 191 193 197 200 203 204

3 Single-crystal and other Solid-state Spectroscopy ‘Simple’ Lattice Types Mixed Oxides, Fluorides, and Ternary Phases Sheet and Chain Structures Silicates Oxoanionic Crystals Complex Cationic Salts Complex Anionic Salts Molecular Crystals

206 207 209 210 21 1 21 2 21 3 215 220

4 Vibrational Spectra of Solutions Water and Aqueous Solutions N on-aq ueous Solution F Solutions in Molten Salts

222 222 225 226

...

Contents Chapter 5 Characteristic Vibrational Frequencies of Compounds 228 containing Main-g roup Elements By P. Gans

Vlll

1 Group I Elements (including Hydrogen)

228

2 Group I1 Elements

229

3 Group I11 Elements Compounds containing B-H Bonds Compounds containing AI-H or Ga-H Bonds Compounds containing M-C Bonds (M = B, Al, Ga, In, or TI) Compounds containing B-N, AI-N, or Ga-N Bonds Compounds containing B-P Bonds Compounds containing M - 0 (M = B, Al, Ga, or In) or Ga-S Bonds Compounds containing M-Halogen Bonds (M = B, A], Ga, or In)

23 1 23 1 232

4 Group TV Elements Compounds containing M-H Bonds (M = Si, Ge, or Sn) Compounds containing M-C Bonds (M = Si, Ge, Sn, or Pb) Compounds containing M-M Bonds (M = Si or Ge) Compounds containing M-N Bonds (M = C, Si, Ge, or Sn) Compounds containing Si-P, Ge-P, Sn-P, or Ge-As Bonds Compounds containing M - 0 Bonds (M = C, Si, Ge, or Sn) Silicates and Related Species Compounds containing M-S (M = C, Si, Ge, or Sn) or C-Se Bonds Compounds containing M-Halogen Bonds (M = C, Si. Ge, Sn, or PG) Compounds containing P-H or As-H Bonds Compounds containing E-C Bonds (E = N, P,As, or Sb) Compounds containing N-N, P-P, or N-E Bonds (E = P, As, Sb, or Bi) Compounds containing N-E Bonds (E = P, As, Sb, or Bi) Compounds containing E - 0 Bonds (E = P, As, or Sb) Compounds containing E-S (E = N, P, or Sb) or E-Se (E = P or As) Bonds Compounds containing E-Halogen Bonds (E = N, P, As, Sb, or Bi)

240 240

233 234 235 237 238

242 244 245 246 247 250 25 1 252 255 257 258 258 26 1 263 265

Contents

ix

6 Group V l Elements Compounds Compounds Compounds Bonds Compounds or Te)

containing E-C Bonds (E = S, Se, or Te) containing S - 0 Bonds containing Se-0, Te-0, S-S, or Se-Se

267 267 268 270

containing E-Halogen

Bonds (E = S, Se, 27 1

7 Group VII Elements

273

8 Group VIlI Elements

274

Chapter 6 Vibrational Spectra of Transition-element Compounds By M. Goldstein

276

1 Introduction

276

2 General and More Significant Aspects Detailed Studies Use of Isotopic Substitution Resonance Raman Spectra Matrix-isolation Studies Metal- Metal Vibrations General Series of Complexes

276 276 27 7 280 28 1 283 284

3 Scandium and Yttrium

287

4 Titanium, Zirconium, and Hafnium

281

5 Vanadium, Niobium, and Tantalum

290

6 Chromium, Molybdenum, and Tungsten

292

7 Manganese, Technetium, and Rhenium

299

8 Iron, Ruthenium, and Osmium

30 1

9 Cobalt, Rhodium, and Iridium

306

10 Nickel, Palladium, and Platinum

310

11 Copper, Silver, and Gold

313

12 Zinc, Cadmium, and Mercury

316

13 Lanthanoids

31 8

14 Actinoids

319

Contents

X

Chapter 7 Vibrational, Spectra of Some Co-ordinated Ligands By G.Davidson

322

1 Carbon Donors

322

2 Carbonyl and Thiocarbonyl Complexes

337

3 Nitrogen Donors Molecular Nitrogen and Azido- and Related Complexes Amines and Related Ligands Oximes Ligands containing C = N Groups Cyanides and Isocyanides N i trosyls

348 348 353 358 359 363 367

4 Phosphorus, Arsenic, and Antimony Ligands

370

5 Oxygen Donors Molecular Oxygen, Peroxo- and Hydroxy-complexes Acetylacetonates and Related Complexes Carbon Dioxide and Carbonato-complexes Carboxylat o-complexes Keto, Alkoxy, Phenoxy, and Ether Ligands 0-Bonded Amides and Ureas Nit rates and Nit rat o-complexes Ligands containing 0 - N or 0 - P Bonds Ligands containing 0 - S Bonds Ligands containing 0-Halogen Bonds

37 1 37 1 373 374 374 378 380 38 1 383 385 386

6 Sulphur and Selenium Donors

387

7 Potentially Ambident Ligands Cyanate and Thiocyanate Complexes and Iso-analogues Ligands containing N and 0 Donor Atoms Ligands containing N and S Donor Atoms Ligands containing 0 and S Donor Atoms

39 1 39 1 394 400 402

Chapter 8 Mossbauer Spectroscopy By R. Greafrex

405

1 Introduction Books, Conference Proceedings, and Reviews

405 406

2 Theoretical

409

3 Instrumentation and Methodology

41 3

xi

Contents

4 Iron-57 General Topics Nuclear Parameters and Isomer-shift Cali brat ions Alloy-type Systems 67FeImpurity Studies 57C0Source Experiments and Decay After-effect Phenomena Compounds of Iron High-spin Iron(r1) Compounds High-spin Iron(rrx) Compounds Spin-crossover Systems and Unusual Electronic States Biological Compounds Low-spin and Covalent Complexes Oxide and Chalcogenide Systems containing Iron Binary Oxides and Hydroxides Spinel Oxides Garnet Oxides Perovskite Oxides Other Oxides Minerals Chalcogeni des

41 5 41 5 41 5 41 6 41 7

5 Tin-119

467 467 470 472 472 476 478

General Topics Tin(r1) Compounds Tin(1v) Compounds Organometallic and Other Mononuclear Compounds Compounds with Tin-Metal Bonds Oxide and Chalcogenide Systems containing Tin

6 Other Elements Main-group Elements Germanium (73Ge) Krypton (83Kr) Tin (l17Sn) Antimony (I2'Sb) Tellurium (126Te) Iodine (12'1, 1291) Xenon (lz9Xe) Caesium (133Cs) Transition Elements Nickel (61Ni) Zinc (*'Zn) Ruthenium (99R~) Hafnium (17'Hf) Tungsten (Inow,lsZW) Tantalum (IR1Ta)

42 I 423 423 432 434 437 44 1 449 449 453 455 457 458 462 464

480 480 480 480 480 480 483 486 488 489 489 489 489 490 49 1 49 1

492

xii

Contents Iridium (lS3Ir) Platinum (laapt) Gold (lo7Au) Lanthanide and Actinide Elements Promethi urn (Ip5Pm) Samarium (lp9Sm) Europium (151Eu, 1 5 3 E ~ ) Gadolinium (lS4Gd,lS5Gd,166Gd,157Gd) Dysprosium (ISoDy,lSIDy) Erbium (lseEr) Thulium (laSTm) Ytterbium (170Yb, 17*Yb) Neptunium (P37Np) 7 Bibliography

Author I ndex

492 493 493 494 494 494 494 496 497 497 497 498 500 500

507

Conversion Factors

1 kJ mol-'

2.3901 1.0364 8.3593 2.5061

x 10-1kcal mol-' x eV atom-] x 10 cm-l

1.1963 2.8592 1.2399 2.9979

x

x lo6 MHz

1 kcal mol-' 4.1840 kJ mol-' 4.3364 x eV atom-' 3.4976 x lo2 cm-l 1.0486 x 107 M H ~

1 cm-I

kJ mol-l x kcal mot-' x eV atom-' x lo4 MHL 9.6485 2.3060 8.0655 2.4180

3.9903 9.5370 4.1357 3.3356

1 MHz x lO-'kJ mol-l

kcal mo1-I eV atom-l x 10-6cm-1 x

x

1 eV atom-l x 10 kJ mol-I x 10 kcal mo1-l x 103crn-l x lo8 M H z

Mossbauer Spectra: EJ6'Fe) = 14.413 keV 1 mm s-l 4.639 x kJ mol-' 1.109 x kcal mol-' 4.808 x lo-* eV atom-l 3.878 x 10-4cm-1 1.162 x 10 MHz

For other Mossbauer nuclides, multiply the above conversion factors by E,,(keV)/14.413

Nuclear Magnetic Resonance Spectroscopy BY B.

E. MANN

1 Introduction The selective approach to the literature introduced last year has been continued, and the same criteria have been used. The polynuclear approach to n.m.r. spectroscopy has continued to grow in importance and papers containing information on nuclei other than ‘H are tabulated at the end of this Report. As usual, no attempt is made to cover n.m.r. spectroscopy in depth, and any reader who requires such an approach is referred to the excellent Specialist Periodical Report on ‘Nuclear Magnetic Resonance’.’ Volume 7 of ‘Advances in Magnetic Resonance’ has appeared and contains chapters on ‘Chemically Induced Dynamic Nuclear Polarization’ by G. L. Closs and ‘Magnetic Shielding and Susceptibility Anisotropies’ by B. K. Appleman and B. P. Dailey.2 ‘Progress in Nuclear Magnetic Resonance Spectroscopy’ has now adopted the form of a journal in which the following reviews have appeared: ‘Chemically Induced Dynamic Nuclear Polarization’ by R. G. L a ~ l e r , ~ ‘Application of Density Matrix Theory to N. M .R. Line-shape Calculations’ by P. D. Buckley, K. W. Jolley, and D. N. Pinder,4 and ‘The “Through-space” Mechanism in Spin-Spin Coupling’ by J. Hilton and L. H. Sutcliffe.6 Volume 6A of ‘Annual Reports on N.M.R. Spectroscopy’ contains ‘Nuclear Magnetic Resonance Spectroscopy of Paramagnetic Species’ by G. A. Webb; ‘General Review of Nuclear Magnetic Resonance’ by K. C . Ramey, D. C. Line, and G . Krow; ‘Nuclear Magnetic Resonance of Alkaloids’ by T. A. Crabb; and ‘Two-bond coupling between Protons and Carbon-13’ by D. F. Ewing.s The series ‘N.M.R. Basic Principles and Progress’ has continued with Volume 9 being devoted to ‘Lyotropic Liquid Crystals’ by C. L. Khetrapal, A. C . Kunwar, A. S. Tracey, and P. Diehl.’ Several books devoted to aspects of n.m.r. spectroscopy have been published, including ‘Nuclear Magnetic Resonance’ by F. A. Rushworth and D. P. ‘Nuclear Magnetic Resonance’, ed. R. K. Harris (Specialist Periodical Reports), The Chemical Society, London, 1975, Vol. 4; 1976, Vol. 5. ‘Advances in Magnetic Resonance’, ed. J. S. Waugh, Academic Press, New York, 1974, VOl. 7. H. G . Lawler, Progr. N.M.R. Spectroscopy, 1973, 9, Pt. 3. P. D. Buckley, K. W. Jolley, and D. N. Pinder, Progr. N.M.R. Spectroscopy, 1974, 10, 1 . J. Hilton and L. H. Sutcliffe, Progr. N.M.R. Spectroscopy, 1974, 10, 27. ‘Annual Reports on N.M.R. Spectroscopy’, ed. E. F. Mooney, Vol. 6A, Academic Press, New York and London, 1975. ‘N.M.R. Basic Principles and Progress’, ed. P. Diehl, E. Fluck, and R. Kosfeld, Vol. 9; ‘Lyotropic Liquid Crystals’, by C. L. Khetrapal, A. C. Kunwar, A. S. Tracey, and P. Diehl, Springer-Verlag, Berlin, 1975.

1

2 Spectroscopic Properties of 1)iorga)iic arid Orgnnornetullic Conipourid.~ Tunstall,8 ‘The Practice of N.M.R. Spectroscopy with Spectra-Structure Correlations for Hydrogen-1’ by N. F. Chamberlain,Q ‘Nuclear Resonance Spectroscopy, Part 1 : Proton Resonance. Textbook for Undergraduate Chemistry Students’ by T. Clerc and E. Pretsch,lO and ‘Pocket Text, Vol. 31 : Use of Proton N.M.R. Spectroscopy. Instruction Program for High Schools’ by P. Hallpop and H . Schuetz,ll and ‘Nuclear Magnetic Resonance in Organic Chemistry, No. 1’ by B. A. Ershov.12 More specialist texts include ‘N.M.R. Spectroscopy Using Liquid Crystal Solvents’ by J. W. Emsley and J. C . Lindon,13 ‘N.M.R. in Liquid Crystalline Solvents. Complications in Determining Molecular , ~ ~ ‘Nuclear Magnetic Resonance in Biochemistry : Geometries’ by J. B u l t h u i ~and Principles and Applications’ by ‘r. L. James.15 The book ‘Dynamic Nuclear Magnetic Resonance Spectroscopy’1Gcontains chapters on ‘Time-dependent Magnetic Perturbations’ by H. S. Gutowsky; ‘Delineation of Nuclear Exchange Processes’ by W. G. Klemperer; ‘Band-shape Analysis’, by G. Binsch; ‘Application of Nonselective Pulsed N.M.R. Experiments - Diffusion and Chemical Exchange’, by L. W. Reeves; ‘Determination of Spin-Spin Lattice Times in High Resolution N.M.R.’ by R. Freeman and H. D. W. Hill; ‘Rotation about Single Bonds in Organic Molecules’ by S. Sternhell; ‘Rotation about Partial Double Bonds in Organic Molecules’ by L. M. Jackman; ‘Dynamic Molecular Processes in Inorganic and Organometallic Compounds’ by J. P. Jesson and E. L. Muetterties; ‘Stereochemical Nonrigidity in Organometallic Compounds’ by F. A. Cotton; ‘Fluxional Ally1 Complexes’ by IS. Vrieze; ‘Stereochemical Nonrigidity in Metal Carbonyl Compounds’ by R. D. Adams and F. A. Cotton; ‘Dynamic N.M.R. Studies of Carbonium Ion Rearrangements’ by L. A. Telkowski and M . Saunders; ‘Conformational Processes in Rings’ by F. A. L. Anet and R. Anet; and ‘Proton Transfer Processes’ by E. Grunwald and E. K. Ralph. Two conference reports have also appeared.“. F. A. Rushworth and D. P. Tunstali, ‘Nuclear Magnetic Resonance’, Gordon and Breach, New York, 1973. N. F. Chamberlain. ‘The Practice of N.M.R. Spectroscopy, with Spectra-Structure Correlations for Hydrogen-1’, Plenum, New York, 1974. l o T. Clerc and E. Pretsch, ‘Nuclear Resonance Spectroscopy, Pt. 1 : Proton Resonance. Textbook for Undergraduate Chemistry Students’, Akad. Verlagsges., Frankfurt, 1973. l1 P. Hallpop and H. Schuetz, ‘Pocket Text, Vol. 31: Use of Proton N.M.K. Spectroscopy. Instruction Program for High Schools’, Vcrlag Chemie-Physik Verlag, Weinheim, West Germany, 1975. la B. A. Ershov, ‘Nuclear Magnetic Resonance in Organic Chemistry, No. l’, Izd. Leningr. Univ., Leningrad, 1974. lS J. W. Emsley and J. C. Lindon, ‘N.M.R. Spectroscopy Using Liquid Crystal Solvents’, Pergamon, Elmsford, New York, 1975. l4 J. Bulthuis, ‘N.M.R. in Liquid Crystalline Solvents : Complications in Determining Molecular Geometries’, International Scholarly Book Services, Portland, Oregon, 1974. T. L. James, ‘Nuclear Magnetic Resonance in Biochemistry: Principles and Applications’, Academic Press, New York, 1975. ‘Dynamic Nuclear Magnetic Resonance Spectroscopy’, ed. L. M. Jackman and F. A. Cotton, Academic Press, New York, 1975 (Chent. A h . , 1975, 83, 88 581). ‘Magnetic Resonance in Chemistry and Biology, Based on Lectures at the Ampere International Summer School o n Magnetic Resonance in Chemistry and Biology’, Basko Polje, Yugoslavia, June 1971, ed. J. N. Herak and K. J. Kresimir, Dekker, New York, 1975. l* P. S. Allen, E. R. Andrew, and C. A. Bates, ‘Magnetic Resonance and Related Phenomena’, Vols. 1 and 2 (Proceedings of the 18th Ampere Congress, Nottingham, September 1974), Elsevier, New York, 1975.

’*

Nuclear Magnetic Resonarice Spectroscopy

3

Several other books have appeared which contain sections or chapters devoted to n.m.r. ~ p e c t r o s c o p y , ~and ~ - ~including ~ the following articles : ‘Principles of Magnetic Resonance’ by K . H. Hausser;22‘Charge Density - N.M.R. Chemical Shift Correlations in Organic Ions’ by D. G. Farnum;23 ‘Metal Complexes (investigated by n.m.r. and e.s.r.)’ by H. J. Keller and K. E. S c h ~ a r z h a n s ; ~ ~ ‘Metal Ions as N.M.R. Probes in Biochemistry’ by S. J. F e r g u s ~ n ;‘Nuclear ~~ Magnetic Resonance of Nuclei other than Hydrogen’ by H . Zimmer and D. C. Lankin;26and ‘Applications of Carbon-13 N.M.R. in Inorganic Chemistry’, by M. H. Chisholm and S. G~dleski.~’ Once again numerous reviews have appeared. Some of the reviews are of n.m.r. spectroscopy in g e n e ~ a l . ~ *Other - ~ ~ reviews cover ‘Laboratory Technique which spies on Molecules’ (a history of n.m.r. spectroscopy and contributions made by British physicists and chemists);33‘Applications of Double Resonance and Fourier Transform N. M.R. Spectroscopy in Organic C h e m i ~ t r y ’ ‘Use ; ~ ~ of a High-resolution Nuclear Magnetic Resonance Method in Coordination Chemistry’;36‘Applications of the N.M.R. Method in the Study of Simple and Complex Hydrides of Light Metals’;36‘N.M.R. Studies for the Determination of the Structure of Alkoxides and Double Isopropoxides for Some Trivalent Metals’ ‘Broad-band N.M.R. and Pulsed Broad-band N.M.R.’ ;38 ‘Recent Analytical Applications of Nuclear Magnetic Resonance Spectroscopy’;39 ‘Chemical Shift Nonequivalence in Prochiral Groups’;40‘Nuclear Spin Relaxation Studies in Multiple Spin Systems’;41‘Spin-lattice Relaxation in Low Magnetic Fields’;42‘Spin-Lattice Relaxation: A Fourth Dimension for Proton N.M.R. 1s 20

21

22

23 24

28 26 27 28

ell 30

‘Critical Evaluation of Chemical and Physical Structural Information’, ed. D. R. Lide, jun. and M. A. Paul, National Academy of Sciences, Washington, D.C., 1974. K. A. McLauchlan, Oxford Chem. Ser., Vol. 1, 1972. ‘Metal Ions in Biological Systems’, Vol. 4, ‘Metal Ions as Probes’, ed. H. Sigel, Dekker, New York, 1974. K. H. Hausser, Method. Chim. ( A ) , 1974, 1, 318 (Chem. Abs., 1975, 83, 95 758). D. G. Farnum, Adv. Phys. Org. Chem., 1975, 11, 123. H. J. Keller and K. E. Schwarzhans, Method. Chim. ( A ) , 1974, 1, 395 (Chenr. Abs., 1975, 83,

123 331). S. J. Ferguson, ‘Technical Topics in Bioinorganic Chemistry No. 305’, ed. C. A. McAuliffe, Wiley, New York, 1975. H . Zimmer and D. C. Lankin, Method. Chim. (A), 1974,1,351 (Chem. Abs., 1975,83,95 759). M. H. Chisholm and S. Godleski, Prog. Inorg. Clwrn., 1975, 20, 299. E. Klesper and G . Sielaff, Monogr. Mod. Chem., 1974, 6 , 189 (Chem. Abs., 1975, 82, 43 745). S. Forsen, Kern.-Kemi, 1974, 1, 484 (Chem. Abs., 1975, 82, 49 345). J. A . S. Smith, Mod. Phys. Tech. Muter. Technol., 1974, 291 (Chem. Abs., 1975, 83, 50 092).

91

W. J. O’Sullivan, K. H. Marsden, and J. S. Leigh, jun., Phys. Tech. Princ. Protein Chem. ( C ) ,

sa

Y . Arata, Kagaku (Kyoto), Zokan, 1975, 66, 63 (Chem. Abs., 1975, 83, 185 559). C. L. Boltz, Spectrum, 1974, 12, 53 (Chem. Abs., 1975, 82, 56 705). W. von Philipsborn, Pure Appl. Chem., 1974, 40, 159. N. A. Kostromina, Zhur. neorg. Khim., 1975, 20, 1731. G. N. Boiko, Yu. I. Malov, and K. N. Semenenko, Russ. Chem. Rev., 1975, 1; Uspekhi Khim.,

a3 34 8S

86

1973, 245.

1975,44, 3.

87

R. C. Mehrotra and A. Mehrotra, Proc. Nat. Acad. Sci., India ( A ) , 1975, 40, 215 (Chem. Abs.,

88

E. Sambuc, Rev. Franc. Corps Gras, 1974, 21, 689 (Chem. Abs., 1975, 83, 17 767). D. M. Rackham, Proc. SOC. Anafyt. Chem., 1974, 11, 335. W. B. Jennings, Chem. Rev., 1975,75, 307. B. D. N. Rao, Pure Appl. Chem., 1974, 40,93. G. P. Jones, Magn. Resonance Chem. Biol., Lect. Ampere Internat. Summer School, 1975. 1971, 171 (Chem. Abs., 1975, 83, 139058).

1975, 83, 199 530).

39 40

41 4s

4

Spectroscopic Properties of Itiorgiriiir cciid Organometallic Comporrtlds

Spectroscopy’;43‘Can we expect any Meaningful Correlations between N. M.R. and E.S.C.A. Shifts?’;44‘isotope Effects on Molecular Properties’;4G‘Nonempirical Calculations of Nuclear Spin-Spin Coupling Constants’ ;l*‘Theories of Chemical Shift and Nuclear Spin Coupling constant^';^^ ‘N.M.R. Spectroscopy of Biochemical Materials’;48 ‘Principles of Low Temperature Nucleus Orientation and Nuclear Orientation/N.M.R.’;49 ‘N.M.R. Spectroscopy of Molecules dissolved in Liquid Crystals’;s0 ‘Molecular Structure Determination by N.m.r. Spectroscopy’;61 ‘Molecular Structure from N.m.r. in Liquid Crystalline Solvents’;52‘(Progress in) 13C N.m.r. Spectroscopy’;63‘Carbon-13 N.m.r.’;54 ‘Carbon-13 in Haems and Haemoproteins’;66 ‘13C Spin-Lattice Relaxation Times and the Mobility of Organic Molecules in Solution’;66 ‘Carbon-13 Nuclear Magnetic Resonance in Biosynthetic Studies’;57‘Use of 13CN.M.R. Spectroscopy for Biosynthetic Investigations’;68 ‘Natural Abundance Carbon-13 Fourier Transform N.ni.r. Studies of Large Molecules’;L9and ‘13C N. M.R. and Conformations of Biological Molecules’.6o In addition to these books and reviews, papers have appeared which are too broadly based to fit into any of the later sections of this chapter and are included here. The Larmor frequencies of 39K,41K, G7Fe,73Ge,87Sr,lo7Ag,1°*Ag, lS3W, and le70shave been measured with respect to 2H in Dz0.6113C N.m.r. spectra ion, of aqueous solutions of trans-l,2-diaminocyclohexane-NNN’N’-tetra-acetate [cydtaI4-, and its metal complexes have been studied for the alkaline-earth metals, Ag+, T1+, the zinc group, Sn2+,Pb2+,A13+, La3+, Co3+,and Th4+. The spectra are generally consistent with sexidentate co-ordination by [cydtaI4except at high pH, where further species of the type [M(cydta)(OH)]”(M = TI1, Hg”, AIII1)were observed. Species of the type [M(cydta)X]”- were confirmed for M = CO”’ (X = Cl) and Hg” (X = C1, Br, NCS, CN). Tentative structures for the latter species were discussed and use was made of 2J(M-13C) (M = Hg”, Pd”, Cd”, Sn“) and of lJ(lH-13C) to give further structural information. In the presence of the univalent cations (including H+) broad L. D. Hall, Chem. SOC.Rev., 1975, 4, 401. I3. J. Lindberg, J. Electron Spectrusc. mnrl Reluted Phenomena, 1974, 5 , 149 (Chmt. A h . , 1975, 82, 78 555). 46 A. D. Buckingham and W. Urland, Cheni. Rev., 1975, 75, 113. 46 J. Kowalewski, Chem. Conirnun. (Univ. Stockholm), 1974 (Chem. Abs., 1975, 82, 131 120). O7 I. Morishinia and K. Yoshikawa, Kagaku (Kyoto), Zokun, 1975, 66, 25 (Chem. Abs., 1975, 83, 185 557). 48 R. E. Richards, Endeavour, 1975, 34, 118. 4n N. J. Stone, Atuniic Energy Rev., 1974, 12, 585 (Chem. Abs., 1975, 83, 50070). L o P. M. Borodin and Yu. A. Ignat’ev, Yudern. Magn. Rezon., 1974, 5, 3 (Chem. Abs., 1975, 83, 105 473). 61 A. D. Buckingham, Pure Appl. Chem., 1974, 40, 1. aa L. C. Snyder and S. Meibooni, Crit. Eval. Chent. Phys. Struct. Inf., Proc. ConJ, 1974,1973, 143 (Chent. Abs., 1975, 82, 30440). 63 G. A. Gray, Analyt. Cheni., 1975, 47, 546A. b 4 E. J. Vincent, Rev. Franc. Corps Gras, 1974, 21, 699 (Chem. Abs., 1975, 83, 17 768). m K. Wuethrich, Pure Appl. Chent., 1974, 40, 127. E. Breitmaier, K.-H. Spohn, and S. Berger, Angew. Chem. Internat. Edn., 1975, 14, 144. 6 7 T. J. Simpson, Chetn. SOC.Rev., 1975, 4, 497. 6 8 A. G. Mclnnes and J. L. C. Wright, Accuunrs Chem. Res., 1975, 8, 313. 60 A. Allerhand. Pure Appl. Chent., 1975, 41, 247. O 0 I. C. P. Smith, H. J. Jennings, and R. Deslauriers, Accounts Chem. Res., 1975, 8, 306. 61 W. Salim and A. Schwenk, Z. Nnturfiwsch., 1974, 29a, 1763.

43

Nuclear Magnetic Hesonarice Spectroscopy

5

temperature-dependent resonances were observed, indicating relatively slow nitrogen inversion in the unco-ordinated or partially co-ordinated ligand.", Values have been assembled for the molecular diamagnetic and paramagnetic components of the proton shielding in the binary hydrides of the elements, and were shown to increase in a periodic fashion with the atomic number of the heavy atom. The dependence of the terms on the size and shape of the molecule and on the position of the hydrogen was illustrated by the values for B2H6 and [BHp]-.63 Similar calculations have also been carried out for the spin-paired binary fluoride molecules. The diamagnetic term increases periodically with the number of electrons in the molecule, but the resultant shielding follows the larger and more irregular variations in the paramagnetic term. These variations were attributed to such factors as empty d(t2,) orbitals and changing covalency The possible existence of spectroscopic subaffecting 2, and I AE l-1.64 stituent constants for ligands X (mainly uninegative ligands) applicable to a variety of metal compounds has been explored, and it was found that a lH n.m.r. spectrochemical series exists.66 The 13C n.ni.r. spectra of a variety of isonitrile complexes have been studied. The isonitrile 13C shielding trend is consistent with the hypothesis that some m back-bonding occurs in zero oxidation state complexes but is not important in positive oxidation state complexes. A metal triad shielding trend was observed with the isonitrile complexes as had been found previously in CO, carbene, and alkyl-metal complexes.6B 14N N.m.r. spectroscopy has been used to investigate the nature of the species in nonaqueous solutions of some covalent diamagnetic metal nitrato-compounds. Certain covalent nitrates of non-metals have also been studied for purposes of comparison. Solutions of metal nitrates in CCll and MeNO, show chemical shifts which clearly indicate their covalent nature but fail to distinguish the bonding mode, The suitability of pure nitric acid as a solvent and reaction medium for covalent metal nitrato-compounds has also been e x a ~ n i n e d .The ~~ factors affecting changes in 31Pchemical shifts of phosphorus chelate complexes with respect to phosphorus non-chelate complexes have been examined for a wide variety of transition metals. A deshielding contribution ranging from -21 to - 3 3 p.p.m. was observed for 15 complexes containing five-membered rings, and three examples show larger deshieldings. Six-membered rings exhibit shieldings in the range + 2 to 25 p.p.m.e8

+

2 Stereochemistry

This section is subdivided into eight parts, which contain n.m.r. information about lithium, sodium, beryllium, magnesium, and transition-metal complexes, presented by Groups according to the Periodic Table. Within each Group classification is by ligand type. As far as possible, cross-references are given at O2

n4

01)

o7 O8

0. W. Howarth, P. Moore, and N. Winterton, J.C.S. Dalton, 1975, 360. J . Mason, J.C.S. Dalfori, 1975, 1422. J. Mason, J.C.S. Dalton, 1975, 1426. L. G . Marzilli, P. Politzer, W. C. Trogler, and R. C. Stewart, Inorg. Chem., 1975, 14, 2389. D. L. Cronin, J. R . Wilkinson, and L. J. Todd, J. Magn. Resonance, 1975, 17, 353. K. F. Chew, M. A. Healy, M. I. Khalil, N. Logan, and W. Derbyshire, J.C.S. Dalron, 1975, 1315. P. E. Garrou, Inorg. Cliem., 1975, 14, 1435.

6

Spectroscopic Properties of Itiorgcmic arid Orgurronietallic Coinyorrrtcls

the beginning of each sub-group to compounds discussed elsewhere in this chapter. In this cross-referencing, it has not proved possible within the space available to include the many compounds that occur within the sections o n dynamic systems, paramagnetic systems, and solid-state n.1n.r. spectroscopy. Thus many more compounds of relevance to this section appear elsewhere. Complexes of Group I and Group I1 Elements.--The n.ni.r. spin-spin coupling constant in HD has been calculated using a variation calculation and a nonsingular contact operator to give a best value of 39.01 Hz, cJ 42.94 Hz (experi13C N.m.r. spectra have been measured for n-, sec-, and tert-butyland isopropyl-lithium as representative alkyl-lithiums. Spectra were also measured for two allyl-lithium compounds and three benzyl alkali-metal compounds as typical compounds where delocalized carbanions might be expected. Although it was found that the benzyl compounds behaved as if the charge was largely delocalized and the C , has an sp2 character, the ally1 compounds were found, in hydrocarbon solvents, to have a less extreme character.'O 'H N.m.r. spectroscopy has been used to study the structure of a-lithio-sulphoxides of the type (1) to determine the stereochemistry." I t has been suggested that 23Na n.m.r. spectroscopy can be used to measure sodium concentrations in solutions as dilute as 0.01 mol l-1.72 Be(B,H,), has been examined by lH (270 MHz) and llB (87.6 MHz) n.ni.r. spectroscopies over a range of temperatures using spin-decoupling and linenarrowing techniques. The low-temperature static configuration was identified.73 The lH n.m.r. spectrum of beryllocene over the temperature range -50 to

(cp, YO,

(CF,),COBe,

B U t e(1) L ; O

,BeOC(F,C), 0 (CF,), C

(2)

(1) 88

70

71

72 73

W. Sgnger and J. Voitlgnder, Cheni. Phys., 1975, 9, 183. S. Bywater, P. Lachance, and D. J. Worsfold, J . Phys. Chent., 1975, 79, 2148. K. Lett and A. Marquet, Tetrahedron Letters, 1975, 1579. A. L. Van Cieet and G . J . Templeman, Anulyt. Chpnt., 1975, 47, 1448. D. F. Gaines and J. €1. Morris, J.C.S. Cheni. Comnt., 1975, 626.

Nrrclenr Magnetic Rcsoiinnce Spectroscopy

7

- 140 "C in CF,C12 is a singlet,74 whereas the IgF n.m.r. spectrum of (2) shows two signals, as would be expected.7s H N.m.r. spectroscopy has been used to provide evidence for a peripheral Mg" complex of methylpheophorbide (3).76 The lH n.m.r. spectrum of Mg(acac), has been examined and evidence was found for conformational equilibria."

Complexes of Y, U, Ti, Zr, and Hf.---Information concerning coriiplexcs of these elements can be found at the following sources: 3-(q8-C8H8)-3,1 ,2-TiC,BDH11,1263 (M = Ti, Zr).12R4 and [R4N]+2[M(C2Me2BloH1,,)2]2The 'H n.m.r. spectrum of (4) shows bridging methyl groups at r 10.32 with 2J(sDY-C-1H)= 5 Hz at -45 "C. At 4 0 ° C there is rapid exchange.'* The n.m.r. spectrum of acetone orientated in the mesophase, uranyl fluoride, has been measured and spin-spin coupling constants have been d e t e r ~ i i i n e d . ~ ~ 1J(18F-235U), Tl for 23sUnuclei, and T, and T, for lgF nuclei have beeen measured; 1J(1DF-236U) = 4240 Hz at 338 K and 4566 Hz at 356 K.so The lH(Me) chemical shifts of MeTiX,, MeTiX(OPr'),, and ($'-C,H,)Ti Me(OEt), have been correlated with the lability of the titanium-carbon bond with respect to reaction with oxygen.*l Demonstration of the chirality of a number of titanium complexes, e.g. (q6-C6H6)(715-RC5H4)TiRcl,has been achieved using 'H n.m.r. spectroscopy,82and similarly the mode of formation of Bu~CHDCHDZrC1(q6-C6HS)has been deduced from 'H n.ni.r. coupling constants.83 A general scheme, utilizing both energy and kinetic data, has been derived for the classification of allylic metal complexes. On the basis of i.r. and lH n.ni.r. spectral data these compounds may be divided into six categories. Many variable temperature lH n.m.r. data were given for a number of compounds, including Zr(+allyl)4 and (cyclo-~ctatetraene)Hf(niethallyl)~.~~ 'H and 13C n.m.r. data, including lJ(lH-J3CC), have been used to characterize (q6-CsHs)(q3--I-MeC3H4)(q4-butadiene)Tiprepared by the reaction of (qS-C5H,)TiCl3and 1-MeC,H,MgBr.85 The influence of a chiral group on the I-H and 13C n.ni.r. parameters of titanocenes and ferrocenes has been studied. The difference of screening due to the diastereotopy of the cyclopentadienyl carbon nuclei is usually larger than the non-equivalence of the corresponding proton chemical shifts. If the chiral group is the titanium atom itself, a diastereotopy is also introduced into the cyclopentadienyl ring. 'H N.m.r. spectra obtained at 250 MHz, INDOR, and offresonance experiments using chemical shift reagents permit a complete analysis 74 76 76

77 iR

7B *O

*?

HG

C.-H. Wong and S.-M. Wang, Inorg. Nuclear Chem. Letters, 1975, 11, 677. R. A. Andersen and G. E. Coates, J.C.S. Dalton, 1975, 1244. H. Scheer and J. J. Katz, J. Amer. Chent. SOC.,1975, 97, 3273. H. G . Brittain, Inorg. Chem., 1975, 14, 2858. D. G. H. Ballard and R. Pearce, J.C.S. Chem. Comm., 1975, 621. V. A. Shcherbakov, L. L. Shcherbakova, and B. V. Semakov, Zhur. slrukt. Khim., 1974, 15, 925. I. Ursu, D . E. Demco, V. Simplaceanu, N. Valcu, and N. Ilie, Magn. Resonance and Related Phenomena, Proc. Congr. AnipPre, 18th (1974), 1975, 2, 533 (Chem. Abs., 1975, 83, 170 51 I). C. Blandy, R. Guerreiro, and D. Gervais, Compt. rend., 1974, 278, C, 1323. A. Dormond, J. Tirouflet, and F. Le Moigne, J . Organometallic Chem., 1975, 101, 71. J . A. Labinger, D. W. Hart, W. E. Seibert, tert., and J. Schwartz, J . Atner. Chem. SOC., 1975, 97, 3851. E. G. HofTmann, R. Kallwcit, G. Schroth, K Seevogal, W. Stempfle, and G . Wilke, J . Organometallic Chem., 1975, 97, 183. A. Zwijnenburg, H. 0. Van Oven, C. J. Groenenboom, and H. J. de Liefde Meijer, J. Organometallic Chciti., 1975, 94, 23.

8

Spec froscopic Properties nf Inorganic and Organometallic Conpounds

of 'H and 13C n.m.r. spectra. The results gave information on stereochemistry, and preferred conformations were identified.8B On the basis of theoretical discussions, the reported ISN chemical shifts for Ti(q6-CsMes),N, are in the wrong po~ition.~'The 'H and 13C n.m.r. spectra of various cyclopentadienyl Ti dialkylamides, e.g. (R'%N)3Ti(q5-C,I-(5R2R3), have been recorded and analysed. Increasing the size of R', R2, and R3 causes a bending of the ring from a +type in the direction of a +type in (R1aN)3Tistructure, as in (R2N)3Ti(q6-C6H6), (v6-C6H3R2R3).The compound (Me,N),Ti(indenyl) probably has a ~ 3 - ~ t r u ~ t ~ r e . 8 The 'H n.m.r. spectrum of (qa-CaH,),Ti in C6DBgives a signal at 7 4.96.89 For (PhO),(acac),Ti, no systematic trends in the variation of the relative chemical shift with the dipole moments or with the a-parameters of the phenoxyligands were In Zr20(0H),(HOCaH4CO2),,the phenolic hydrogen is still present but its n.ni.r. signal is shifted to lower field by co-ordination of the oxygen atom to the z i r c ~ n i u r n .The ~ ~ IH and 13C n.m.r. spectra of [Et,N], [Zr(S2C6H3Me),]show only one methyl resonance, indicating that the molecule is fluxional or the signals are accidentally degenerate. 13CN.m.r. data were also given for [RpE]n[M(SaC6H3Y)3] (E = N, As; M = Ti, Hf, Ta, Nb).92 A detailed investigation of the reaction of a series of pyridines with TiF4 has been carried out using 19F n.m.r. spectroscopy. Instead of the formation of only simple di-adducts, a mixture of products was found in MeCN. The main species are TiF4D2, [TiF3D3]+,and [TiF,D]- (D = pyridine base). An extensive series of [TiF,D]- complex ions was studied. Linear correlations of chemical shifts of fluorine in TiF,D2 and [TiF5D]- complexes were found with the pK, values of the pyridine. In some cases bidentate and sulphur ligands were also used and some data were given for GeF,,D, a d d ~ c t s .TiCI4 ~ ~ is a shift reagent for 13C n.m.r. spectra of carbonyl compounds, producing shifts of up to 16 ~ . p . r n . ~ ~ The The hydride resonance of HV(CO),(diars) is at T 14.48 but is 13C n.m.r. spectrum of (T~J'-C~H,),T~M~(CH,)shows a signal at 6 228, lJ(IHJ3C) = 132 Hz, attributable to the carbenoid methylene group and a signal at 8 -4, lJ('H-13C) = 122 Hz, due to the methyl group. Data have also been given for (~6-CsH5),Ta(CHBut)C1 and (+CsH5),Ta(CHPh)CH2Ph.g6 The lH n.m.r. spectrum of (T~-C~H~)V(CO), is consistent with the q3-formulation.g7 Orthovanadium acid esters of the type O=V(OCHR1R2)3 (R1= H, R2) have been investigated by lH n.m.r. spectroscopy. The signals of the protons attached to the or-carbon atoms are shifted considerably to low field. A linear dependence The 170,%'Al,31P, was found between the shifts and the u* Taft M. L. Martin, J. Tirouflet, and B. Gautheron, J. Organometallic Chem., 1975, 97, 261. J. Mason and J. G . Vinter, J.C.S. Dalton, 1975, 2523. U. Dgmnigen and H . Burger, J. Organometallic Chem., 1975, 101, 307. M. T. Anthony, M. L. H. Green, and D . Young, J.C.S. Dalton, 1975, 1419. J. F. Harrod and K. R. Taylor, Inorg. Chem., 1975, 14, 1541. I. A. Sheka, K. F. Karlysheva, L. A. Malinko, and N. A. Kostromina, Ukrain. khim. Zhur., 1974, 40, 1248 (Chem. Abs., 1975, 82, 131 603). O 2 J. L. Martin and J. Takats, Inorg. Chem., 1975, 14, 73. u ~ J H. G. Lee, S. D. Lessley, and R. 0. Ragsdale, USNTIS, Ad Rep. No. 784921/9GA, 1973 (Chent. Abs., 1975, 82, 145 906). A. K. Bose and P. R. Srinivasan, Tetruhcdron Letters, 1975, 1571. g b J. E. Ellis and R. A. Faltynek, J. Organometullic Chem., 1975, 93, 205. R. R. Schrock, J . Amer. Chcm Soc., 1975, 97, 6577. 87 M. Schneider and E. Weiss, J. Organometallic Cheni., 1974, 73, C7. ux A. Lachowic7, W. lIiibold, and K.-H. Thiele, Z . unorg. Chem., 1975, 418, 65.

Re

n7

Nuclear Magnetic Resonance Spectroscopy 9 and "Co n.m.r. spectra of [XO4M12-,V,O:~6]"- have been studied in the solid state and solution.QQThe 61V n.1n.r. spectra of [VO,l2+, isopoly- {[V0,l3-, [V10028]6-,[HnV10028]'+6},and heteropoly-acids ([PWllV04]4-, [H,W1,VO4,,l7-, [PM011V0401~-, [vw5Ol9l3-, [v2w401914-,[HVZW401913--,[V2M0,01814-, and [PV12040H8]7-) have been discussed. Chemical shift measurements were used to study the effect of heteroatoms.Io0 Variable-temperature 1 7 0 n.m.r. spectra have been recorded for [Nb601e]8-,[TasOlel8-, and [ M O ~ O ~ ~and ] ~ three -, resonances observed.1o1 The 31P 1i.m.r. spectrum of [PWlz03,]3- is at 14.96 p.p.m. upfield of H,P04 and as the tungsten is replaced by vanadium or molybdenum, the signals move to lower field, the lowest so far being [PV3Moe040]6-at 1.68 p.p.m. For H6PV2M~10040, three signals were found which were attributed to isomers of the five possible ones. Similarly [PV4W8040]7shows 21 lines from isomers of the 27 possible ones.lo2

'lv,

Complexes of Cr, Mo, and W.-Information concerning complexes of these elements can be found at the following sources: [l ,2-B,,HloCHGeM(CO),]( M = Cr, Mo, W),lZG6Me,Sn complexes of (q7-C7J-I,)Mo(CO),(PB10H12),123e[PWllV0J4-, [V2M~4019]4-,100 [PM12040]3-,(M = Mo, W),'"' and [PV3M O ~ O ~ lo2 ~]~-. The lH n.m.r. spectrum of (v6-C,HG)(q5-C5H5)WHshows coupling between the hydride and the benzene protons of 3 Hz and the cyclopentadienyl protons of 1.2 Hz. The 13C n.m.r. spectra of ( ~ 7 - C , H 7 ) ( ~ 6 - C 7 H gand ) M ~(+C5H5)(q7-C,H7)Mo have been reported.Io3 The 'H n.m.r. spectrum of [HW(CO),(dppe),][BF,] shows a hydride signal as a triplet of triplets at T 14.91.1°4 A series of cyclometallated complexes of the nitrogen donor ligands azobenzene, NN-dimethylbenzylamine, 8-methylquinoline, and benzo[h]quinoline, e.g. ( 5 ) ,

has been examined by 13C n.m.r. spectroscopy. The total number of expected aromatic quaternary and C H carbon atom resonances were determined by comparison of the noise-decoupled and single-frequency off-resonance decoupled spectra of a given complex. In this manner it can be readily determined that cyclometallation may have occurred. In those cases where M-13C coupling is L. P. Kazanskii, A. 1. Gasanov, V. F. Chuvaev, and V. I. Spitsyn, Fiz. Mat. Melody Koord. Khim., Tezisy Dokl., Vses. Soueshch., 5rh, 1974, 98, 'Shtiintsa', Kishinev, U.S.S.R., 1974 (ChPm. A h . . 1975, 83, 18 440). l o o L. P. Kazanskii and V. I. Sintsyn, Doklady Akad. Nuuk S.S.S.R., 1975, 223, 381. l o l A. D. English, J. P. Jesson, W. G. Klemperer, T. Mamouneas, L. Messerle, W. Shum, and A. Tramontano, J . Amcr. Ch~rn.SOC.,1975, 97, 4785. l o a M. T. Pope, S. E. O'Donnell, and R. A. Prados, J.C.S. Chem. Comm., 1975, 22. I o 3 E. M . Van Dam, W. N. Brent, M. P. Silvon, a n d P. S. Skell, J. Amer. Chenr. SOC.,1975, 97, 465. B. D. Dombck and R. J. Angelici, J . Atner. Chptrr. Stic., 1975, 97, 1261.

10

Spectroscopic Properties of Inorganic and Organometallic Compounds

observed an unambiguous determination of metal-carbon u bond formation is achieved.lo5 lH N.ni.r. spectroscopy has been used to show that only the transisomer of (r15-C,H,)RMo(CO)(PR',R2) exists in 13C N.m.r. data, including J(13C-18sW), have been reported for (q6-C6H5)(+CHz=CHCH2)W(CO),, ($'-CbH5)(+HC=CCH2)W(CO)3, (OC),WC(OEt)C=CPh, (OC),BrWCCH=CPh(NMe,), and (OC)4BrWCC=CPh.107 ,lP N.m.r. data have been reported for MO,((CH,),PM~,),.~~~ The lH n.m.r. spectrum of ( T ~ - C ~ H ~ ) (+C5H6)3M~(C0)2shows that the Tl-ring is static at room temperature.10e H and 13C n.m.r. data have been reported for (NC)2C=CClM(C0)3(~6-C6H6), C3(CN),NH2M(CO),(+C6H5) (M = Mo, W),l10 cis-(OC),Mo(CNMeCH,CH,NMe),, (6),l*l Me,NCCMe,COW(CO),(~5-C,H,),'12 (7),113 [Me,N]+[(OC),CrCOC(0 Me,Ph)]-, and (OC),CrC(O Me)C(OM e),Ph.ll4*116 vfe de

(OC),Cr-C,

R"

YR2 c

'OMe

13CN.m.r. parameters for a series of transition-metal carbene complexes of the type p-XC6H4SMeCW(CO), have been reported. Comparison of the (T" and o+ substituent constants for X with the carbene carbon shielding constants reveals that both D and 7~ interactions between the aromatic ring and carbene carbon atom are occurring. This idea was also supported by quantitative evidence derived from the shieldings of the aromatic carbon atoms of the carbene complexes and para-substituted benzene thiols. A direct relationship was found between the carbene carbon atom shieldings of a series of complexes of the type R1R2CW(C0)5 (R' = p-CsH,X; R2 = OMe) and the central carbon atom shieldings for carbonium ions of the type [(p-XC6H4)3C]+.116The carbene carbon chemical shift in (OC),WCPh, is 6 358.4, but treatment with PMe, causes this signal to move to 6 40.62, and (OC),WCPh,PMe, is formed.'l7 13C N.m.r. chemical shifts of a number of carbyne complexes have been reported. This includes trans-[Me,PCr(CO),CMe]+[BX,]-' carbyne carbon shift (6 365.4),ll8 A. R. Garber, P. E. Garrou, G. E. Hartwell, M. J. Smas, J . R. Wilkinson, and L. J . Todd, J . Organometallic Chem., 1975, 86, 219. P. J. Craig and J. Edwards, Chem. Uses Molybdenum, Proc. Conf., Ist, 1974,1973, 104 (Chem. Abs., 1975, 82, 30 714). l o 7 F. H. Kohler, H. J . Kalder, and E. 0. Fischer, J. Organometallic Chem., 1975, 85, C19. lofl E. Kurras, H. Mennenga, 0. Oehme, U. Rosenthal, and G . Engelhardt, J . Organometallic Chem., 1975, 84, C13. H. Rrunner and R. Lukas, J . Organometallic Chem., 1975, 90, C25. ] l o R. B. King and M. S. Saran, Inorg. Chem., 1975, 14, 1018. ll1 B. Cetinkaya, P. B. Hitchcock, M. F. Lappert, and P. L. Pye, J.C.S. Chem. Comm., 1975,683. 1 1 2 R. B. King and K . C. Hodges, J . Amer. Chem. Soc., 1975, 97, 2702. K. H . Dotz and C. G. Kreiter, J . OrganometaNic Chem., 1975, 99, 309. 114 U. Schubert and E. 0. Fischer, Annalen, 1975, 393. E. 0. Fischer, U. Schubert, W. Kalbfus, and C. G. Kreiter, 2. anorg. Chern., 1975. 416, 135. llUC. V. Senoff and J. E. H. Ward, Inorg. Chem., 1975, 14, 278. F. R . Kreissl and W. Held, J . Organometallic Chem., 1975, 86, C10. E. 0. Fischer and K. Richter, Angew. Chrm. Internat. Edn., 1975, 97, 345.

lo6

loo

Nuclear Magnetic Resonance Spectroscopy 11 Br(OC),CrCC,H,Me (6 319.12), cf. carbene carbon atom at 6 31 1.14, 1J(13C-31P)= 4.9 Hz in Br(OC),CrC(PMe,)C,H,Me 119 and Br(OC),CrCNEt, (6 264.12).120 ,*P N.1n.r. spectroscopy has been used to show that the 31P chemical shift of (OC),MC(PPh,)(SPh), is the same as C(PPh3)(SPh)2.121 lH and ]OF n.m.r. data have been reported for [M]C=CRC(CF3)20CH2 and [M]CR1CR2R3C(CF3),0CH2 where [MI = (q5-C5Hb)M~(C0)3,(r15-C6H6)W(CO),, (q6-C6H6)Fe(Co)L, or Mn(C0),,lZ2 (q5-C5H~)M(CO),SiF,Me3-, (M = Mo, W),12, and (hfac),SnM(CO), (M = Cr, Mo, W) and related Dithiocarbamato-complexes of the type (qS-C5H5)Mo(C0)2(S2CNPriH)and (776-C6H6)Fe(Co)(s2CNPriH)are chiral. The isomers which can be identified at low temperatures by 'H n.m.r. spectroscopy racemize or epimerize at room temperature as a consequence of rotation around the S2CNR2bond.125 'H and 13C n.m.r. data have been reported for (q4-n~rbornadiene)Cr(CO),PPh3,126and cis- and tmns-(+C6H6)M(CO)2(PPh3)X (M = Mo, W ; X = Br, I).',' 1°F N.m.r. chemical shifts of free fluoroarenes have been correlated with the SwainLupton field and resonance parameters. Comparison of these data with the corresponding Cr(CO), complexes shows little change in the transmission of mesomeric effects by para-su bst it uen ts. meta-Substituen ts which interact primarily by a field effect have very little influence on the fluorine chemical shift in the complexes and it was suggested that the a-framework of the ring interacts with the chromium.12BThe 13C n.m.r. spectra of a series of (OC),Cr(arene) complexes have been determined. The spectra were interpreted in terms of electronic effects of the substituent together with effects arising from conformational preferences of the Cr(CO), residue. No evidence for kinetic restriction of rotation could be found for any of the complexes at temperatures greater than -60 0C.120 As part of an effort to delineate the structure and properties of (arene-chelate)Cr(CO), compounds, 13C n.m.r. data have been measured for benzonorbornadiene, L, syn-LCr(CO),, and (8). The data were interpreted as showing that little molecular distortion accompanies the formation of synLCr(CO), from L; the introduction of appreciable strain in the alkyl portion of the arene-olefin ligand is concomitant with conversion of syn-LCr(CO), into (8).13* The lH n.m.r. spectra of alkylarylcarbenium ions, e.g. (9), complexed to Cr(CO), have been reported and the charge distributions compared with those in the corresponding free ligands.131 The chirality of (q6-PhC02Me)Cr(CO)[P(OMe),][P(OEt),] and related compounds has been demonstrated by 'H n.m.r. llD 120

F. R. Kreissl, J. Organometallic Chem., 1975, 99, 305. E. 0. Fischer, G. Huttner, W. Kleine, and A. Frank, Angerv. Chem. Internut. Edn., 1975, 14, 760.

E. Lindner, J . Organometallic Chem., 1975, 94, 229. D. W. Lichtenberg and A . Wojcicki, Znorg. Chem., 1975, 14, 1295. 123 W. Malisch and P. Panster, Chem. Ber., 1975, 108, 2554. A. €3. Cornwall and P. G . Harrison, J.C.S. Dalton, 1975, 1486. H. Rrunner, T. Rurgermeister, and J. Wachter, Chem. Bcr., 1975, 108, 3349. lee G. Platbrood and L. Wilputte-Steinert, J . OrgunomPtallic Chem., 1975, 85, 199. D. L. Beach and K. W. Barnett, J . Orgnnonicfallic Chetn., 1975, 97, C27. Iz8 J . L. Fletcher and M . J. McGlinchey, Cunad. J . Chcm., 1975, 53, 1525. lZH W. R. Jackson, C. F. Pincombe, I. D. Rae, and S. Thapebinkarn, Austral. J . Chent., 1975, 12*

Iaa

In" 131

28, 1535.

B. A. Howell and W. S. Trahanovsky, J . hfagn. Resonance, 1975, 20, 141. M. Acampord, A. Ceccon, M. Dal Farra, and G . Giacometti,J.C.S. Chem. Conrt~.,1975, 871.

12

Spectroscopic Properties of Inorganic, and Organometnllic Compounds Cr(CO), I

The 31P n.m.r. spectra of (qR-PhX)Cr(CO),PPh, and related complexes have been investigated in neutral and acidic media. The protonation of (yR-PhX)Cr(CO),PPh3 and (q6-C6H,Me3)Cr(CO),PPh3results in the greater upfield shielding of the 31P[1H]n.m.r. signal. The temperature dependence of the 31P n.ni.r. spectra was investigated and the degree of protonation was found to increase with decreasing Even at low temperatures, the 13C n.m.r. spectrum of (qe-C7H,)Mo(CO),L [L == P(OPh),, PPh,, PPh,Me, or PPhMe,] shows only one 13C0 signal which is consistent with a C , structure.134 lH and 13C n.m.r. data have also been reported for (y6-C7H7R)Mo(CO)2L, and [(q7-C,H,)M~(C0)2L]+.13C 13C N.m.r. chemical shift and J(13C-31P) coupling-constant data have been given for PMe,Ph,-,, P(OPh)3, PEt,, AsPh,, and ligands and the corresponding LNi(CO),, LCr(CO),, and (q5-C,H,)Mn(CO),L complexes. Analysis of the 13C n.m.r. chemical-shift data for the C(4) resonance in these C,H,X derivatives suggests (i) a resonance-substituent parameter, R = 0,005 for X = PPh,, and R = 0.09 for X = (OC),CrPPh,; (ii) a decrease in the resonance interaction of the Group VB atom with the phenyl ring in EPh, derivatives in the order E = P > As > Sb; and (iii) an increase in the electron density at the phosphorus atom in PPh,-,Me, derivatives in the order PPh3 < PPh,Me < PPhMe,. There appears to be an anomalous shielding of the C-1 resonance in these derivatives upon complcxation and with increasing electronegativity of the Group VB atom. The electron-withdrawing character of the metal carbonyl moiety appears to increase in the order (q5-CSH5)Mn(C0),L< LNi(CO), < LCr(CO),. The magnitudes of J(13C-31P) were also extensively 13CN.m.r. spectra have also been obtained for a series of compounds L,M(CO),-, [M = Cr, Mo, W ; L = CO, PC13, P(OPh),, P(OMe),, PH,, PPh,, AsPh,, SbPh3, PEt,, PBun3, NH2CsH11, NHCBHIO,CI-1. For all derivatives studied where L is formally a two-electron donor, the resonance for the CO trans to L is deshielded relative to the resonance for the carbonyl groups cis to L whereas the converse has been observed when L is formally a one-electron donor. The effect of the sequential replacement of CO ligands by phosphine or phosphite ligands would appear to be additive. A monotonic shielding of the CO resonance in L,M(CO),-, derivatives was observed upon replacement of Cr by Mo and W, G. Jaouen, A. Meyer, and G. Simonneaux, Tetrahedron, 1975, 31, 1889. L. A. Fedorov, P. V. Petrovskii, E. I. Fedin, N . K . Baranetskaya, V. I. Zdanovich, V. N . Setkina, and D. N. Kursanov, J . Organometallic Chc,m., 1975, 99, 297. 134 E. E. Isaacs and W . A. G. Graham, J . Organotnetallic Chem., 1975, 90, 319. 136 D. Seyferth and C. S. Eschbach, J . Organotnrlallic C’hem., 1975, 94, C5. lJ0 E. E. Isaacs and W. A. G. Graham, J . Organonietallic Chenr., 1975, 90, 319. G . M. Rodner and M . Gaul, J . Organometallic. Chent., 1975. 101, 6 3 . lJ3

Nuclear Magnetic Resonance Spectroscopy 13 and it was suggested that there is a contribution to the chemical shift from neighbouring diamagnetic screening. A linear correlation was observed between the cis-COchemical shift for LM(CO)5 derivatives and both the k2 stretching force constant and the CO chemical shifts for the analogous LNi(CO), derivatives. These data were interpreted in terms of the relative a-donor-r-acceptor character of the ligands. The 2J(13C-M-31P) value correlates with previously published 2J(31P-M-31P) ~ a 1 u e s . lThe ~ ~ lH n.m.r. spectrum of (1 1) has a broad resonance for H(3) which sharpens on co-ordination in LM(CO), (M = Cr, Mo, W). This behaviour was attributed to more rapid 14N relaxation in the complex effectively decoupling lJN from 1H.13913C N.1n.r. data have been reported for (12).140 Glyoxaldi-imines, RN=CHCH=NR, show in the 'H n.m.r. spectrum

a downfield shift of the glyoxalic protons when complexed to M(CO), (M = Mo, W) but increasing high-field shifts when complexed to M(C0),PR3 and M(C0)2(PR3)2complexes.141 The lH and 31P n.m.r. spectra of cis-Mo(CO),(Me,PH), have been analysed to give 2J(31P-31P)= 26 Hz. Data were also given for (OC)4MoPMe2EMeEMePMe2(E = P, As), and related species.142 R1P(CH2CH,PRZ2),, 31PN.m.r. spectra of metal complexes of Me2P(CH2)2PPh2, Me2PCH2CH2PPhCH2CH2PPh2, and P(CH,CH2PR3)3 have been reported and discussed on the basis of known structures of the metal complexes. The anomalously large downfield shifts of the phosphorus atoms in five-membered chelate rings are increased if the phosphorus atom belongs to two or three fused five-membered rings. Thus the central phosphorus atom in [{P(CH2CH2PR3)3}NiCl][PF,] which belongs to three fused five-membered chelate rings exhibits a downfield co-ordination shift in excess of 150 p.p.m. In [{ R1P(CH2CH2PR22)2}PtCl]+ derivatives, 1J(31P-10aPt)for the phosphorus atom trans to C1 is lower that that found in the corresponding complexes in unidentate p h ~ s p h i n e s . ~ " ~ N.m.r. data have been reported for rner-{(PhO),P},Cr(CO)3, ("P) ;144 M(CO)&L, Fe(CO),L [M = Mo, W ; L = (13)], [Ph2P(0)CHPrnPPh2]M1(CO),[Ph2P(0)CHPrnPPh2]M2Xz(M1= Cr, Mo, W ; M2 = Cd, Hg), (31P);146 C~S-MO(CO)~(R,-~P(NH~),)~, C ~ ~ - M O ( C O ) ~ ( M ~ ~ P N H ) , S(31P);147 ~ M ~ , , (141, 13'

143

lPS lP4 146

14'

G. M. Bodner, Znorg. Chem., 1975, 14, 2694. K. H. Pannell, C. C.-Y. Lee, C. PhrkBnyi, and R. Redfearn, Znorg. Chim. Acta, 1975, 12, 127. A. R. Siedle, Znorg. Nuclear Chem. Letters, 1975, 11, 345. H. Tom Dieck, 1. W. Renk, and K. D . Franz, J . Organornetallic Chem., 1975, 94, 417. 0. Stelzer and E. Unger, Chem. Ber., 1975, 108, 2232. R. B. King and J. C. Cloyd, jun., Znorg. Chern., 1975, 14, 1550. W. A. Schenk and M. Schmidt, J . Organometallic Chc.m., 1975, 96, 375. M. Y. Darensbourg and D . Daigle, Znorg. Chem., 1975, 14, 1217. S. 0. Grim, L. C. Satek, C. A. Tolman, and J. P. Jesson, Znorg. Chem., 1975, 14, 656. G . Johannsen, 0.Stelzer, and E. Unger, Chon. Ber., 1975, 108, 1259.

14

Spectroscopic Properties of Inorganic and Organome faliic Compounds

(E = P, As), (31P);148(OC),WPPh2CH2CH2PPh2R(R = lone pair, But, 0,

+Hg2C14,gPtCI,), M(CO),Me,AsCHC(CF,)=C(CF3)CH~sMe2,(l9F);l6O C ~ ~ - M O ( C O ) ~ ( P P ~ ~ C H , N M(31P);151 ~ C H ~ )(OC),Mo(PPh,CH,PPh,),, ~, (31P);162 and C~~-{(M~,S~),NPF~)~MO(CO)~, (31P).153 l H N.m.r. spectroscopy, including J(lH-15N), has been used to establish the structure of (l5).ls4 'H and 31P n.m.r. data have been reported for Mo(N2)(RC6H4CN)(dppe),.155 9 5 M and ~ 9 7 Mrelaxation ~ times have been measured for

(1 5 )

aqueous solutions of sodium molybdate in the pH range 7-12. From the relaxation times at high pH where exchange effects are negligible, the quadrupole moment ratio I Q(g7Mo)/Q(e5Mo)I = 11.4 k 0.4 was obtained. This large ratio allowed a particularly simple determination of kinetic parameters of interest such as the protonation rate constant and the relaxation time of the protonated 157 The n.m.r. signal of lS3Win a liquid diamagnetic sample has been detected for the first time by using a Fourier transform n.m.r. spectrometer especially developed for nuclei with weak n.m.r. signals. The IB3W Larmor frequencies and chemical shifts of WF,, [WO4I2- in aqueous solution, and wc1, dissolved in CS2 were determined. The lS3W resonance was referred to that of the proton in H 2 0 and the magnetic moment of le3W in WF, is p = 0.1 16 224 5(7)p.,-. An upper limit for 1J(170-183W)in [WO4I2- was given. Values of TI and T, for leaW in WF, were also measured.168 The structures of Mo" and Mo"' complexes of 8-quinolinol and 2-Me-8-quinolinol in D M S O solution have been investigated by IH n.1n.r. and i.r. spectroscopies. The n.m.r. results indicate strong covalent metal-ligand oxygen bonding but only weak labile metal-nitrogen interaction^.'^^ lH N.ni.r. spectra of H3PM120ao,nH20 (M = Mo, W) in acetone and MeCOEt have been measured at room temperature. A singlet was observed, the position of which depended on the acid concentration and the water content.lsO 31P Chemical shifts and TI have been measured for 0. Stelzer and E. Unger, J. Organometallic Chern., 1975, 85, C33. R. L. Keiter, K. M. Fasag, and L. M. C a w , Inorg. Chem., 1975, 14, 201. I J 0 W. R. Cullen and L. Mihichuk, Canad. J. Chent., 1975, 53, 3401. lS1 S. 0. Grim, L. J . Matienzo, D . P. Shah, J . A. Statler, and J. M. Stewart, J.C.S. Clzenz. Cottiin., 1975,928. 15t E. E. Isaacs and W. A. G . Graham, Inorg. Chcni., 1975, 14, 2560. lS3 G.-V. Roschenthaler and R. Schmutzler, Z . anorg. Chem., 1975, 416, 289. lS4 A. A. Diamantis, J. Chatt, G . A. Heath, and G. J. Leigh, J.C.S. Chenr. Contm., 1975, 27. 165 T. Tatsumi, M. Hidai, and Y. Uchida, Inorg. Chem., 1975, 14, 2530. I6O R. R. Vold and R. L. Vold, J . M q n . Resonance, 1975, 19, 365. lh7 J . Kaufmann, J . Kronenbitter, and A. Schwenk, Z . Phpsik ( A ) , 1975, 274, 87 (Chenr. Ahs., 1975, 83, 155 244). 15" J . Hanck and A. Schwenk, Z . Physik (B), 1975, 20, 75 (Cliem. Ahs., 1975, 82, 131 623). I). T. Sawyer, J. N. Gerber, L. W. Amos, and L. J. D e Hayes, Chcm. U s ~ Molyhdenunr, s Proc. ConJ, Ist, 1974, 1973, 257 (Chem. Abs., 1975, 82, 82267). lEo A. I. Gasanov, V. F. Chuvaev, and V. I. Spitsyn, Doklady Ah-ad. Nauk S.S.S.R., 1974, 218, 379. 14a

Nirck~arMagnetic Resojiance Spectroscopy

15

solutions of molybdo- and tungsto-phosphoric heteropolyacids in HzO, Me,CO, EtOH, and Bu"0H. The value of Tl is influenced by solvent and pH.lel For ROWF5, the 19Fchemical shifts of both the axial and equatorial fluorine atoms move to progressively lower field, in the order R = Me, CICH,CH,, CI,CHCH,, Br,CCH,, CI,CCH,, F,CCH2, F2CH(CF2)3CH2,CF,CF,CH,, and (CF,),CH, the change being twice as great for axial as equatorial fluorines. The results were interpreted in terms of u- and 7r-bonding contributions.ls2 Raman and 18Fn.ni.r. spectroscopy have been used to show that the adducts XeF,,WOF, and XeF2,2WOF, are best formulated as covalent structures containing Xe-. F.- W bridges. l'F N.m.r. spectra of XeF2,2WOF, dissolved in S02ClF also show that complex equilibria involving Xe-0-W and Xe- F-. W bridged species occur.163 19F N.m.r. data have also been reported for WC1(OTeF5)6,164 [PF,]-, [AsF,]- (including 1eF{75As}INDOR), and [WFs]-.ls5

Complexes of Mn and Re.--Information concerning complexes of these elements can be found at the following sources: (Me,C=C=NMe,)Mn(CO),, 77

Me2C=C(NMez)Re(C0)5,112 (OC)5MnC=CRC(CF3)20CH,,122 (+C5H5)Mn(CO),L,137and SiH,C1Mn(C0)5.1336 13C N.m.r. data have been reported for XRe(CO), (X = Me, MeCO, Ph, PhCO, Br, CI3Si, Me,Si, Me,Ge, Me,Sn, Me,Pb). In the XRe(CO), series, the carbonyl carbon atom trans to X is more shielded than the carbonyl atom cis to X. However, in the cationic complex [MeCNRe(CO),][PF,] the carbonyl carbon atom trans to MeCN is less shielded than those in the cis-position. There is a linear relationship between the 13C chemical shift and the stretching force-constant for cis-CO in the XRe(CO), series.lG6The lH n.m.r. spectrum of {(Me,SiCH2),Re(0)}20 shows only one CH2 signal even at -90 "C but at that ~ compounds of the type (16), the lH temperature there is b r ~ a d e n i n g . ' ~For n.m.r. spectrum is first order.les 'H and 13C n.m.r. data have been reported for (vS-C5H5)Mn(C0)2(p-CH2)Mn(C0)2(r15_CgH5) (two isomers),1eo (q1-C5C16)lH and Mn(CO),, (T~-C,CI,)M~(CO)~, and Rh(~5-C5Cl,)(~4-cyclo-octadiene).170 19F 1i.m.r. data have been reported for Mn(COCH2CsF5)(C0)5,171 FCsH,MnI

(CO),PPh3, (17),17, (18), (M = Mn, Re),173 (OC),MC=CPh-C(CN)(CF,)I C(CN)(CF,)CH, (M = Mn, Re),174 R~CU(C~C~F,),(CO)~(PP~~),,~~~ and (1% including n.m.r. data.176 L. I. Lebedeva and E. V. Vanchikova, Zhur. neorg. Khim., 1974, 19, 3285. F. E. Brinckman, R. €3. Johannesen, R . F. Hammerschmidt, and L. B. Handy, J . Fluorine Chem., 1975, 6, 427 (Cheni. Abs., 1975, 83, 211 049). le3 J. H. Holloway, G. J. Schrobilgen, and P. Taylor, J.C.S. Chem. Comm., 1975, 40. K. Seppelt, Chem. Ber., 1975, 108, 1823. A. Prescott, D. W. A. Sharp, and J. M. Winfield, J.C.S. Dalton, 1975, 934. M . J. Webb and W. A. G. Graham, J . Organometallic Chent., 1975, 93, 119. Ie7 K. Mertis, D. H. Williamson, and G. Wilkinson, J.C.S. Dalton, 1975, 607. ta* C. P. Casey and C. A. Bunnell, Inorg. Chem., 1975, 14, 796. lBOW. A. Herrmann, B. Reiter, and H. Biersack, J . Organometallic Chem., 1975, 97, 245. l 7 O K. J. Reimer and A. Shaver, Inorg. Chem., 1975, 14, 2707. 171 R. L. Bennett, M. 1. Bruce, and F. G. A. Stone, J . Organometallic Chem., 1975, 94, 65. 17* R. J. McKinney, R. Hoxmeier, and H. D. Kaesz, J . Amer. Chem. Sac., 1975, 97, 3059. M. I. Bruce, B. L. Goodall, G. L. Sheppard, and F. G. A. Stone, J.C.S.Dalton, 1975, 591. J. P. Williams and A. Wojcicki, Inorg. Chim. Acta, 1975, 15, L21. 176 0. M. A. Salah and M. I. Bruce, J.C.S. Dalton, 1975, 231 1. R. J. McKinney and H. D. Kaesz, J. A n m . Chent. SOC., 1975, 97,3066. lea

16

Sptv*~t*oscopic Properties of Inorganic and Orgunornetcillic Compounds

OMe

F

lH Chemical shifts of R,SnMn(CO), have been interpreted in terms of deshielding by the Mn-Sn bond.'77 leF N.m.r. data have been reported for (CF,),AsMn(CO), and (CF~),ASCO(CO),.'~~ The 'H n.m.r. spectrum of cis(q2-R02CC=CC0,R)Mn(CO),HgBr shows hindered rotation about the Mn-acetylene bond.17BA solution of (+allyl)Re(CO), dissolved in a nematic phase has been examined by 'H n.m.r. spectroscopy. The dipolar coupling constants obtained were used to investigate the structure of the allyl ligand, and it was concluded that the protons do not lie in one plane. The effect of averaging dipolar couplings over vibrations was investigated with the aid of a normalco-ordinate analysis of the vibrations of the allyl ligand.laO For a series of (benzoylcyclopentadienyl)Mn(CO)3 derivatives, the shifts in T values in the lH n.m.r. spectra on substitution were interpreted in terms of both electronic and steric effects.lal lH and 13C n.m.r. data have been reported for (q5-C5H2Ph(CO,Me),}Mn(CO),. For this compound the ,,Mn signal is 2588 p.p.m. upfield from aqueous [MnOJ- with a line width of 5742 Hz.lE2Trends in the 3lP n.ni.r. co-ordination shifts for the complexes M(CO),BrL,, [Mn(CO),L,(NCMe)]-'-, (qe-MeCSH,)Mn(CO)L2, and {(y6-MeC5H4)Mn(CO)2>2L2 (M = Mn, Re; L, = Ph2PCH,PPh2, dppe) have been The 'H n.1ii.r. spectrum of (20) in CH2Cl, indicates that the ring is locked. The values of ,J(lH-'H) indicate strong puckering of the chelate ring about the carbon-carbon axis, although the derived AsCCC dihedral angle is less than the solid-state value.lE4 31P N.m.r. data have also been reported for (2l),ls5 and (776-C6H6)(OC)MnPPhHNBut.1~* S. Onaku and H. Sano, Bull. Chem. SOC.Japan, 1975, 48, 258. G. Beysel, J. Grobe, and W. Mohr, 2. anorg. Chem., 1975, 418, 121. 17@ W. A. Herrmann, J. Organometallic Chem., 1975, 97, 1. 1 8 0 I. R. Beattie, J. W. Emsley, J. C. Lindon, and R. M. Sabine, J.C.S. Dalton, 1975, 1264. lU1 N. J. Gogan and C.-K. Chu, J. Organonietallic Chem., 1975, 93, 363. J. P. Williams and A. Wojcicki, Znurg. Chim. Acta, 1975, 15, L19. lgs D. A. Edwards and J. Marshalsea, J. Organometallic Chem., 1975, 96, C50. ln4 W. R. Cullen, F. W. B. Einstein, R. K. Pomeroy, and P. L. Vogel, Inurg. Chem., 1975, 14, 3017. lBS R. Colton and C. J. Commons, Austral. J . Cfien~., 1975, 28, 1673. lS6 G. Huttner and H.-D. Miiller, Angew. C h ~ mInternat. . Edn., 1975, 14, 571. 17'

17*

Nuclear Magnetic Resotiatire Spectroscopy

17

leF N.m.r. spectra have been reported for (22),lS7 (CF,),Ehln(CO), (E = P, (23),lee and [R~(CO),NSF,]+[ASF~]-.~~~ The n.m.r. signals of 2H and 65Mnhave been studied in aqueous permanganate solution. The concentration dependence of the 65Mnsignals was determined in a solution of KMn04 in H 2 0 and D 2 0 and a large solvent isotope effect upon the chemical shift of 66Mnwas observed which gave a shielding difference a(H20)o(D20) = -(0.76 k 0.05) p.p.m. The ratio of the Larmor frequency for infinite dilution in [M~O,]-)/V(~Hin D 2 0 ) was determined to be 1.614 865 4(4), which gave the magnetic moment of 65Mnin [MnO,,]- hydrated by D 2 0 as p = 3.461 446 4(22)pN.le1 The 6SMn n.m.r. spectrum of KMnO, has been measured in a mixture of water and acetone. As acetone is added, the chemical shift of 66Mn moves to high field by ca. 4p.p.m. at cn. 40% acetone and then back to low field; in pure acetone the signal is ca. 10 p.p.m. to low field of the aqueous position. The minimum coincides with the maximum viscosity of the acetone-water mixture and the maximum rate of decomposition.lQ2 lH N.m.r. spectroscopy has been used along with DCI-D20 exchange to determine the number of exchangeable protons in NH4ReOl.5F3,H20.1g3

Complexes of Fe, Ru, and 0s.-Information concerning complexes of these elements can be found at the following sources : (q6-C6H6)Fe(C0)2(7,8-BeH~~C,Me),1264 {(0C),Fe},(q6-C6H,)Co( Me2C2B4Hp),1233 (BBCzHll)R~(C0)3,1266

(q6-C6H6)Fe(CO)2k=CPhC(CF,)(CN)C(CF,)(CN)bH2,174 (q6-C,H,)RuCu(CO)2SiF,Me3-,,123 (q6-CSH,)Fe{q4-c6F6~C(CF,)=C(CF,)C(CF,)=~(CF,)},1a7 J. L. Davidson and D. W. A. Sharp, J.C.S. Dalton, 1975, 2283. J. Grobe and R. Rau, Z . anorg. Chem., 1975,414, 19. l a 0 W. R . Cullen and F. K. Hou, Znorg. Chem., 1975, 14, 3121. l o o R. Mews and 0. Glemser, Angew. Chem. Internat. Edn., 1975, 14, 186. 0. Lutz and W. Steinkilberg, Z . Naturforsch., 1974, 29a, 1467. le2 D. Gudlin and H. Schneider, J. Mugn. Resonance, 1975, 17, 268. F. Pintchovski, S. Soled, R. G . Lawler, and A. Wold, Znorg. Chern., 1975, 14, 1390. 18’

ln8

18

Spectroscopic Properties of horgnrlic and Organonietallir Cornpourids

(+C,H,CH MeCH2COC5H,-q5)Fe,86 (qS-CbH,)Fe(CO){P(CH,CH,PR,),)COMe,14, (qS-C5H6)Fe(C0)2PBl,H,,,'239 Fe(CO),(phosphatria~a-adamantane),~~~ (v~-C~H~)F~(CO)(S~CNP~*H),~~~ and Fe2(CO)6S,BNMe,.12sP

A review, entitled 'Polyolefin Carbonyl Derivatives of Iron, Ruthenium, and Osmium', contains IH and 13Cn.m.r. data.ls4 The 'H n.m.r. spectrum of F~RU,H,(CO)~, and FeRu3H,(CO),, shows only one hydride signal even at - 120 "C or - 130 "C. On standing, FeRu3H,(CO),, changes to FeRu,H,(CO),,, RU,H,(CO)~~, and a third species.le5 The n.m.r. spectrum of (24) is a quartet.lg6 The lH and 31Pn.m.r. spectra of (25) shows one

hydride signal and four different phosphorus lea Extensive use has been made of lH n.m.r. spectroscopy to investigate the protonation behaviour of (diene)Fe(CO), complexes in solution, and species such as (diene)FeH(CO), were identified.lD9 The lH n.m.r. spectrum of RuHCl(PPh,), shows marked broadening of the hydride resonance in the presence of H, or D2and this behaviour was attributed to a fast ligand-exchange process.2ooFor (+C5H5)Fe(CO)LCH2R, interconversion between rotamers in both systems is rapid on the n.1n.r. timescale. Variable-temperature n.m.r. studies of the tertiary phosphine derivatives suggest that steric considerations determine the rotamer preferences and that the stablest rotamer is that in which the bulky (q5-C5H5)is gauche to both methylene hydrogen atoms.201 When Yb-optishift I was added to (+C,H5)Fe(CO)(PPh3){(CH,),CN), the enantiomeric protons were resolved when n = 0 or 1 but not when n = 2. The 13C n.m.r. spectra were also recorded for these compounds 202 and ( T ~ - C ~ H ~ ) F ~ ( C O ) L C H P ~ SlH~ M and ~ , .leF ~ ~ ~n.m.r. spectra have been recorded for (26).204The 31Pn.m.r, spectrum of a compound originally formulated lP4

G. Deganello, P. Uguagliati, L. Calligaro, P. L. Sandrini, and F. Zingales, Inorg. Chim. Actu,

1975, 13, 247. S. A. R. Knox, J. W. Koepke, M. A. Andrews, and H. D. Kaesz, J . Anrer. Chent. Suc., 1975, 97,3942. loo P. Dapporto, S. Midollini, and L. Sacconi, lnorg. Chem., 1975, 14, 1643. lo' J. W. Rathke and E. L. Muetterties, J. Amer. Chem. SOC.,1975, 97, 3272. H. H. Karsch, H.-F. Klein, and H. Schmidbaur, Angew. Chem. lnrernnr. Edn., 1975,14,637. lo9 T. H. Whitesides and R . W. Arhart, Inorg. Chem., 1975, 14, 209. *O0 G. Strathdee and R. Given, Canad. J . Chent., 1975, 53, 106. K. Stanley and M. C. Baird, J . Amer. Chem. SUC.,1975, 97, 4292. *Oa D. L. Reger, Inorg. Chem., 1975, 14, 660. *OS K . Stanley and M. C. Baird, J . Amer. Chern. SOC.,1975, 97, 6598. B. L. Booth, R . N. Haszeldine, and N. I. Tucker, J.C.S. Dalton, 1975, 1446. lo6

N ~ c l e n rMogiie f ic Resonatice Spectroscopy

19

as [(y5-C,H,)Fe{P(OPh),},], shows that i t is really o-metallated as (27), with the unmetallated phosphorus at 6 - 166.4 and the metallated phosphorus at 6 - 200.0 p.p.m., from comparison with the known compounds (q5-C5H5)Fe(P(OPh),}(CO)Ph and (y5-C5H5)~eC,H40~(OPh)2(~o).205 Shift reagents have been used to assist the determination of the structure of compounds such as (28),206and O S ~ ( C O ) ~ ~ ( C , IH H ~and ) . ~ I9F ~ ~ n.m.r. spectra have been reported for (29),208 (y6-C5H,)~e(CO)C(CF,)=NC(CF3)=lhH,209 (y6-c5H,)Ru(cO)C(CF,)=CH(CF,), and (30).,1° The asymmetric tin in PhCMe,CH,SnMePhFe-

(Co),(+C6Ha) causes an inequivalence of 77 Hz in the 13Cmethyl carbons of the PhCMe, group, and the methyl carbon atoms of PhSnMe,Fe(CO)(PPh,)(y6-C5H5) are at 6 -3.98 and 6 -5.08. Thus the iron and tin atoms are configurationally stable.211 13C N.m.r. data have also been reported for (3 1),212 (32),213and (C,HB)R~(C0)2GeMe3.214 IH and l9Fn.m.r. data have been reported for [(hfa~)~SnFe(CO),]~ and related 201L

"07

2a8

211 212

R. P. Stewart, jun., J. J. Benedict, L. Isbrandt, and R. S. Ampulski, Znorg. Chem., 1975, 14, 2933. B. F. G. Johnson, J. Lewis, D. J. Thompson, and B. Heil, J.C.S. Dalton, 1974, 567. W. G. Jackson, B. F. G. Johnson, J. W. Kelland, J. Lewis, and K. T. Schorpp, J. Organometallic Chenr., 1975, 88, C17. A. Bond, B. Lewis, and M. Green, J.C.S. Dalton, 1975, 1109. M. Bottrill, R. Goddard, M. Green, R. P. Hughes, M. K. Lloyd, S. H. Taylor, and P. Woodward, J.C.S. Dalton, 1975, 1150. J. L. Davidson, M. Green, F. G. A. Stone, and A. J. Welch, J.C.S. Chem. Comm., 1975,286. M. Gielen, C. Hoogzand, and I. Van den Eynde, Bull. SOC.chim. belges, 1975, 84, 939. J. D. Edwards, R. Goddard, S. A. R. Knox, R. J. McKinney, F. G. A. Stone, and P. Woodward, J.C.S. Chem. Comm., 1975, 828. S. A. R. Knox, B. A. Sosinsky, and F. G. A. Stone, J.C.S. Dalton, 1975, 1647.

p18

m A. Brookes, ala

1975, 1641.

S. A. R. Knox, V. Riera, B. A. Sosinsky, and F. G. A. Stone, J.C.S. Dalton,

A. B, Cornwell and P. G. Harrison, J.C.S. Dalton, 1975, 2017.

2

20

Specti-oscopic Properties of Inoqwnic nnd Orgnnonietnllic Co,mnpoiind.y

The ‘H and I9F n.m.r. spectra of compounds such as (fluoro-olefin)Fe(CO), have been discussed in terms of the cyclopropane formalism.21s The reaction of But2C=C=C=C=C=CBut, with Fe,(CO), or Fe,(CO),, gives a compound which on the basis of ‘H and I3C n.m.r. spectroscopies is formulated as (33).217 13C N.m.r. data for (776-C6H6)Fe(C0)2(r12-cH2=CHY)were discussed in terms of conformations,2fs and those for Fe(CO),L [L = (34); Y = C02R] were

Bu~,C=C=C=C=C=CBU+,

I

Fe(CO)4

HC,” Y

(34)

(33)

K

RN (35)

used to investigate the nature of the bonding between the metal and the olefin;“’” slP n.m.r. data were also recorded in the case of Fe(CO),L [L = (29); Y = The 13C n.m.r. spectrum of (35) shows a 36.4p.p.m. difference for the vinylic carbon atoms, which was considered to be evidence for the structure shown.221 13C N.m.r. spectra have been studied for three series of allyliron derivatives, (~3-C3H6)Fe(CO),X,(q3-RC3H,)Fe(CO),X, and (q3-RC3H4)Fe(CO),X. The spectra reveal the effect of the nature of the ligand X and substituent R on the chemical shifts of the ally1 and CO carbon atoms. These compounds exist in solution as two isomers.222 Eu(fod), has been used to differentiate between

(OC),Fc -C’/O ‘ 0

I

/;y Mc

Me

21e

*17

*I8

(3 7)

R. Fields, G . L. Godwin, and R. N. Haszeldine, J.C.S. Dalton, 1975, 1867. R. B. King and C. A . Harmon, J. Organometallic Chem., 1975, 88, 93. A. Cutler, D . Ehntholt, P. Lennon, K . Nicholas, D. F. Marten, M. Madhavarao, S. Raghu, A. Rosan, and M. Rosenblum, J. Amer. Chem. Soc., 1975, 97, 3149. J. Kagan, W.-L. Lin, S. M. Cohen, and R. N. Schwartz, J. Organometallic Chem., 1975, 90, 67.

120

p21 22a

M. Green, J. A. K. Howard, R. P. Hughes, S. C. Kellett, and P. Woodward, J.C.S. Dalton, 1975,2007.

H. Tom Dieck and A. Orlopp, Angew. Chem. Internat. Edn., 1975, 14, 251. A. N. Nesmeyanov, L. A. Fedorov, N . P. Avakyan, P. V. Petrovskii, E. I. Fedin, E. V. Arshavskaya, and I. I. Kritskaya, J. Organometallic Chem., 1975, 101, 121.

21

Nirciear Miigtietic Resomtice Spectroscwpy

isomers of the type (36).223 N.ii1.r. data have bcen reported for (37) and related compounds (1eF),224 and (38), (13C).225 A critique of work on conforniations of (+tr'ans-trans-3,5-heptadien-2-01)Fe(CO), and related compounds using Eu(fod), and Yb(dpm), has been published.220'H N.ni.r. spectroscopy has been used to show that whereas (39)

is not (40) undergoes rapid degenerate valence isomerism.228 Compound (41) was made from (q4-~y~lo-~~tatetraene)Fe(CO), and the deuteriated Simmons-Smith reagent. 13C N.m.r. spectroscopy was used to demonstrate deuteriation at the positions Compound (42) shows only one 13C0signal even at - 30 "C, and this behaviour was attributed to exchange.230 N.m.r. data have also been reported for ( V ~ - C ~ H ~ ) F ~ ( (C4H4)Fe2(CO),, CO)~,

Fe(CO), (44)

Mc

Mc

H FB)-=4BF M e Me R u (CO)

p24 22b 22e

K.-N. Chen, R. M. Moriarty, B. G . DeBoer, M. R . Churchill, and H . J. C. Yeh, J . Amer. CIiem. SOC.,1975, 97, 5602. M. Green and B. Lewis, J.C.S. Dalton, 1975, 1137. R. 9. King and C. A. Harmon, J . Organomerallic Chem., 1975, 86, 239. M. R. Willcott, W. H. Bearden, R. E. Davis, and R. Pettit, Org. Magn. Resonance, 1975, 7 , 557.

227

A. Eisenstadt, J . Organometallic Chem., 1975, 97, 443. R. Aumann, H. Averbeck, and C. Kruger, Chem. Ber., 1975, 108, 3336. D. L. Reger and A. Gabrielli, J . Amer. Chem. Soc., 1975, 97, 4421. 1. Fischler, K. Hildenbrand, and E. Koerner von Gustorf, Angcw. Chem. Internat. E h . , 1975, 14, 54.

22

Spectt*oscopic Properties of Iriorganic arid Organontetallic Co)?1pourrd.y

(13C);230( ~ 4 - ~ y ~ l o h e p,j-dienejRu(CO),, ta-l ( I T ) ;2:31 (43), (13C);232 (713-Ph,Ccyclo-octatetraene)Fe(CO), which is fluxional. (13C);233(44), (llB, 13C);234 (45), (13C);235 (q4-1,2-dimethyl-4,5-bis(trifluoroniethyl)cyclohexa-1,3-diene)Fe(C0j3, (1sF);23e LFe(CO), [L = (46)], (”B, 19F);237and compounds of the type (1-4-q4-5-CF3CH FCF,-cyclohexa- 1,3-diene)Fe(CO),, (19F).238 The 13C n.m.r. spectra of “Fe-enriched samples of ferrocene, acetylferrocene, ethylferrocene, (q6-C6H5)Fe(q5-C5H4CHOH Me), and [(q5-C5H5)Fe(qfi-C,H4CHMe)]+ have been studied. For ferrocenc, 1J(13C-57Fe)= 4.88 k 0.12 Hz. By use of 13C{lH,“Fe} INDOR, the 57Fechemical shifts were determined, and acetylferrocene is 21 5.55 p.p.ni. from f e r r ~ c e n e ,240 ~ ~while ~in ethylferrocene the 67Fesignal is 36.66 p.p.m. downfield from ferrocene. The 13C n.m.r. signals of the a- and @-carbon atoms in methyl-, ethyl-, isopropyl-, and tert-butylferrocenes were assigned using deuterium labelling. The electronic influcnce of the alkyl groups in alkyl ferrocenes was discussed.231 13C N.ni.r. data for substituted ferrocenes indicate that elect ron-donat ing subs t i t uen t s increase the electron density in the p-position and decrease the electron density in the a-position whereas electron-accepting substituents show the opposite Selected bis- and mono-, -1,2-, and -1,3-disubstituted ferrocenes have been examined by 13C n.m.r. spectroscopy. From J(’H-13C) and chemical shifts, methods have been derived for peak assignments based on (i) analysis of the fine structure generated by the coupling with protons in a position of the substituent, (ii) evaluation of the numerical value of lJ(’H--13C), and (iii) comparison of the 6 values for mono- and di-substituted molecules. The limits of these aids for assignment were also The 13C n.m.r. spectra of some p a w - and mera-substituted phenylferrocenes have been analysed. The substituent-caused shifts have been discussed, and compared with similarly substituted biphenyls and correlated with Hainmett parameters and with the reactivity parameters of Swain and L u ~ t o n . , ~The * proton-coupIed and -decoupled I3C n.m.r. spectra of a series of neutral ferrocene derivatives and ferrocenylalkylium ions have been recorded and analysed. The influence of a substituent group upon the 13Cshifts of the carbon atoms of the ferrocene ring was investigated The spectra of the asl 239 234

yy6

236

237 *38

*so 240

24l ~2 243

244

B. A. Sosinsky, S. A. R. Knox, and F. G. A. Stone, J.C.S. Dalton, 1975, 1633. S. Sadeh and Y. Gaoni, J. Organontetallic Chetn., 1975, 93, C31. B. F. G . Johnson, J. Lewis, and J. W. Quail, J.C.S. Dalton, 1975, 1252. W. Siebert, G. Augustin, R. Full, C. Kruger, and Y.-H. Tsay, Angew. Chwi. Intprtiat. Edn., 1975, 14, 262. R. Goddard, A. P. Humphries, S. A. R. Knox, and P. Woodward, J.C.S. Chctir. Conltn., 1975, 507. R . Davis, M. Green, and R. P. Hughes, J.C.S.Chem. Cotnm., 1975, 405. P. S. Maddren, A. Modinos, P. L. Timms, and P. Woodward, J.C.S. Dultoti, 1975, 1272. M. Green, B. Lewis, J. J. Daly, and F. Sanz, J.C.S. Dalton, 1975, 1 1 18. A. A. Koridze, P. V. Petrovskii, S. P. Gubin, E. I . Fedin, A. I. Lutsenko, I . P. Amitin, and P. 0. Okalevich, Izoest. Akad. Nauk S.S.S.R., Ser. khitn., 1975, 7 , 1675. A. A. Koridze, P. V. Petrovskii, S. P. Gubin, and E. 1. Fedin, J. Organornetullic Chetn., 1975, 93, C26. A. A. Koridze, P. V. Petrovskii, E. I. Fedin, and A. I. Mokhov, J. Orgunometallic Chem., 1975, 96, C13. A. A. Koridze, A. I. Mokhov, P. V. Petrovskii, and E. I. Fedin, Izoest. Ahnd. Nuuk S.S.S.R., Ser. khim., 1974, 9, 2156. F. H. Kohler and G.-E. Matsubayashi, J. Organotttetallic Chem., 1975, 96, 391. S. Gronowitz, I. Johnson, A. Mnholanyiova, S. Toma, and E. Solcaniovi, Org. Mugn. Resonance, 1975, 7, 372.

Nuclear Magnetic Resonance Spectroscopy

23

ferrocenylalkylium ions were discussed in relation to the distribution of positive charge and to the various structural models which have been proposed for such 246 The protons adjacent to the carbonium centre in [(rl5-C,H5)Fe(q5-C5H4CR1R2)]+ and on the carbon atoms in the substituted cyclopentadienyl ring are non-equivalent because of conformational effects.247The 13C n.m.r. spectra were also The ‘H n.m.r. spectra of homoannular isomeric diethyl- and diacetyl-ferrocenes have been studied. The chemical shifts were determined and the results were discussed in terms of inductive and hyperconjugative effects of the substituent groups.24gThe n.ni.r. spectra of a series of mono- and di-acetyl[3]ferrocenophanes have been investigated by computer matching and n.m.r. shift reagents. Accurate chemical shifts and coupling constants have been obtained. Changes in chemical shift of the ‘aromatic’ or ‘ring’ protons induced by the introduction of the acetyl group into various positions of the cyclopentadienyl rings cannot be explained solely by the anisotropy of the acetyl groups. These differences in chemical shift have been interpreted in terms of the anisotropy of the non-bonding hybridized ‘d’ orbitals of the iron atom and the perturbations of these orbitals caused by the introduction of the acetyl group.25oOptical isomers of (q5-C5H5)Fe(q5-C5H4CHOHPh) have been differentiated by an optically active shift reagent,261and lH n.m.r. spectroscopy has been used to establish the conformation of some /3-methylated homocondensed ferrocene alcohols and 13CN.m.r. data have been reported for some f e r r o c e n o p h a n e ~ . ~Asymmetric ~ ~ - ~ ~ ~ shift reagents have been used to demonstrate the optical purity of compounds such as (ys-C5H,)Fe(CO)(PPh,)S02Me.256The 13C n.m.r. signals of C(4) and C(3),(5) in (q5-cyclohexadienyl)(q5-cyclopentadieny1)Feand its derivatives are shifted, with respect to ferrocene, to low field, and the signals of C(2),(6) are strongly shifted to high field. An uneven distribution of electron density in the CsH7 ligand was N.m.r. data have also been reported for [(+arene)(~5-CKHK)Fe]+, (13C),258 (47), (11B),2sa (diazabicy~loheptane)Fe~(CO)~,(13C),260 (OC),FePBut,(EMe,),-, 246 246 947

248 2 OR 260

251 252

“53 254

“65

266 267

368

S. Braun and W. E. Watts, J . Organometallic Cheni., 1975, 84, C33. S. Braun, T. S. Abram, and W. E. Watts, J . Organometallic Chem., 1975, 97, 429. A. N . Nesmeyanov, B. A. Surkov, 1. F. Leshcheva, and V. A. Sazonova, Doklady Akad. Nairk

S.S.S.R.,1975, 222, 848.

G. Olah and G . Liang, J . Org. Chem., 1975, 40, 1849.

A. N . Nesmeyanov, E. V. Leonova, E. I. Fedin, P. V. Petrovsky, and N . S. Kochetkova, J . Organometallic Chem., 1975, 96, 279. R. R. McGuire, R. E. Cochoy, and J. A . Winstead, J . Organonietallic Chem., 1975, 84, 269. S. Allenmark and K. Kalen, Tetrahedron Letters, 1975, 3175. R. Broussier and B. Gautheron, Bull. Soc. chim. France, 1975, 1814. P. Batail, D. Grandjean, D. Astruc, and R. Dabard, J . Organometallic Chern., 1975, 102, 79. A. N . Nesmeyanov, G . B. Shul’pin, and M . I. Rybinskaya, Doklady Akad. Nauk S.S.S.R., 1974, 218, 1107.

A. N. Nesmeyanov, M. I. Rybinskaya, G . B. Shul’pin, and A . A . Pogrebnyak, J . Organometallic Cliem., 1975, 92, 341. T. C. Flood, F. J. Di Santi, and D. L. Miles, J.C.S. Chem. Comm., 1975, 336. A. N. Nesmeyanov, E. I. Fedin, P. V. Petrovskii, B. V. Lokshin, L. S. Kotova, and N . A. Vol’kenau, Koord. Khim., 1975, I, 550 (Chem. Abs., 1975, 83, 88 063). R. G. Sutherland, S. C. Chen, J. Pannekoek, and C. C. Lee, J . Organometallic Chem., 1975, 101,221.

280

A. J. Ashe, tert., E. Meyers, P. Shu, T. Von Lehmann, and J. Bastide, J . Amer. Chem. Soc.,

260

A. Albini and H. Kisch, Angew. Chem. Internat. Edn., 1975, 14, 182.

1975, 97, 6865.

24

c:".

Spectroscopic Properties of Inorgaiiic arid Organometnllic Conipoirnds ,_!

_I

I

Fc

(E = Si, Ge, Sn; 31P),261 and [(OC),Fe],(P,O,), (31P).262In order to examine the stereochemical behaviour of Fe(CO), derivatives of several bidentate ligands a polynuclear n.m.r. investigation was carried out on Me2PCF2CH2PMe2, PhaP(CH&PPh2, and o-C,H,(AsMe,), and the corresponding Fe(CO), derivatives by 'H, 13C, leF, and 31P n.m.r. spectroscopies. They are stereochemically nonrigid down to -70 "C, and in the case of Fe(diars)(CO), non-rigid down to -140°C.263 The possibility of nitrogen exchange has been examined in [RuC1(CO),(HN,Ph)(PPh,),l+[C104]- by preparing the Ph14N2H,Phl5N=I4NH, Ph1sN=16NH, and Ph14N=15NH analogues, but no evidence for exchange has been lH and 13Cn.m.r. spectra have been determined for a number of Fe" complexes [Fe(CN),L]"- in aqueous solutions. For ligands L related to pyridine and pyrazine, the effects of nitrogen co-ordination in [Fe(CN)J3- on the lH and 13C n.ni.r. spectra are similar, showing downfield shifts for the a-carbon (ca. 8 p.p.m.) and hydrogen (ca. 0.6 p.p.ni.) and smaller upfield shifts for the p- and y-carbon atoms and their substituents. The 13CN resonances in [Fe(CN),L]"-(aq) are shifted upfield according to the sequence L := pyridine z 4-methylpyridine < isonicotinamide z cyanide z pyrazine < N-Me-pyrazinium z DMSO 4 [NO]+. The results were discussed in terms of the character of the iron(r1)ligand bond and compared with the 'H n.m.r. spectra of several analogous ruthenium(I1) complexes.265 'H N.ni.r. spectroscopy has been used to examine the binding of iron porphyrins to 1,2,3,4-tetramethylpyridiniumiodide.2a6 The 'H 1

I

n.m.r. spectrum of [(H,N),RuNH=CMeCMe=NHI2+ shows two NH and two NH, signals while 1H{14N}lNDOK shows two ammine nitrogen signals.267 Concentrated H2S04 has been demonstrated to be a suitable solvent for obtaining the 'H n.m.r. spectra of a large variety of ruthenium nitrosyl complexes. The n.m.r. spectra obtained in H2S04 confirm the earlier assignments of the geometric isomers of cis- and trans-nitrosyl tetra-ammines of Ru". Further, the protons on the trans-ammine of [Ru(NH3),N0I3+ demonstrate 261

ma 263

aac 161

26e

207

H. Schumann, L. Rosch, H.-J. Kroth, H. Neurnann, and B. Neudert, Chem. Ber., 1975, 108, 2487. M. L. Walker and J. L. Mills, Inorg. Chem., 1975, 14, 2438. G. R. Langford, M. Akhtar, P. D . Ellis, A. G . MacDiarmid, and J. D. Odom, Inorg. Chern., 1975, 14, 2937. B. L. Haymore and J. A. Ibers, J. Amcr. Chem. Soc., 1975,97, 5369. J. M. Malin, C. F. Schmidt, and H . E. Toma, Znorg. Chem., 1975, 14, 2924. W. Scheler, P. Molir, R. Hintsche, and K. Pornrnerening, Symp. Pap.-Int. Riophys. Congr. 4th, 1972. 2, Pt. 2, 653, ed. G . M . Frank and 1,. P. Kayushin, Akad. Nouk S.S.S.R., Inr. B i d . Fiz.. Pushchino-on Oka, U.S.S.R. I. P. Evans, G. W. Everett, jun., and A. M. Sargeson, J.C.S. Chem. Comnr., 1975, 139.

25 markedly enhanced 'H exchange when compared to the ammines of the isoelectronic [ R U ( N H , ) , C O ] ~ + . ~31P ~ ~ N.m.r. data have been reported for [RuCI(PMe2Ph),(tetramethylphenanthroline)CH2Cl~]+Cl- and related comspectroscopy has been used to demonstrate geometric p o u n d ~ .lsF ~ ~N.rn.r. ~ isomers for (Ph3P)2(F3P)R~(p-CI)3Ru(PF3)(PPh3)CI, where three sets of signals were Nuclear Magnetic Resonance Spectroscopy

Complexes of Co, Rh, and 1r.-Information concerning complexes of these elements can be found at the following sources : 3-(Ph,P),IrHCI-1 ,2-C2B10H11,1267 { (OC)3Fe}2(y5-C5H5)CoMe2C2B4H4,1233 2,3,8,1,6-(y5-C5H5)3C03C2B6H7,'238 (r7s-C6H6)CoNiCB7HB,1237 1-(y5-C5H5)1-Co-2,4-Me2-2,4-C2B8H8,1246 [BloH121r(CO)(PPh3)2]-,1247 B9C2H11RhCI(PPh3)2,1266 3-[1-Ph-(ys-C5BH5)1-3,1,2-Co( M ~ , P ) , C O P M ~ , C H ~ , (F5CBN=NC6H4)2Rh(p-C1)2Rh~~~ (CO)2,173(PhN=NC6H4),Rh2C12,105(H3Si)Co(C0),,1336L,M(acac) [L = (34); M = Rh, Ir],2z0 (r15-C5H5){q3-C3H3MeCH2C(CF3)20}Rh,224 LCo(q5-C5H,) [L = (46)],237(r14-Cs(CF3)6}CO(q6-c5H5),187 (q4-cyclo-octadiene)(q5-C5C15)Rh,2"s

r\J

(0C)(Ph3P),irN H C(C F3)=N C(C F3)= H ,209 (CF,),ASCO(CO),,'~~ transRhF(CO)(PPh3)2,3g0and [XO,CO~,~,V,O,,]~-.~~ lH N.m.r. spectroscopy has been used to establish the composition of IrH6(PPri3)2and to distinguish it from IrH3(PPri3)2.271The lH and llB n.m.r. spectra of IrH2(BH4)(PBut2Me),show that the BH., group is static, and pairs of hydrogen signals are found at 6 - 19.5 (hydride), 8 -6.87, and 6 6.86. The llB broadening may be removed by either decoupling or N.m.r. data have also been reported for 1rHCl(C6H4N=NPh)(PPhs), and related [Ir(dppe),HX]+, compounds, (13C),273(OC)2Rh(NR1=CHC6H4R2)Cl,(13C),274 (31P),275 and mer-(PMe,),Me,CoX, (31P).276I3C N.m.r. spectra of aqueous (D20) solutions of methyl-, ethyl-, and adenosyl-cobalamin and methylaquocobinamide selectively enriched with 13C in the alkyl group attached to cobalt have been recorded over the temperature range 5-90 "C. Small temperature-dependent shifts were found which were interpreted in terms of conformational changes rather than changes in the co-ordination number of the cobalt. 13C N.m.r. spectroscopy was also used to study homolytic cleavage of the cobalt-carbon bond and p h o t o l y ~ i s .13C ~ ~N.m.r. ~ spectra of a series of alkylcorrinoids selectively enriched in 13Chave been measured. The nature of the axial ligands had a marked effect on the alkyl ligand (trans) and the corrin ring (cis). Tl was also determined. For adenosylcobalamin, severe restriction of rotation of the cobalt-carbon bond was found from T1 n i e a s ~ r e r n e n t s .From ~ ~ ~ a 13C n.m.r. study of several 2 6 8 J. Mastone and J. Armor, J . Inorg. Nuclear Chem., 1975, 37, 413. om

2io

*71 2i2

2i4 2i6

~6 377 2iR

L. Ruiz-Ramlrez and T. A. Stephenson, J.C.S. Dalron, 1975, 2244. R. A. Head and J. F. Nixon, J.C.S. Chem. Comm., 1975, 135. M. G. Clerici, S. di Gioacchino, F. Maspero, E. Perrotti, and A . Zanobi, J . Organometallic Chem., 1975, 84, 379. H. D. Empsall, E. Mentzer, and B. L. Shaw, J.C.S.Chem. Comm., 1975, 861. J. F. Van Baar, K. Vrieze, and D. J. Stufkens, J . Organometallic Chem., 1975, 85, 249 J. F. Van Baar, K. Vrieze, and D. J. Stufkens, J . Organometallic Chem., 1975, 97,461. A. F. Williams, G. C. H. Jones, and A. G . Maddock, J.C.S. Dalton, 1975, 1952. H.-F. Klein and H. H. Karsch, Clzem. Ber., 1975, 108. 956. H, P. C. Hogenkamp, P. J. Vergamini, and N. A. Matwiyoff, J.C.S. Dalton, 1975, 2628. H. P. C. Hogenkamp, R. D. Tkachuck, M . E. Grant, R. Fuentes, and N. A. Matwiyoff, Biochcrnistry, 1975, 14, 3707.

26 Spectroscopic Properties of Inorganic and Organometaiiic Compounds alkylcobaloximes, RCo(dmg),B, it has been possible to estimate the a, /3, and y-effects of the Co(dmg),B group on the 13Cchemical shifts of the carbon atoms of the various alkyl groups, R. The carbon atoms belonging to the equatorial ligands are not significantly affected by structural modifications of the R group. Values of 6 (C,,,,) in benzylcobaloximes (XCeH,CH,)Co(dmg),B agree well with a donor effect of the CH,Co(dnig),B radical. Values of 'J('H-13C) = 137 Hz for methylcobaloximes do not vary appreciably when B is changed and are close to the value obtained for methylcobaloxime.27DThe lDFn.m.r. spectrum of C,F,Co(salphen)C,F,,H,O shows two sets of resonances due to two C,F, groups, and it was suggested that reaction of C,F,I with [Co'salphenl-l has given (48) as one product. The 13C n.m.r. spectrum of C,F,Co(salphen)H,O has a signal at 6 200 attributable to the CH=N group.2eo N.m.r. data have been rep or ted for RCo(dmg),PR,, ("P) (49), (13C) IrC12(COCF,-,H,)L2(C0) (L = PPh,,

Q (48)

(49)

,

(Ph 0) P -co I

(q4-butadiene)PMePh,), ('OF) ;2*n Zrans-CF,CF= CFCo(CO),PPh,, (1gF)7284 (CF,CH=C(CF,)}Ir(CO)PPh,, ('OF, 31P);285rnev-RhC1(CGH40Me-o)(PMe2Ph)3, (31P);2ee [R!h(CeH3RCONNC,H,),(H,O)?IC,

(13C);287 XC6F4 M(C0)2(PPh3)2 1

(50) and related compounds, (1DF);289 and L(CF2)4CF=C(M = Co, Ir), (1DF);288 27e

zRo 282

C . Bied-Charreton, B. Septe, and A. Gaudemer, Org. Magn. Resonance, 1975, 7, 116. A . M. Van den Bergen and B. 0. West, J . Organometallic Chem., 1975, 92, 55. G. R. Tauszik, G . Pellizer, and G. Costa, J . Inorg. Nuclear Chem., 1975, 37, 1532. N. W. Alcock, J . M. Brown, J. A. Conneely, and D. H. Williamson, J.C.S. Chem. Comm., 1975, 792.

D. M. Blake, A. Winkelman, and Y. L. Chung, Inorg. Chem., 1975, 14, 1326. lS4 K. Stanley and D. W. McBride, Canad. J . Chem., 1975, 53,2537. M. Green and S. H . Taylor, J.C.S. Dalton, 1975, 1142. C. Eaborn, K. Odell, and A. Pidcock, J . Organometallic Chem., 1975, 96, C38. S. A. Dias, A. W. Downs, and W. R . McWhinnie, J.C.S. Dalton, 1975, 162. 288 B. L. Booth, R . N. Haszeldine, and 1. Perkins, J.C.S. Dalton, 1975, 1843. M. I. Bruce, B. L. Goodall, and F. G. A. Stone, J.C.S. Dalton, 1975, 1651. 283

Nuclear Magnetic Resonance Spectroscopy 27 M(CO)p(PPh3)2,( M = Rh, Ir), (1eF).*90The 31Pn.m.r. spectrum of (51) has been analysed as ABCz to give JAB = 7 127 Hz, JAC = J 212 Hz, and JBC = T 1 0 0 H z . ~The ~ ~apical cluster carbon 13C n.m.r. resonances in some neutral RCCo,(CO), complexes have been observed in the region S 255310p.p.m. Apical cluster carbon atom resonances occur in the 13C n.m.r. spectra of concentrated sulphuric acid solutions of [(OC)gCo3CCR1R2]fcations in the region 6 255 --286. Further discussion of the structure and bonding in these charged species is given.292 N.m.r. data have also been reported for (0C),Co(CF,),Co(C0),, (19F),293 and Co3(CO),COBX2NEt3,(11B).294 The 19F n.m.r. spectrum of [(q4-cyclo-octa-l,5-diene)(q2-hexafluorobut-2-yne)IrCl], shows the CF, groups to be i n e q ~ i v a l e n t .13C ~ ~ ~N.m.r. spectra have been obtained for a series of quinones, hydroquinones, and quinonoid complexes of Ni, Co, Rh, and Ir in CDCI,, EtOH-D,O, and D2S04solution. Evidence was presented which suggests that neutral q4-duroquinone complexes of the type (7,-duroquinone)(q5-C5H5)M are protonated in strongly acidic media to produce dications [(r)s-CloH1401)(q5-c6H6)M]2f in which the quinone functions as a r)s-hydroduroquinone ligand.296 The 31Pn.m.r. spectrum of (52) is ABX with

(52)

2J(31P-31P)= 36 Hz, and 13Cn.ni.r. data were also given.297For RhCl(pyridine)(ASM~,P~)~(C,(CF,),} and related compounds, the lH and 19F n.m.r. spectra are temperature dependent; this was attributed to pyridine exchange.298The effect of Eu(fod), and Pr(fod), on the lH and laF n.m.r. spectra of some (q4-cyclopentadienone)(q5-C5H5)Cocomplexes have been investigated as an aid to structure determination in this series. The lanthanide complexes with the lone pair of the carbonyl group. Pseudo-contact shifts were observed for the hydrogen atoms attached to each ring. With Eu(fod), contact shifts were also observed for the cyclopentadienone ring hydrogen atoms.29g N.m.r. data have also been reported for (53), (54), (13C),3003r(q2-CF,=CF,)(q3-allyl)COL, zD1 2B3

28p 20 6

2B5 997

2gH

38B

300

B. L. Booth, R. N. Haszeldine, and I. Perkins, J.C.S. Dalton, 1975, 1847. L. W. Gosser, Inorg. Chem., 1975, 14, 1453. D . Seyferth, C. S. Eschbach, and M. 0. Nestle, J . Organometallic Chem., 1975, 97, C11. B. L. Booth, R. N. Haszeldine, and T. Inglis, J.C.S. Dalton, 1975, 1449. G. Schmid, V. Biitzel, G. Etzrodt, and R. Pfeil, J . Organometallic Chem., 1975, 86, 257. D. A. Clarke, R. D. W. Kemmitt, D. R. Russell, and P. A. Tucker, J. Organomefailic Chem., 1975, 93, C37. G. M. Bodner and T. R. Englemann, J . Organornetallic Chem., 1975, 88 391. W. Winter, A n g w . Chem. Internat. Edn., 1975, 14, 170. J. T. Mague, J.C.S. Dalton, 1975, 900. R. S. Dickson, S. H . Johnson, and I. D . Rae, Austral. J . Chenr., 1975, 28, 1681. N. W. Alcock, J . M. Brown, J. A. Conneely, and J . J. Stofko, jun., J.C.S. Chem. Comm., 1975, 234.

-

28

Spectroscopic Properties of Itiorganic and Orgaitonietnllic Compounds

('OF, 31P),301(hexafluoro-Dewar benzene)Rh(~~-C,H~)(acac), (10F),3u2 { Me,As-

C=C(AsMe,)CF,CF,}(+PhC=CPh)Co,(CO),. (10F),303 ( ~ ~ - a l l y l1igand)ic ( 5 9 , (31P),305 (Xi), (11B),306 and (~s-C,H5)M{C,(C,F,H)2Co(PF3),(PPh3), (19F),304 Ph,CO} (M = CO, Rh), (*9F).307

L ?C'I

Rh (hfac) ( 5 31

At - 82 "C, the 13Cn.m.r. spectrum of CO,(CO)~~P(OM~), shows two bridging CO groups in the ratio 2 : I with the remainder in the ratio 3 : 3 : 2, while the 59C0n.m.r. spectrum of CO,(CO)~~ shows two signals in the ratio 1 : 3 at room ternperature.,O8 The 13C n.m.r. spectrum of (57) shows t w o doublets of equal intensity at 6 186.32 and 6 185.02, with lJ(13C-lo3Rh) = 6 - 7 0 Hz, which were

attributed to two unsymmetric solution species.3o9 The n.m.r. spectra of compounds such as [Co(CO)(PMe,),]+ even at - 80 'C show o n l y one 31Pn.m.r. signal.31o For complexes of the type (58), the lH and 31Pn.m.r. spectra show a complex temperature dependence which is probably due in part to the complexity of the spin system and the presence of rotational isomers.311 N.m.r. data have also been reported for L,(OC)MCu(R'N-N-NR2)X (L = Ph,P, Ph,As, PhMe,P; M = Rh, Ir), (13C),312 [(Me,AsC=C(PPh,)CF,CF,)Co(CO),I,, (19F),313 I

303 306 307

30n

310 313 31B

1

M. Green and S. H. Taylor, J.C.S. Dalton, 1975, 1128. B. L. Booth, R. N. Haszeldine, and N . 1. Tucker, J.C.S. Dalton, 1975, 1439. L. S . Chia, W. R. Cullen, M. Franklin, and A. R. Manning, Znorg. Chem., 1975, 14, 2521. M. A. Cairns and J. F. Nixon, J. Orgonometallic Chem., 1975, 87, 109. W. Winter, J. Organometallic Chent., 1975, 92, 97. G. E. Herberich and H. J. Becker, Angew. Chem. Internal. E h . , 1975, 14, 184. R. S. Dickson and L. J. Michel, Austral. J. Chem., 1975, 28, 1343. M. A. Cohen, D. R. Kidd, and T. L. Brown, J. Anier. Chem. SOC.,1975, 97, 4408. S. W. Kaiser, R. B. Saillant. and P. G . Rasmussen, J. Amer. Chem. SOC.,1975, 97, 425. H. F. Klein and H . t i . Karsch, Innorg. Chcnz., 1975, 14, 473. H. D. Empsall, E. M. Hydc, and B. L. Shaw, J.C.S. Dalton, 1975, 1690. J. Kuyper, P. I. Van Vliet, and K. Vrieze, J. Orgonontetullic Chem., 1975, 96, 289. L. S. Chia and W. R . Cullen, Inorg. Chcm., 1975, 14, 482.

Nuclear hfugnetic Resonance Spectroscopy

29

[IrLlpL2]+ [L1 = P(OCH,),CMe], ("P) [including zJ(31P-31P)] ;314 trans-RhCI(CO)[Ph2P(CH2),PPh2]2RhC1(CO)-trans, ("P) ;315and Ir(CO)(PPh,),X, (,lP).,16

16N Chemical shifts have been determined for [CoX(NH,),]"+ (X = NH,, H 2 0 , Br-, [NO2]-). Chemical shifts induced by the paramagnetic anisotropy of the cobalt(1n) ion are of minor importance to 15N chemical shifts; this contrasts with previous reports that they are of dominant importance to lH chemical shifts. The 15N chemical shifts show a different cis and trans dependence on X.317 A theory has been developed which couples the lH n.m.r. chemical shift

induced by the paramagnetic anisotropy with the chemical shift of the central 59C0 nucleus. The theory has been successfully applied to 20 cobalt(rI1) a-aminocarboxylate complexes. It was shown that it can be used not only to assign 'H n.m.r. signals but also to determine the structure of the complexes and, in certain cases, the conformation of the ligand molecules.318 The 59C0 n.m.r. spectra of 12 polynuclear cobalt(n1) complexes have been reported. The chemical shifts and linewidths were discussed in relation to the spectra of mononuclear species. Complexes containing chemically non-equivalent cobalt(1rr) atoms exhibit discernible resonances with differing chemical shifts.319 Similarly, 6 D C ~ n.m.r. spectra of 24 ~-carboxylato-di-~-hydroxybis{triamminecobalt(~~I)~ complexes have been examined. The chemical-shift values are constant for all the complexes; however, the linewidths differ significantly. It was shown that the 6 9 C relaxation ~ is a function of the basicity of the oxygen atoms of the symmetrically bonded carboxylato-bridging groups (affecting the electric field gradient at the cobalt nuclei) and of the size and shape of the complex (affecting the rotation correlation time).320 13C and 59C0n.m.r. relaxation-time measurements have been reported which permit evaluation of the electrostatic contribution to field gradients from ions external to the first co-ordination sphere of the observed nucleus. It was concluded that for [Co(en),13+, the presence of a phosphate ion in the second co-ordination sphere makes little, if any, contribution to the electric field gradient at the cobalt nucleus.321 The 13C n.m.r. spectra have been measured for mer-A(ob), fnc-A(ob), and fa~-A(ieZ)[Co(l-pn),]~+ions. There is a clear difference between the A and A configuration. However, no appreciable difference was observed between the mer- and fac-isomers of A(~b)-[Co(Z-pn),]~+'.~~~ 13C N.m.r. spectra of a-amino-acids and trans-[Co(en),(a-amino-acid)l3f complexes have been measured. Changes in the chemical shift on protonation of the carboxyl anion group of the amino-acid were 2.5-3.2 and 1.1-2.1 p.p.m. upfield for the carboxyl and a-carbon atoms respectively; on co-ordination of the CO group to the Co"' ion, the shifts were 3.8-4.4 and ca. 0 p.p.m. downfield, 13C N.m.r. measurements have been s14 s16

s17

318 318

s20 321

J. S. Miller and K . G. Caulton, Znorg. Chem., 1975, 14, 2296. A. R. Sanger, J.C.S. Chem. Comm., 1975, 893. A. F. Williams, S. Bhaduri, and A. G . Maddock, J.C.S. Dalton, 1975, 1958. Y . Nakashima, M. Muto, I. Takagi, and K. Kawano, Chem. Letters, 1975, 10, 1075 (Chem. Abs., 1975, 83, 199 931). H. Yoneda, U . Sakaguchi, and Y. Nakashima, Bull. Chem. SOC.Japan. 1975, 48, 209. W. Hackbusch, H . H. Rupp, and K. Wieghardt, J.C.S. Dalton, 1975, 1015. W. Hackbusch, H. H. Rupp, and K. Wieghardt, J.C.S. Dalton, 1975, 2364. K . L. Craighead and R. G. Bryant, J. Phys. Chem., 1975, 79, 1602. M. Kojima and K . Yamasaki, Bull. Chem. SOC.Japan, 1975, 48, 1093. T. Ama and T. Yasui, Chem. Letters, 1974, 11, 1295 (Chem. Abs., 1975, 82, 49646).

30 Spectroscopic Properties of Inorganic and Organoinetnilic Compounds performed on Co"' complexes of HO,CCH,NH(CH,),NHCH,CO,H ( n = 2, 3) with various unidentate (NH,, H 2 0 , pyridine, [NO,]-) or bidentate (en, 1,3-pn, 2,2'-bipyridyl, 1,lO-phenanthroline, ethanolamine, [C0312-, oxalate, malonate) ligands occupying the remaining two octahedral co-ordination sites. The complex spectra of sym-cis and unsym-cis complexes along with selective decoupling and deuteriation techniques allow assignment of most of the resonances to individual carbon atoms. It was found that 13C n.m.r. spectroscopy is useful in investigations of inorganic stereochemistry insofar as it allows the determination of those parts of ligands in unsym-cis complexes which experience the greatest change in environment, relative to the free ligand or the ligand in the syni-cis complex.324 cis- and trans-[Rh(en),X,]+ (X = Br) shows only one 13C n.m.r. signal but when X = CI, three different signals were observed; these were attributed to slow r i n g - i n v e r s i ~ n .13C ~ ~ ~N.m.r. spectroscopy has also been used to investigate the involvement of uro'gen 111 and heptacarboxylic uro'gen in corrinoid b i o s y n t h e ~ i s ,and ~ ~ ~for distinguishing between cis- and trans-[Co(en),X2]+.327The published spectrum of [1r(bipy)J3+ has been The lH n.m.r. spectrum of MeSO,Co(dmg),pyridine has been interpreted as showing that the MeSO, group is a worse electron donor than Me.329 The lH n.ni.r. shift of the M e 0 protons in [R,PCo(dmg),MeOH]+ is sensitive to the steric bulk of R3P and can be used to estimate the size of PR3.330 lH N.m.r. spectroscopy has proved to be very useful in distinguishing between linkage isomers of cobalt(rr1) complexes of [MeCOC(CHO)CMeO]- and related c o m p ~ u n d s , " ~ and the lH chemical shifts of M(EtOSacsac), (M = Co, Rh, Ir), have been l9F N.m.r. data have also been reported for (F,P),Rh(pO,CCF,),Rh(PF3)2.333

Complexes of Ni, Pd, and Pt.-Information concerning complexes of these elements can be found at the following sources: (y5-C6Hb)2CoNiCB,H8,12 [(~S-CKHK)Ni(ys-BDHg)]-,1240 6,6-(Et,P),-5,9-Me,-6,5,9-NiC2B7H9,1241 (dPPe)PtBloHl10Et,1248 [(B11H11)Ni(y5-C,H5)]-,126g 1-(y4-cyclo-octa-l ,5-diene)-2,4(M = Ni, Pd, Mez-l,2,4-NiC2BDH9,12681 ,I-(ButCN),-2-Me,N-1,2-MCBloHl,

m

I &

(Ph,P= CH,)pt),12" PhN= NC6H4Pd(acac),105C6F6N=NC6H4Pd(y5-C5H5),173 Ni(C0)3,1497 LPt(PPh3)2 [L = (34)],320 (hexafluoro-Dewarbenzene)M(PPh,), (M = Pd, Pt),,02 LNi(~4-cyclo-octa-1 '5-diene) [L = (46)],237quinone complexes of Ni,2D6 LNi(C0)3,137and [PhP(CH,CH2PR2)2PtCI]+.143 The lH n.m.r. spectrum of trans-PtH,(P(C,H,,),}, shows a hydride signal at T 13.16 with 2J(1H-31P) = 17 Hz and 1J(1H-1Q5Pt)= 794 H z , ~ and ~ * the 31P and 324

326 327 3D*

329 330 331 333

334

K . D. Gailey, K . Igi, and B. E. Douglas, lnorg. C/tc17i., 1975, 14, 2956. C. Burgess and F. R . Hartley, Inorg. Cliim. Acra, 1975, 14, L37. A. I. Scott, N. Georgopapadakou, K. S. Ho, S. Klioze, E. Lee, S. L. Lee, G. H. Temmc, lert., C. A. Townsend, and 1. M. Armitage, J . Amer. Chcm. SOC.,1975, 97, 2548. D. A. House and J . W. Blunt, Inorg. Nuclear Chem. Letters, 1975, 11, 219. C. M. Flynn, jun. and J. N. Demas, J . Amer. Chem. Soc., 1975, 97, 1988. J. M. Palmer and E. Deutsch, Inorg. Chem., 1975, 14, 17. W. C. Trogler and L. G. Marzilli, Inorg. Cheni., 1975, 14, 2942. R. J. Balahura and N. A. Lewis, Canad. J . Chem., 1975, 53, 1154. A. R. Hendrickson and R. L. Martin, Inorg. Chrm., 1975, 14, 979. J. F. Nixon, J. S. Poland, and B. Wilkins, J . Organomefallic Chem., 1975, 92, 393. A. Immirzi, A. Musco, G. Carturan, and U . Belluco, Inorg. Chim. Acfa, 1975, 12, 1 2 3 ,

Niiclcas Mtigttet ic Resotiutrce Spectr4oscopy

31 lur,Pti1.m.r. spectra have also been given for this compound, and for ( T ? - C ~ H ~ ) ~ P ~ and (cyclo-octa-l,5-~Iiene)~Pt.~~~ The llB n.m.r. spectrum of trans-PtH(PEt,)(N=CBPh:,) and trans-PtH(PEt,),(C=NBPh,) shows signals at 8 27.5 and 6 17.5 which are very broad, and the broadening was attributed to 14Ncoupling.333" A number of Lewis acid (L) adducts of the type trans-HPt(PEt,),CN L have been prepared. The coupling constant lJ(lH--lg5Pt)was used as a measure of the relative acceptor strengths of the Lewis acids, and co-ordination of CN to a Lewis acid weakens the Pt-C bond.337 'H and 31P n.m.r. data have also been reported for PtH,(SnR,),( PMe,Ph)2,338and Pt(SiR3)2L2.339 ' H and 13C n.ni.r. spectra have been obtained for a series of platinum(i1) carbene complexes of the type trans-[RPtQ,(carbene)]+[PF,I-, where R is an anionic ligand and Q is a neutral donor. The n.ii1.r. parameters were discussed and compared with the I3C 1i.m.r. parameters derived from related platinum(i1) complexes. The stereochemical orientations of the substituents on the heteroatoms of the carbene ligands were considered in 13C N.m.r. spectra have been measured for three series of n-bonded (q4-cyclo-octa-l,5-diene)platinum(i1) derivatives of the type (q4-cyclo-octa-l,5-diene)PtMeR,[(q4-cycloocta-l,5-diene)Pt MeL]+[PF,]-, and (q4-cyclo-octa-1 ,5-diene)PtR1R2. The I3C shieldings and J(13C-195Pt) were discussed and compared with 13C n.ni.r. parameters derived from related platinum(ii) complexes containing o-bonded carbon atoms. The 13C shielding and coupling-constant trends of the nbonded carbon atoms are generally found to parallel those trends for the o-bonded carbon 13C N.m.r. parameters for a series of transition-metal carbene complexes of the type trans-[Pt M~(ASM~~)~(~-XC~H~NHM~C)]+[P have been given. Comparison of the o+ substituent constants for X with the carbene carbon atom shieldings reveals that both o- and winteractions are occurring between the aromatic rings and the carbene carbon atoms. An inverse relationship between these carbene carbon atom shieldings and those of the analogous phenylthio-carbene complexes was discussed. The phenyl rings were shown to adopt cis-orientations with respect to the carbene methyl groups. The carbene carbon atom chemical shifts covered the range from 8 246.2 (X = C1) to 6 252.0 (X = OMe).342 A nuclear magnetic double resonance method for determining the sign and magnitude of J(XX') in [A,X],M, spin systems by the observation of the M resonance only has been described and applied to transPtCl Me(PMe,Ph),, MeN(PPh,),, and Me2C(PPh,),.343 A H o has been measured for the reaction --f

[MePt(PMe,Ph),(THF)]+ RJ5 310

J:17 :I3"

34u

342

343

+L

-+ [MePt(PMe,Ph),L]+

M. Green, J. A. Howard, J . L. Spencer, and F. G. A. Stone, J.C.S. Chem. Comm., 1975, 3 . L. E. Manzer and W. C. Seidel, J . Anlor. Chem. SOC.,1975, 97, 1956. L. E. Manzer and G. W. Parshall, J.C.S. Chenl. Comnr., 1975, 227. C. Eaborn, A. Pidcock, and B. R. Steele, J.C.S. Daffon, 1975, 809. C. Eaborn, T. N . hletham, and A. Pidcock, J.C.S. Daffon, 1975, 2212. M . H. Chisholm, H . C. Clark, J. E. H. Ward, and K. Yasufuku, Znorg. Chem., 1975, 14, 893. M. H . Chisholm, H . C. Clark, L. E. Manzer, J . B. Stothers, and J. E. 14. Ward, J. Amer. Chem. SOC., 1975, 97, 721. H. C . Clark, J. E. H. Ward, and K. Yasufuku, Cunad. J . Chem., 1975, 53, 186. I . J. Colquhoun, J . D. Kennedy, W. McFarlane, and R. 3. Puddephatt, J.C.S. Chem. Conitti., 1975, 638.

Spectroscopic Properties of Inorganic and Organonietallic Compoltnds

32

and a good correlation was found with 2J(1H-105Pt).In some cases the stereochemistry of the product was confirmed by 31Pn.m.r. ~pectroscopy.~4~ Previously published 13Cn.m.r. data for MePtXL, have been lH N.m.r. spectroscopy has been used to show the presence of a static ally1 group in (773-CsH6)Ni(C6C15)(PMe2Ph) and related The 'H n.m.r. spectrum of (59) shows broad lgaPt satellites, the broadening of which was attributed to rapid relaxation of the lg5Ptarising from the interaction with the . large quadrupole of 7 5 A ~The coupling to lB5Ptwas proven by decoupling the 'H, 13C,and 31Pn.m.r. spectra have been reported for compounds such as

,c \

F, C F,

CH,OMe (59)

-

trans-Pt(CH=CHCMe,OH),(PMe,Ph),. There are two isomers due to hindered rotation about the platinum-carbon bond,348and Eu(fod), was The observation O ~ J ( ' ~ ~ P ~ - ' ~=C70 N )Hz has been taken as evidence for the structure

'

(Ph,P),PtC(CN),CMe,OO rather than (Ph3P),PtOC(CN),CMe,0.350 1BF(1B5Pt} INDOR of (60) has been used to measure 1J(195Pt-1g5Pt) = 5355 H Z . ~ ~ N.m.r. ' I

data have also been reported for (C,Hll),PNi{C(CFs)=C(CF3)},~, (1BF),36e I

(BU~NC)~P~(C(CF~)= C(CFs)]>,

(1BF),353trans-PtCl(CH,CN)(PPh,),,

(Ph,MeP),Pt(CF=CF,)X, (1gF),s55 and LF,SiCH=CButSiF,di(CO),, (1gF).366 The lH n.m.r. spectrum of a freshly prepared CDC1, solution of trans-PtC1,(+C,H,)(isoquinoline) shows no 3J(1H-C-N-1g6Pt) owing to fast exchange s44

L. E. Manzer and C. A. Tolman, J. Amer. Chem. Soc.,

1975, 97, 1955.

355

M. H. Chisholm, H. C. Clark, L. E. Manzer, J. B. Stothers, and J. E. H. Ward, J. Amer. Chem. Soc., 1975, 97, 1987. M. Wada and T. Wakabayashi, J. Organometallic Chem., 1975, 96, 301. M. K. Cooper, P. J. Guerney, J. H. Ling, and R. S. Nyholrn, J. Organometallic Chem., 1975, 91, 117. H. D. Empsall, B. L. Shaw, and A. J. Stringer, J. Organometallic Chem., 1975, 96, 461. H. D. Ernpsall, B. L. Shaw, and A. J. Stringer, J. Organometallic Chem., 1975, 94, 131. R. A. Sheldon and J. A. van Doorn, J. Organometallic Chem., 1975, 94, 115. M. Green, J. A. K. Howard, A. Laguna, M. Murray, J. L. Spencer, and F. G. A. Stone, J.C.S. Chcm. Comm., 1975, 451. 14. C. Clark and A. Shaver, Canad. J. Cheni., 1975, 53, 3462. J. Browning, M. Green, A. Laguna, L. E. Smart, J. L. Spencer, and F. G. A. Stone, J.C.S. Chem. Comm., 1975,723. R. Ros, J. Renaud, and R. Roulet, Helc. Chim. Acta, 1975, 58, 133. V. A. Mukhedkar, B. J. Kavathekar, and A. J. Mukhedkar, J. Znorg. Nuclcar Chem., 1975,

yLo

C.4. Liu and C.-W. Cheng, J. Amer. Chmi. Soc., 1975, 97, 6746.

946

s40 347

34s yp9 350

381

YG2

363 sb4

37, 483.

Nirrlear Mugitetic Resonurice Spectroscopy

33

with a small aniount of adventitious free isoquinoline. However, after storage

at room temperature in the dark for several days the spectrum of the solution

clearly shows 3J(1H-C-N-1D5Pt). During the elapsed time, the uncomplexed isoquinoline is slowly consumed by the reaction with the complex to form trans-PtC12(isoquinoline)z.357'H,13Cn.m.r., and vibrational spectra and extended Hiickel MO calculations have been studied for a series of (q2-ethylene)platinum(I1) n-complexes. It was concluded that the co-ordinate bonding is dominated by the o-donation from ethylene to p l a t i n u m ( ~ i ) .The ~ ~ ~13C n.m.r. chemical shifts of trans-PtCl,X(pyridine) (X = CO, CzH,) and of a series of 4-substituted pyridine derivatives have been studied. Because of a linear correlation between the 13C chemical shifts of the 4-substituted pyridine ligands and both the corresponding benzenes and the trans-PtCl2(q2-CzH4)(4-R-pyridine) complexes, similar shielding mechanisms were suggested for these three classes of compounds. The 13C shifts of the C-2 atom of the 4-R-pyridine ligand in the complexes were correlated with a charge-transfer transition from the platinum to the 4-R-pyridine ligand. A relationship was found between the lSC chemical shifts of the co-ordinated ethylene and the Hammett up parameters of the 4-R-pyridine group and an explanation was given for the observed high upfield shift of the C2H, group in the complex. The upfield shift of the 13C0 signal was attributed to the anisotropy of the paramagnetic susceptibility of the platinum.3GDThe 13C and lU5Ptn.m.r. parameters for trans-PtCl,(piperidine)(r12-but-2-ene)have been reported. It was suggested that conclusions concerning metal-olefin bond strengths drawn from n.m.r. studies of nuclei not directly involved in bonding can be 'H and 13C n.m.r. chemical shifts and lJ(lH-13C) have been reported for the series (q2-olefin)Ni(P(O-o-tol),),. The relationship between 'H and 13C n.m.r. data and metal-olefin bonding was The complexes tuans-Cl,(r12-RMeCHCH=CHz)Pt(pyridine)have been prepared and their lH n.m.r. and c.d. spectra investigated. The two diastereoniers formed in the complexation of the chiral n-olefin to platinum(I1) are present in different concentrations in solution; the diastereomer with opposite absolute configurations at the two chiral centres is more prevalent. The extent of stereoselectivity according to evaluation by n.m.r. and c.d. spectra varies from 32% to 75% depending on the bulkiness of the R group. The preferred conformations of the two diastereomers for each complex were established by n.m.r., using the deshieiding effect on the protons bound to saturated carbon atoms, as well as J(lH-1H) and J(1H-1D5Pt).362The triplet observed for the CF groups in (q2-CF3CF=CFCF3)Pt(PPh3), has been attributed to the two 3J(1DF-31P) coupling constants being equal rather than the more usual explanation Extensive use has been made of lH n.m.r. as a second-order spectroscopy to identify the products of chloropalladation of cyclopropane i n F. Pesa and M. Orchin, Inorg. Chein., 1975, 14, 994. T. lwayanagi and Y. Saito, Inorg. Nuclear Chem. Letters, 1975, 11, 459. s60 M. A. M. Meester, D. J. Stufkens, and K. Vrieze, Inorg. Chim. Acta, 1975, 15, 137. 360 P. S. Pregosin and L. M. Venanzi, H d v . Chirn. Acta, 1975, 58, 1548. 3(r1 C. A. Tolman, A. D. English, and L. E. Manzer, Inorg. Chem., 1975, 14, 2353. R. Lazzaroni, P. Salvadori, C . Bertucci, and C. A. Veracini, J . OrganoniPtallic Chem., 1975, 99, 475. 3a3 J. M. Baraban and J. A. McGinnety, J . Arner. Cheni. SOC.,1975, 97, 4232. Ob7

Spectroscopic Properries of liiorgnrric nrtd Orgartonretulfic Cornporitrd.s

34

bicyclo[5, I ,010ct-3-ene and the subsequent I ,4,5-q-cyclo-octenyl to 1 -3-v-cyclooctenyl N.m.r. spectra have also been reported for Ni4(C0)4(CF3C2CF3)3, Ni3(CO)S(CsHs)(CF3C,CF3), (1YF),365 (q2-quinone)Pd(PBu1l,),, (13C),366 and (rle-C2F4)Pt(CNR),,(19F).3fi7 ‘H N.1n.r. spectroscopy shows for [Pd(~~3-allyl)(triazenide)], two conformers in solution, one with equivalent ally1 groups and the other N.m.r. data have also been reported for (~~-norbornadiene),Pd,(13C),3s9 (p-C5H6)(p-Br)Pd2(PPri3),, (130),370 [(1--3-q3-cyclohep ta- 1,3-dienyl)Pd(dppe)]f, and [(4-6-q3-cyclohept-1 -en-4-enyl)Pd(dppe)]+,

7 = Me,AsCH,-

For both L12Ni(CO), and L12NiOC(CF3)2C(CF,)20 (L1,

CHButCD,AsMe,), the conformations of the chelate rings are locked with the tert-butyl groups equatorial. The dihedral angles are very similar in spite of the anticipated differences in angles at the central atom. The square-planar complexes LZ2Pt(bipy)Cl2,(L2,),PtCI,, and the palladium analogues (L2,= H,NCH,CHButCD2NH,) also have their chelate rings locked in a chair conformation. The ,J(IH-lH) coupling constants indicate that the dihedral angles are similar in Group VIII complexes, with a degree of puckering which could be less than in the related complexes of L2.37213C N.m.r. spectra have been measured for a series of L,Ni(CO)4-, derivatives n = 0-3; L = PRl,, P(OR2),, or PCI,. The effect upon the 13C0chemical shift of the replacement of X by Y substituents in X3--,Y,PNi(CO)3 derivatives appears to be additive, as is the effect of the sequential replacement of CO by phosphorus ligands. An excellent correlation was observed between the 13C0 chemical shifts and either the i.r. stretching force constants or Kabachnik’s (T parameters. These data were analysed in terms of the electron donor-acceptor abilities of the ligand~.,~,A linear relationship has been found between the 31P chemical shift in the complex (OC)3NiPR1R2R3 (R1,R2, R3 = EMe,; E = Si, Ge, Sn) and the chemical shift of the free Iigand.374 13C N.m.r. chemical shifts, 8, and 1J(13C-195Pt) coupling constants have been obtained for a series of anionic, neutral, and cationic platinuni(rr) carbonyl complexes incorporating 13C0. In the series PtX(CO)L1L2 with the group X trans to the labelled CO group, for constant X, a decrease in 8 was observed for the 13C0 with increasing negative charge on the complex. Little variation in 8 was observed with change in the cis-ligand. Two ranges of values for 1J(13C-1s6Pt)were obtained for variation of the rums-group X ; for ligands with a high trans-influence, the coupling constant is in the range 960- 990 H z whereas for 366 3(L6 308

G . Aibelo, G. Wiger, and M. F. Rettig, J . Amcr. Chcm. Sac., 1975, 97, 4510. J. L. Davidson, M. Green, F. G . A. Stone, and A . L. Welch, J . Amer. Chem. SOC.,1975, 97, 7490.

H. Minematsu, S. Takahashi, and N. Hagihara, J . Organometallic Chem., 1975, 91, 389. G . A. Larkin, R. Mason, and M. G . H . Wallbridge, J.C.S. Dalton, 1975, 2305. S. Candeloro de Sanctis, L. Toniolo, T . Boschi, and G. Deganello, Inorg. Chitn. Acra, 1975, 12, 251.

R. M. Atkins, R. Mackenzie, P. L. Timms, and T. W. Turney, J.C.S. Chem. Comni., 1975,

164.

370

971

371 373 s74

A . Ducruix, H. Felkin, C. Pascard, and G. K . Turner, J.C.S. Chem. Comm., 1975, 615. D. J. Mabbott and P. M. Maitlis, f. Orgunometallic Chem., 1975, 102, C35. W. R. Cullen, L. D. Hall, J. T. Price, and G . Spendjean, Cunad. J. Chem., 1975, 53, 366. G. M. Bodner, Inorg. Chem., 1975, 14, 1932. H. Schumann, L. Rosch, H. Neumann, and H.-J. Kroth, Chem. Ber., 1975, 108, 1630.

Nuclear Mugtietic Resomiice Spectroscopy 35 ligands with low trans-influence the coupling constants fall in the range 1658- 1817 ~ 2 . 3 7 5 The 'H n.m.r. spectra of ethylenediamine complexes of platinuni(ii) in trifluoroacetic acid have been studied. The coupling constants 3J(1H-C-N-1DBPt) are the most informative parameters and are characteristic of the electron distribution in the complexes studied. The data were correlated with data on 'J(N-1Q5Pt) and 1J(31P-1D5Pt)for the corresponding compounds with nitrogen and phosphorus l i g a n d ~ .13C ~ ~ N.ni.r. ~ spectra of a series of aqueous squareplanar platinum(ri) chelates, [Pt(bipy)(substituted-1,2-ethyIenediamine)l2+, have been measured. The 13C chemical shifts of the bipy carbon atoms are fairly constant and in chelates of non-symmetric diamines, non-equivalent resonances were found for the two bipy rings. The 13C resonances of the aliphatic diamine portion resemble those of the free ligand, with the carbon atom a to nitrogen showing a 2-10 p.p.ni. downfield shift due to platinum bonding. 2J(13C-195Pt) for N-Me is 10-25 Hz and decreases on further N-methyl substitution while 3J(13C-1D6Pt)= 2CL-50 Hz. These data and known conformational properties for gauche five-membered diamine rings were used to show a Karplus-like dependence for 3J(13C-1Q5Pt). Using this 3J(13C-1Q5Pt) information and 3J(1H-1H), 3J(1H-1D5Pt),and 4J(1H-1D5Pt)n.m.r. data, an analysis of the conformational properties was made. substantial preference for a C-Me equatorial orientation was found for propane-l,2-diamine and N1N1-Me2-propane-l,2-diamine while N2N2-Me2-propane-1,2-diamine has a nearly equal distribution of axial and equatorial C-Me conformers. J(13C-lD5Pt)of the five-membered rings is highly structurally dependent, being ca. 0 Hz for symmetric rings and 10-15 Hz for unsymmetric rings. It was found that the lD5Ptsatellites in the '€1 n.ni.r. spectrum broaden at higher fields.377 13C N.ni.r. spectroscopy has also been used to investigate the Nil' complex of cu-mercaptopropionylglycine.378 The water content of K4[Pt(C204)2(SCN)2],4H20 has been analysed by lH n.ni.r. spectroscopy as a solution of the compound in D,0.37DAnalysis of the l H n.m.r. spectrum of (61) has been assisted by the use of E u ( f ~ d )and ~ P r ( f ~ d ) ~ ,and ~~O Me Me

376 376

s77 a78

W. J. Cherwinski, B. F. G. Johnson, J. Lewis, and J. R. Norton, J.C.S. Dalton, 1975, 1156. V. S. Petrosyan, L. V. Popov, S. G. Skaharov, and N. N. Zheligovskaya, Vestnik. Moskoii. Uniu., Khim., 1975, 16, 91 (Chem. Abs., 1975, 83, 18481). L. E. Erickson, J. E. Sarneski, and C. N. Reilley, Inorg. Chem., 1975, 14, 3007. Y. Sugiura, Y. Hirayama, H. Tanaka, and H. Sakurai, J . Znorg. Nuclear Chem., 1975, 37,

2367.

A. C. Villa, A. G. Manfredotti, A. Giacomelli, C. Guastini, and A. Indelli, Inorg. Ciiem., 1975, 14, 1654.

s80

L. F. Lindoy and W. E. Moody, J . Amer. Chern. Soc., 1975, 97, 2275.

36

S P C C ~u-opic. ~ * O Properties of' Irrorgarric crtid Orgcrtronlptu//ic Cornpout1d.y

n.1ii.r. spectroscopy has been used to determine the co-ordination mode of the ligand in coniplcxes such as (62).,,l The 19F and 31P n.1ii.r. spectra of cis- and trans-Ni(1,2-(F,P),cyclohexane], show that the ligand is a mixture of cis- and trans-i~omers.382 The 31p n.m.r. spectra of cis-PtXz{P(OPh)3}z (X = CNS or C15NS) show the independent existence of dithiocyanato-, di-isothiocyanato-, and mixed linkage isomers in solution, and the appearance of distinct resolvable J(31P-31p), J(14N-31p), and J(15N-31P) coupling constants in the spectra of the mixed species suggests a means of measuring these coupling constants in co-ordination complexes.383 For the complexes MeC(CHzPPhJ3PtL there are marked differences in 1J(1gsPt-31P) which were discussed in terms of hybridization at platjnum.384 13CN.m.r. spectroscopy has been shown to be a valuable analytical tool, offering considerable advantages over other physical methods, for the investigation of the site, and in some cases the degree, of deuterium incorporation in several simple alkenes and also in various tertiary phosphine complexes of p l a t i n u m ( ~ r ) . ~ ~ ~ The 13C n.1n.r. spectra of a series of complexes of the type PtCI,(PR3), and PtC14(PR3)2have been measured. The values of zJ(13C-1g5Pt)were shown to reflect changes i n the metal hybridization while the values 13J(13C-31P) + 5J(13C-31P)I were found to vary only slightly. It was suggested that the phosphorus hybridization in these complexes shows little change.38s lH, 13C, and 31P n.m.r. spectra of (4-ZCGHd)nPMe3-n ( Z = C1, H, Me, OMe), its derivatives, and palladium complexes have been measured. Linear correlations were found between the Hammett CT constants and lH chemical shifts for the free phosphines, phosphine oxides, phosphine sulphides, and most palladium(1i) complexes. The azide complexes have larger zJ(31P-31P) values and smaller co-ordination chemical shifts than the The 1J(31P-196Pt)coupling constant in the complexes cis-PtCI,(R,PCH,CH,PPh,) (R = CF3, C6F5) and the bond lengths in the complex with R = CF, indicate that the metal-ligand bonding is strongly influenced by substituents on the p h o s p h o r ~ s . ~ *The " values of 3J(19F-195Pt)in trans-PtX(SCF,)(PEt,), and cis-Pt(SCF3),L2 complexes have been used to establish a scale of trmns-influence for the X and L ligands, and the results were discussed in terms of existing theories of the Fernii-contact interaction. I t was concluded that an equation similar to those used previously for directly bound and two-bond coupling constants is still approximately valid for the longer range 3J(19F-195Pt)coupling constants. The question of non-zero intercepts in plots relating zvans-influence derived from coupling constants to different indicator ligands was discussed. A perturbation approach to the problem shows that non-zero intercepts arise when the indicator ligands have different sensitivities to the perturbation,38g '€3, l9F, and 31P1i.ni.r. spectra have IH

381

383 Sa3 384

386 SRe

3"'

8*8

3"B

D. B. Bonfocy and G. A. Melson, Iworg. Chct?1., 1975, 14, 309. N . R. Zack, K . W. Morse, and J. G. Morse, Znorg. Chem., 1975, 14, 3131. A. J. Carty and S . E. Jacobson, J.C.S. Chem. Comm., 1975, 175. J. Chatt, R. Mason, and D. W. Meek, J . Amer. Cliern. SOC.,1975, 91, 3826. A. D. H. Clague and C. Masters, J.C.S.Dalton, 1975. 858. p. S Pregosin and R. Kunz, Helv. Chini. Actrr, 1975, 58, 423. A. W. Verstuyft, L. W. Cary, and J. H. Nelson, Inorg. CItent., 1975, 14. 1495. 1. Macleod, L. Manojlovic-Muir, D. Millington, K. W. Muir, D. W. A. Sharp, and R. Walker, J . Orgnnotiirtallic C'hetn., 1975, 91, c 7 . K . K. Dixon, K . C. Moss, and M. A. R. Smith, J.C.S. Dalton, 1975, 990.

Nuc-lecrr Magne f ic. Resorrcirrc-r Speclroscopy

37

been reported for a number of fluoro-compounds, e.g. [Pt(PEt,),F]+[BF,]where 1J(1gF-1g5Pt)= 250 Hz, 1J(31P-196Pt)= 3455 Hz (trans to fluorine). It was concluded that there is only a small contribution from the platinum 6s and fluorine 2s N.1n.r. data have also been reported for [Ni{P(OCH,),CMe},NO]+[BF4], (31P),3D1 trans-NCPt(PPh,),X, and

(NCS),$dPPh2CH=C(CF3)CH,bPh2, (lgF, 31P).393The 13C n.m.r. spectra of a series of MC1,(AsR3), and M,CI4(AsR3), ( M = Pd, Pt) complexes have been measured. It was suggested that the 13C chemical shifts of the atoms directly bound to arsenic are useful structural probes. The chemical shift of the second carbon atom in the chain was interpreted in terms of interactions within the chains of any one ligand.3g4 The nematic-phase 'H n.m.r. spectra of bis(ethane-l,2-dithiolato)nickel(w) at several temperatures have been recorded. These spectra are consistent with a fluxional geometry in which the two organic ligands rotate rapidly with respect to one another on the n.m.r. time-scale. More than one orientation parameter is required to describe the molecular orientation, implying that this rotation is slow compared to the molecular reorientation time of the liquid lH N.m.r. spectra of dithioformate ligands in an extensive range of new platinum metal dithioformate complexes permit unambiguous assignment of the stereoThe linkage isomers of Pt(CNS)s(SMe,), have been identified by the coupling patterns of the 1H(1Q5Pt} INDOR spectra, and it was suggested that the le5Ptchemical shift provides a further distinction; the chemical shifts of the 14N nuclei coupled to lg5Pt (from lH(lg5Ptl4N}triple resonance measurements) are typical of N-bonded thiocyanate species.397 The values of 1J(77Se-1g5Pt) and 1J(125Te-1g5Pt)for [PtX,SeMe,]-, [PtX,SeMe,]-, and [PtX,TeMe,]- (X = C1, Br, I) have been obtained by heteronuclear lNDOR spectroscopy and decrease markedly in the order C1 > Br > 1. They are much less than the values of 1J(125Te-1g5Pt)in [(PtX,),TeMe,12- (X = C1, Br) which were obtained by direct A number of chlorofluoro-, fluoroFourier-transform n.ni.r. hydroxo-, and chlorofluorohydroxo-platinate(iv)species have been characterized in solution by lgF n.ii1.r. spectroscopy. The 19F chemical shifts, 6, are given to a good approximation by

6

= pC

+ qT

where C and T are constants characteristic of CI- and [OH]- and p and y are the number of substituents cis- and trans- to the fluorine atom respectively. The fluorohydroxyplatinate complexes are protonated in acid solution and pK, values of the aqua-species have been determined from the 19F chemical shifts as a function of pH. Solvent shifts of 1J(1gF-19SPt)were also r e p ~ r t e d . " ~ sBO

3u4

3y7 yu8

38B

M. A. Cairns, K. R. Dixon, and J. J. McFarland, J.C.S. Dulron, 1975, 1159. J. 11. Meiners, C. J . Kix, J. C. Clardy, and J. G. Verkade, Inorg. Chem., 1975, 14, 705. W. Beck and K . Schorpp, Chem. Ber., 1975, 108, 3317. A. J. Carty, S. E. Jacobson, R. T. Simpson, and N. J. Taylor, J. Ainer. Chetn. Suc., 1975, Y7, 7254. G. Balimann and P. S. Pregosin, Helu. Chini. Acta, 1975, 58, 1913. D. Bailey and J. P. Yesinowski, J.C.S. Dalton, 1975, 498. S . D. Robinson and A. Sahajpal, J . Organonietallic Chcni., 1975, 99, Ch5. S. J. Anderson and R . J . Goodfellow, J.C.S. Cherti. Conim., 1975, 443. P. L. Goggin, R. J. Goodfellow, and S. R. Haddock, J.C.S. Cheni. Conini., 1975, 176. D. F. Evans and G . K . Turner, J.C.S. Dullon, 1975, 1238.

38

Spec t roscop ic Properties of Inorganic at id 0rgaiiome tnllic c‘o tnpo1rrtcls

Complexes of Cu, Ag, and Au.--Information concerning complexes of thesc elements can be found at the following sources: ~ , ~ - ~ - ( P ~ : , P ) , C U B , H , , ~ ~ .-- --- - - _-

RUC~(C,C~H,F),PP~,(~~-C~H~),*~~ L,(OC)MCu(RIN-N-NR2)X (M 1

-

1

= K h , 1r),312 and [AUF6]-.1671 The ‘H, 13C, and 31P n.m.r. data have been reported for [Ph,PCHRMCHRPPh,]+CI- (M = Cu, Ag; R = H , Me, Pri). When M = Ag and R = H, 1J(13C-107* loSAg) = 96.5 Hz;~OO 1J(1H-C-107*lo9Ag) has been observed for Me2As{CH2AgCH,}2AsMe2.401 The 31P n.m.r. linewidth of C1(( MeO),P}Cu varies from sample to sample and correlates with catalytic 31PN.ni.r. spectroscopy has been used to show that addition of C1, to AuBr(PEt,) in CHCl, gives all six isomers of AuBr,-,CI,(PEt,). The relative stability constants were N.1n.r. data have also been reported for MeAuCHRPMe, (R = H, SiMe,), (31P);404 Me,P(CH,AuCH,),PMe,, (63), (31P),40s XMe,AuCH,PMe,, and (65), (31P).408 (31P),406(64;M = CU, Ag), (”C, 31P),407

(65)

Complexes of Zn, Cd, and Hg.-information concerning complexes of these elements can be found at the following sources: [Ph3PMe]+[B,oH12HgMe]-,124e and C~~-(~~-RO,CC=CCO,R)M~(CO),H~B~.~~~ l13Cd Pulsed Fourier-transform n.1n.r. studies have been carried out on a variety of l l T d metal-containing systems. It was shown that rnillimolar ‘0°

(04 ‘06

406 ‘07

‘On

Y. Yamamoto and H. Schmidbaur, J. Orgunornctullic Cltet~i.,1975, 96, 133. H . Schmidbaur and W. Richter, C/icm. Ber., 1975, 108, 2656. D. S. Wulfman, N. van Thinh, R. S. McDaniel, B. W. Peace, C. W. Hcitsch, and M. T. Jones, jun., J.C.S. Dalton, 1975, 522. B. T. Heaton and R. J. Kelsey, Inorg. Nucleur Cltem. Letters, 1975, 11, 363. H. Schmidbaur, Chem. Ber., 1975, 108, 1321. H. Schmidbaur and R. Franke, Inorg. C/titti. A d a , 1975, 13, 85. 1-1. Schmidbaur and R. Franke, Inorg. Chim. Actu, 1975, 13, 79. Y. Yamamoto and H. Schmidbaur, J. Orgatiomctallic Cliern., 1975, 97, 479. H. Kanter and K. Dimroth, Tetrahedron Letters, 1975, 545.

Nirclear Magnetic Resoriarice Spectroscopy

39

concentrations of " T d are readily observable for chemical shift and Tl studies. The chemical-shift range for lI3Cd exceeds 640 p.p.m., which is consistent with large paramagnetic contributions to the shielding constant. As much as 300 p.p.m. of this chemical-shift range can be attributed to substituent effects which occur in llsCd organometallic compounds. In addition to these findings, certain dialkylcadmiuni compounds were shown to undergo homo-exchange with an upper limit to the rate constant of 4.5 x lo2 s-1 for the self-exchange process. Organic solvent interactions also play a major role in affecting the chemical-shift range and the rates of exchange processes in dialkylcadmium compounds. A discussion of data concerning lI3Cd Tl times was presented. It was shown that Tl times in inorganic and organic cadmium compounds arise from a variety of competing A general study of legHg Fourier-transform n.m.r. spectroscopy has been completed. In sensitivity studies, a 25 inmol I-] solution of isotopically normal HgCI, exhibited a resonance with a r.m.s. signal : noise ratio of 9 : 1 in 10.2 h. lQ9HgChemical shifts of several mercury-containing pesticides were reported, and possible lgeHgchemical-shift reference compounds were compared. Measurements of the lQ9Hgchemical shift of Me,Hg and Et,Hg in many solvents demonstrate a very large solvent effect. The spin-lattice relaxation times of lo9Hg i n neat HgMe, and Hg(CH=CH,), are 0.87 and 0.25 s-l, respectively. The dependence of the TI values and the nuclear Overhauser effect indicate that the predominant relaxation mechanisms in these two compounds are chemical shift anisotropy and spin rotation, but the data do not allow detailed interpretation in terms of these mechanism^.'^^ Natural-abundance ln0Hg spectra of several organomercury carboxylates and organomercury chlorides have been reported. Both series of compounds show quite large solvent cffects on the mercury shifts and exhibit substantial substituent effects.411 The lH and 13C n.m.r. spectra of 'T-enriched Me,Hg orientated in a nematic solvent have been recorded at 270 MHz and 22.6 MHz. From the lH n.m.r. spectrum it was possible to calculate a precise value for the position of the carbon atoms with respect to the protons by use of the non-bonded proton-carbon anisotropic coupling. By comparison with the bonded proton-carbon coupling, it was found that the former is affected o n l y little by vibrational averaging. Furthermore, for theoretical reasons, it should only contain a negligible indirect contribution. Using the carbon positions, the anisotropy tensors of the indirect carbon-mercury and, with less precision, the carbon-carbon couplings were determined. It was found that in both cases the anisotropic part is about onehalf of the indirect couplings.412 Solvent effects on J(13C-199Hg)in Me,Hg, Et,Hg, and Pri,Hg and their fluorinated derivatives have been discussed in terms of mercury-carbon bond polarization and s-character of the mercury at on^.^^^ The 13C chemical shifts and J(13C-1SgHg)have been determined for a series of 11 symmetrically substituted organoinercurial compounds. Empirical substituent parameters can be calculated which correlate observed and predicted do@

410 4'1

A. D . Cardin, P. D . Ellis, J. D . Odom, and J. W. Howard, jun.,J. Amer. Chem. Soc., 1975,97,

1672. M. A. Sens, N. K . Wilson, P. D . Ellis, and J. D. Odom, J. Mugn. Resonance, 1975, 19, 323. M. Borzo and G . E. Maciel, J . Magn. Resonance, 1975, 19, 279. C . Schumann, D . Dreeskamp, and K. Hildenbrand, J. Magn. Resonance, 1975, 18, 97. L. A. Fedorov, 2. Stumbreviciute, and E. I. Fedin, Zhur. srrukr. Khim., 1974, 15, 1063.

40

Spectroscopic Properties of' Inorganic and Orgartometallic Compourlds

chemical shifts for dialkylmercurials.414 'H and 13C n.m.r. data of Me,SnX, (ButCH2),SnX, Me,PbX, (ButCH2),PbX, and BufCH,HgX, where X = Me, Et, Prl, But, ButCH2, CH=CH2, C1, Br, I, or OH, have been reported. The effects of electronic and steric factors on 'J(M-l3C) and 2J(M-1H) (M = Sn, Pb, Hg), were studied. Linear relationships which exist between lJ(M-13C) and *J(M-lH) were discussed in terms of the mechanisms of the coupling constants.41s A number of model benzyl-organometallic systems, e.g. BzMMe, (M = Si, Ge, Sn, Pb) and Bz,Hg, have been synthesized and the I3C n.m.r. spectra assigned. Comparison of 13Cchemical shifts of carbon atoms formally para to the carbonmetal bond strongly supports the importance of hyperconjugative interactions in the neutral ground state for metallo-methyl substituents. Further, an analysis of J(13C-M) coupling constants was used to determine the generality and origin (hyperconjugation) of a large 5J(13C-M) coupling in benzylic lH N.m.r. spectra of eight organomercury compounds, especially (CF3CH2)2Hg, have been measured in up to 57 solvents and correlated with structure and solvent nu~leophilicity.~ ~ ~ configurations of the peroxyniercurials RICHA(O,Hut)The CHB(H~O,CCF,)R~ have been assigned on the basis of the vicinal 3J('H~-1H~3) coupling constants. The structures of the cyclohexene and norbornene products are readily assigned from spectral similarity with other oxymercurials, and they result from trans- and cis-addition respectively. The relative magnitudes of 3J(1H~-1H~) and their behaviour upon addition of pyridine or replacement of 02CCF3by Br indicate that there is intramolecular ButO-. Hg co-ordination in the adducts and that the peroxymercurations involve trans addition.418 leF N.m.r. data have been reported for PhHgCFBrCF, and related corn pound^.^^^ A useful angular dependence of the vicinal 13C-lg9Hg spin-coupling constants has been found for compounds such as cis- and trans-4-Me-cyclohexylmercuric 13C Chemical shifts and J(13C-199Hg)coupling constants indicate 0-n conjugation between the C-Hg and C=O bonds occurs in R'HgCI and R12Hg but not in R2HgCI or R22Hg [R' = (66), R2 = (67)].421 I3C N.m.r. spectroscopy has been used to determine whether mercuration gives the ortho or meta product for (68).422 The gem spin-spin interaction of fluorine and mercury

'14

J. Casanova, H. R. Rogers, and K. L. Servis, Org. Magn. Resonance, 1975, 7 , 57.

ub G . Singh, J . Organometallic Chem., 1975, 99, 251.

W. Adcock, B. D. Gupta, W. Kitching, and D. Doddrell, J. Organometallic Cheni., 1975, 102, 297. '17 L. A. Fedorov, Z . Stumbreviciute, and E. I. Fedin, Zhur. org. Khim., 1975, 11, 913. (lRA. J. Bloodworth and I. M. Griffin, J.C.S. Perkin ZI, 1975, 531. D. Seyferth, G . L. Murphy, and R. A. Woodruff, J . Organornetallic Chem., 1975, 92, 7. Tetrahedron Letrers, 4 z 0 W. Kitching, D. Praeger, D. Doddrell, F. A . L. Anet, and J. Krane, 1975, 759. A. N . Nesmeyanov, V. A. Blinova, E. 1. Fedin, I . I . Kritskaya, and L. A. Fedorov, Doklady Akad. Nauk S.S.S.R., 1975, 220, 1336. Q2a Yu. S. Shabarov, L. D. Sychkova, and S. G. Bandaev, J . Organometallic Chem., 1 9 7 5 , 9 9 , 2 13.

Nuclear Magnetic Resonance Spectroscopy 41 atoms has been studied in (CF3)2Hgand p-XC6H4HgY(X = H, CF3, F, Me,N, MeO; Y = Me, OCOCF3, SCF,, S02CF3).423l9F N.m.r. spectra have been reported for (CF3),Hg and CF,HgI.424 Solvation of {(CF&2F},Hg, (CF,CF&Hg, and (CF,),Hg by pyridine, BuNH,, ethylenediamine, THF, dimethoxyethane, dioxan, and benzene has been correlated with structure uia 19Fand lQ9Hgn.m.r. s p e c t r ~ s c o p i e s . ~The ~ ~ 13C 17.m.r. spectrum of bis(thiodibenzoy1methanato)mercury(1i) indicates bonding to mercury via The 31P n.m.r. spectra of (69; M = Zn, Cd) have also been lH, 2QSi,and lS9Hgchemical Me,

,PPh, /CK, Et,M, ,Si, ,CH, A, CH, Me PPh,

/c,

shifts and coupling constants have been reported for Me,SiHgSiH,, (€4dSi)2Hg, Me,SiHgGeH,, and (H,,Ge),Hg.42'8 Based on 13Cchemical shifts and 1J(1H-13C), the nature of the bonding in the ethylene-mercuriniuni ion is best characterized by the predominance of the forward-donating o-component with a significant decrease in the electron density at the olcfinic carbon. The norbornadiene and I ,5-cyclo-octadiene complexes were also i n v e ~ t i g a t e d . ~ ~ ~ The lineshape of optically orientated 201Hg atoms in a non-homogeneous magnetic and r.f. field has been studied. The signal is a superposition o f a narrow peak (< 10 HI) and a broad (CCI. l 0 0 0 H z ) Lorentiian line.130 The complexes Zn(bipy)CI, and Zn(bipy),CI, have been examined in D,O. The changes in chemical shifts of bipy protons for the complexes Zn(bipy),CI, and Zn(bipy)CI, have confirmed explicitly the influence of diamagnetic currents on the n.m.r. spectrum of Zn(bipy),Cl,. Comparison of the lH n.ni.r. spectra of 2,2'-bipy and of Zn(bipy)CI, may also suggest the presence of the non-bonding metal-proton (6) interaction.33* Similar studies have been carried out on some cadmium bipyridyl complexes, and, i n the case of Cd(bipy)S04,4H,0, t h o kinds of hydration isomers were detected.432 The I3C' n.ni.r. spectra of nreso-tetraphenylporphyrin (TPP), and some zinc(ll), cadmium(ii), mercury(ii), and thallium(Iri) derivatives have been assigned. The introduction of zinc(ir), E. V. Konovalov, E. P. Saenko, T. Ya. Lavrenyuk, N . V. Kondratenko, and V. I. Popov, Teor. i eksp. Khint., 1975, 11, 248. R. Eujen and R . J . Lagow, Innrg. Chenl., 1975, 14, 3128. m6 L. A. Fedorov, Z. Stumbreviciute, B. 1. Martynov, and B. L. Dyatkin, Zhur. org. Khini., 1975, 11, 489. ue G . Engelhardt, B. Schuknecht. and E. Uhlemann, Z . Clieni., 1975, 15, 367. H . Schmidbaur and W. Wolf, ChPni. Ber., 1975, 108, 2851. ( 2 8 S. Cradock, E. A V. Ebsworth, N. S. IIosmane, and K . M. Mackay, Angew. Cliem. Internat. Edn., 1975. 14, 167. G . A. Olah and S. H. Yu, J . Org. C f i ~ t ~1975, i., 40, 3638. 4a0 S. L. Votyakov, V. V. Zverev, and L. N. Novlkov, Izrest. V. U. Z . , Radiofiz., 1975, 18, 869 (Chem. A h . , 1975, 83, 139 483). 431 B. Jezowska-Triebiatowska, H. Kozlowski, I,. Latos-Graiynski, and T. Kowalik, Chem. Ph-vs. Lctrers, 1975. 30, 355. pJa B. Jezowska-Trzebiatowska, G . Formicha-Kozlouska, 11. Kozlowski, L. Latos-Graiynski, and T. Kowalik, Clictn. Pliys. Lettrrs, 1975, 30, 3 5 8 .

424

42

Spectroscopic Properties of Inorganic and Organontetaiiic Compounds

cadrnium(ri), or [Hg"(OAc)], into the TPP nucleus does not significantly change the 13C n.m.r. shifts, but the thallium(rr) derivative shows both extensive J(13C-2039 2O5Tl) coupling and non-equivalence of the o-phenyl carbon atoms; the latter being due to the exo-planar position of the thallium atom. Specific J(13C-2031205Tl)coupling constants to the o-phenyl carbon atoms were also lH N.m.r. spectroscopy has been used to show that the octaalkylporphyrinmercury(l1) complex can exist as a dimer (70) which is stable to disproportionation and r e c ~ m b i n a t i o n . ~ ~ ~

Hg

Hs I

OAc

Tn the 67Z11n.m.r. spectra for various solutions of zinc salts in H,O and D,O for ZnT,, ZnBr,, and ZnCl,, a remarkable shift to higher frequency was observed, whereas for Zn(ClO,),, Zn(NO,),, and ZnSO, no shift was observed. The shifts in the zinc halide solution depended on the isotopic composition of the solvent. Substitution of H by D in the solvent gave for the s7Znline an anomalous solvent isotope effect to high frequency. With increasing temperature, a linear increase in the shift and a non-linear decrease in the linewidth for the zinc halide solutions were observed. The ratio of the Larmor frequency of 67Znand 37Clwas measured in aqueous Zn(C10,), solution. The magnetic moment of 67Zn2+(aq)was determined to be 0.873 664 4(12)pus. The shielding constant of 67Zn2+(aq) 033

R. J. Abraham, G . E. Hawkes, M. F. Hudson, and K . M. Smith, J.C.S. Pcrkin 11, 1975, 204. M. F. Hudson and K . M . Smith, Tetrahedron, 1975, 31, 3077.

43

Niiclear Magnetic Resonance Spectroscopy

uersus atomic 67Zn is (-6.9 k 0.1) x The n.m.r. spectrum of zinc lactate (71% enriched) has been noted in a study of the fermentation of 13Cenriched sugars.436The structure of Hg(S2CNEt2),in solution is highly symmetric, unlike the helical polymer in the solid 3 Dynamic Systems The layout of this section is in three parts: (i) ‘Fluxional Molecules’, dealing with rate processes involving no molecular change, (ii) ‘Equilibria’ dealing with the use of n.m.r. spectroscopy to measure the position of equilibria and ligandexchange reactions, and (iii) ‘Course of Reactions’ dealing with the use of n.m.r. spectroscopy to monitor the course of reactions. Each section is ordered by the Periodic Table. A book entitled ‘Dynamic Nuclear Magnetic Resonance Spectroscopy’ has appeared,16 and reviews published include ‘Fluxionality in Organometallics and Metal Carbonyls’ ;43M a review of cyclo-octatetraene chemistry which contains a section on dynamic metal ‘The Role of CIDNP in a Mechanistic Investigation of Alkyl Lithium-Alkyl Halide Reactions’;440 ‘Applications of Density Matrix Theory to N.m.r. Line-shape calculation^';^^^ ‘Proton, Deuterium, and Alkali N.m.r. Studies on Alkali Naphthalene Ion Pairs’;d42 ‘N.m.r. Studies of Pure Water’;443‘N.m.r. Methods. Aqueous Non-electrolyte Solutions’ ;444 ‘N.m.r. Methods. Aqueous Electrolyte Solutions’;445 and ‘Possibilities of Nuclear Magnetic Resonance in the Study of Polyelectrolyte The review, ‘Effect of the Nature of the Alkali Metal and Halogen on the Stability of Complex Compounds in Tin(x1) Halide-Alkali Metal Halide Systems’ includes the use of n.m.r. and the review ‘Water Molecules in the Solid and Liquid State’ includes a section on the relation between the anomalies in the temperature dependence of Tl in liquid Fluxional Molecules.---Li and Be. The influence of Li+ and BeS+on the rotational barrier of Me,NCHO has been investigated by ‘H n.m.r. line-shape analysis. The changes in the activation energy at various ion concentrations were discussed and compared with LCGO-MO-SCF calculations for 1 : 1 complexes of Li+ and Be2+ with formamide and Me,NCHO and 2 : 1 complexes of Li with formamide. Good agreement was +

4.15 4.16 437 4.J8

419 440

441 441 443

444 440

447

44*

R. W. Epperlein. H . Krueger. 0. Lutz, and A. Schwenk, Z. Naturforsch., 1974, 29a. 1553. R. E. London, V. H. Kollman, and N. A. Matwiyoff, J. Amer. Chem. Sor.., 1975, 97, 3565. G . S, Nikolov, DoXIudy Bolg. AXad. Nuuk, 1975, 28, 635 (Chem. Abs., 1975, 83, 171 934). F. A. Cotton, J. Org~noni~tullic Chem., 1975, 100, 29. L. A. Paquette, Tctruhedron, 1975, 31, 2855. €1. R. Ward, R. G . Lawler, and R. A. Cooper, Client. Induced Magn. Polariz., 1973, 281 (Chem. Abs., 1975, 82, 30 45 1). P. D. Buckley, K. W. Jolley, and D. N. Pinder, Specfrosc. 1975, 10, Pt. I , I . E. De Boer and €3. M. P. Hendriks, Pure Appl. Chem., 1974, 40,259. J. A. Glasel, ‘Struct. Water Aqueous Solutions’, Proceedings of International Symposium, 1973. ed. W. A. P. Luck, Verlag Chem., Marburg, Germany, 1974, p. 425. M. D. Zeidler, ref. 443, p. 461. H. G . Hertz, ref. 443. p. 439. G. Weill and P. Spegt, Chnrgtd React. Po1.vm. I Polyelectrulytcs, Pap. NATO A h . Study Inst. Chrrrg~dRpuct. Po!,,ni., 1972, 1972, 371 (Clieni. Abs., 1975, 83, 43 766). N. V. Karpenko and T. N. Sevast’yanova, Proh. Sourcm. Khini. Koord. Socdin., 1974, 4, 177 (Chem. Abs., 1975, 82, 90 884). Y. Kakiuchi, Busspi, 1974, 15, 427 (Chenl. Ahs., 1975. 82, 90 141). B. M. Rode and R. Fussenegger, J.C.S. Furaday It, 1975, 1958.

44

Spectroscopic. Properties of Inorganic and Organometullic Compolrnds

Ti, Zr, and Hf. The compounds (r15-C5H5),M(BH4),(M = Zr, Hf) and (v5-c6H5)ZrH(BH,) exhibit exchange of the cyclopentadienyl and borohydride hydrogen atoms which is rapid on the 'H n.m.r. time-scale. The process was found to be predominantly uniniolecular with AG,,,* of 21.3 k 0.4, 19.4 0.4, and 19.6 k 0.4kcal n m - ' respectively. For (r15-C5H5)ZrH(BH4), the hydride hydrogen also appears to become involved in the exchange process at higher temperatures, with AG395* = 20.9 ? 0.5 kcal mol-l. The interchange process also occurs for (~5-C6H5)Zr(BD4), in the solid state but more slowly.45o The 'H n.m.r. spectra of some organo-zirconium-aluminium compounds having the M1-C-C-M2 type structure, e.g. (q5-C5H5)2ZrC1(CH,CH,)AIEt2, have been described. Their structures, conformations, and complexation with alkylaluminium were discussed in terms of coalescence temperatures.451 13C N.m.r. spectroscopy has been used to show that (?)5-C6H5)4Zr is fluxional, (q6-C5H5)Zr(acac),CI is stereorigid with a cis-C5H5--C1 pseudo-octahedral structure, while ( ~ ~ - C ~ H ~ ) M ( d b(M r n )=~ Hf, Zr; dbm = dibenzoylmethyl) and (q6-C5H5)Zr(acac).(dbn-r),_, are pentagonal bipyramids with the q5-C6H5group axial. Two chelate rings in (q5- C,H,)M(acac)-(dbni),-, are in an equatorial plane and are equivalent, while the third ring is axial-equatorial. (q5-C5H5)Zr(acac).(dbm),-, is probably a mixture of conformational 'H N.m.r. signals for the nonequivalent 0- and rn-protons in indium(RC,H,), porphyrin chloride (R = Pri, CF,) and the Ti0 and Ru(CO)(THF) analogues have been shown to average on the n.m.r. time-scale between 10 and 140 "C by a concentration-independent pathway. In the same temperature range there is no evidence of averaging non-equivalent methyl 'H n.m.r. signals in the o-tolyl and mesityl analogues. In the l8F n.m.r. spectrum of In(C,F,), porphyrin chloride, the signals for the non-equivalent o- and m-fluorine atoms do not average up to 130 "C. The averaging of lH n.m.r. peaks was attributed to rotation of the phenyl rings. Addition of Bun4NC1to the indium compound causes a concentration-dependent averaging which was attributed to chloride exchange. Addition of CO to the ruthenium compound also affects averaging.453 A variable-temperature n.m.r. study of Ti(acac),(OCMe,(CH,),CMe,O) and related compounds shows that the relative rates of degenerate enantionierization and site exchange of the dionato-methyl groups vary with A similar investigation on cis-(RO),Ti(acac), has led to the conclusion that these experiments provide 'compelling evidence for the reversal of helicity in the stereoisomerization mechanisms of such m01ecules',~~~ A number of complexes, Ti(acac),(OR),, and related complexes, have had A H * and A S * determined for inversion or exchange and the mechanisms have been Variable-temperature n.m.r. spectra of Ti(RCOCHCOR),(NCE), (E = 0, S ) show that the 6-diketonate rings undergo a rapid intramolecular configurational rearrangement which exchanges the methyl groups between the .i50 45 1

m

T. J. Marks and J. R. Kolb, J. Amcr. Chem. SOC.,1975, 97, 3397. W. Kaminsky and H.-J. Vollmer, Annnfen, 1975, 438. M. Kh. Minacheva, E. V. Arshavskaya, L. A. Fedorov, and E. M. Brainina, Koord. Kliim.,

1975. 1, 831. S. S. Eaton and G . R. Eaton, J . Anier. Cficm. SOC.,1975, 97, 3660. p 5 p N. Baggett, D. S. P. Poolton, and W. 13. Jcnnings, J.C.S. Chpm. Comm., 1975, 239. 4 b 6 P. Finocchiaro, J. Atiier. Client. SOC.,1975, 97. 4443. m R . C. Fay and A. F. Lindmark, J. Anier. Chcrn. Soc., 1975, 97, 5928. 453

Nuclear Mugiretic Resonance Spectroscopy 45 two non-equivalent sites of the cis-isomer. The first-order rate constants were extrapolated to 25 "C, and A H * and A S * were given. The Ti(RCOCHCOR)2(NCS), complexes rearrange faster (by a factor of ca. 10,) than the Ti(RCOCHCOR),(NCO), analogues, but precise kinetic data could not be obtained because of the low coalescence t e n i p e r a t ~ r e . ~ ~ '

V, N b, and Ta. For (q5-C5H,)2VBH4,the free-energy barrier to bridge-terminal hydrogen interchange is surprisingly high (AG* = 7.6 f 0.3 kcal mol-I) and the fluxional behaviour can be slowed on the n.m.r. time-scale. The process in the Nb analogue is too rapid to be Compound (71) shows two

CH(CH,) signals at room temperature which coalesce on heating due to rotation about the Ta-CH, bond.459 lH N.ii1.r. total lineshape analysis of [Ta(S2CNMe,).,]+[TaCI,]-shows two methyl signals at low temperature and one at high temperature, with A H * = 10.4 k 0.4kcal mol-1 and A S * = - 3.1 k 2.0 ~ . u . ~ , O

Cr, Mo, and W. For H(~jW~H,),Mo(dppe), and HMo(r13-C3H,)(dppe),, exchange occurs between the hydride and ethylene and ally1 protons, respectively. The 31P n.ni.r. spectrum of (q2-C2H4),Mo(dppe),was also reported.'R1 The 13C n.1n.r. spectrum of (72) has been examined from - 122 to + 92 * C . There is Pri

Mc

local scrambling of the three CO groups on each molybdenum atom but at vastly disparate rates; resonances for one set coalesce below - 112 "C whereas those of the other set coalesce at ca. - 30 "C. No scrambling of CO groups from one metal atom to the other was observed.46z The 13C n.m.r. spectra of some LM(CO), complexes (L = cycloheptatriene or cyclo-octa-l,3,5-triene; M = Cr, Mo, W) have been reported. Two novel ligand movements have been detected in these compounds: a hindered rotation of the cyclopolyene ligands A. F. Lindmark and R . C. Fay, Inorg. Chein., 1975, 14, 282. T. J. Marks and W. J. Kennelly, J . Amer. Chem. SOC.,1975, 97, 1439. t n Q L. L. Guggenberger and R . R. Schrock, J . Amer. Chern. SOC.,1975, 97, 6578. u 0 R. C. Fay, D. F. Lewis, and J . R. Weir, J . Amor. Chem. Soc., 1975, 97, 7179. 401 J. W. Byrne, H . U. Hlaser, and J . A. Osborn, J . Anrpr. Chem. SOL'.,1975, 97, 3871. u2 F. A. Cotton, D. L. Hunter, and P. Lahuerta, J . Orgunornetallic C'hem., 1975, 87, C42. 451

45A

46

Spectroscopic Properties of Inorganic and Organometallic Compounds

around the prolonged three-fold axis of the (,OC),M groups with AG* from 11.3 to 12.7 f 0 . 3 kcal niol-', and the cyclo-octa-1,3,5-triene ligand in (qe-C,H,,)Cr(CO), is frozen at - 120 "C into a chiral conformation. The enantiomers can be interconverted with an energy barrier463 of 8.3 k 0.1 kcal 11101-'. The 13Cn.ii1.r. spectrum of Rr(l=CHCH=NRh(CO), (M = Cr, Mo, W) shows cis-trans exchange of the CO ligands, and the activation barrier was determined."' 31P N.ni.r. spectroscopy of (73) shows a temperature-

dependent exchange.465 The 'H 1i.tn.r. spectra of (MeSeCH,CMe,CH,SeMe)M(CO), are temperature-dependent and were analysed in terms of total inversion of the six-niembered ring system.466The lH n.m.r. spectra of W,(O,CNMeR), (R = Me, Et) show only one N-methyl signal at room temperature but two, in the ratio 2 : 1, at low temperature^.^^' Mn, Tc, aid Re, The 'H n.ni.r. spectruni of (74) shows one hydride signal at r 20.57 at room temperature, which splits into two types at -39 0C.468 The

Me), j met hoxy-signals i n the 'H n.111.r. spectrum of (qs-C,H,) M n(CO),{ 7l2-C2(O show a definite temperature dependence. I n CS, solution, the variations of thc signals were observed within a single temperature range while i n [zHH,]toluene, two regions of change were found to exist. These data were explained on the basis of two mutually independcnt ligand movements, a hindered rotation of the olefin around the metal-olefin bond (AGIQ4* = 9.8 2 0.6 kcal mol-l) and a hindered movement of the M e 0 groups (AG263* = 13.8 L- 0.3 kcalmol-I). Chiral conforniations of the ligand were assumed to be formed when the niovenient of the methoxy-substituents had ceased.46QLow-temperature ,*P n.ni.r. studies of (q4-diene)M1(CO),L,-, and (r15-dienyl)M2(CO),,L,_, [diene = cycloC. G . Kreiter, M . Lang, and H . Strack, Chent. B w . , 1975, 108, 1502. W. Majunke, D. Lcibfrit7, T. Mack, and H. Tom Dieck, Chcm. Ber., 1975, 108, 3025. G. Schmid and H.-P. Kenipny, 2.cinorg. Chrm., 1975, 418, 423. p n 6 G. Hunter and K. C. Massey, J.C.S. Dcrlfon, 1975, 209. .ie7 M . H . Chisholm and M . Extine, J . Anwr. Cheni. Snc., 1975, 97, 5625. r n s V. G. Albano, G . Ciani, M. Freni, and P. Romiti, J . OrgunomefaNic Cheni., 1975, 96, 259. p 6 B M. Herberhold, C. Ci. Kreiter, S. Stiiber, and G. 0. Wiedersatz, J . Orgunornefallic Cheni., 1975, 96, 89.

463

4R4

47

Nitclear Magnetic Resortailre Spectroscopy

hexadiene, cycloheptadiene; M 1 = Fe, Ru; dienyl = cyclopentadiciiyl, cyclohexadienyl, cycloheptadienyl; M 2 = M n , Re, Fe+, R u t ; L = P(OCH,),CEt] show that most of them exist as mixtures of ligand isomers and that these isomers are undergoing rapid interconversion at ambient temperature. The rate of ligand scrambling depends principally on the metal for both diene and dienyl species, decreasing in the order Mn = Re > Fe+ > Ruf for dienyl compounds and Fe > Ru for the diene compounds. Surprisingly, the formally five-co-ordinate diene compounds scramble only slightly faster than the formally six-co-ordinate dienyl complexes. The total range of rates is only a factor of ca. lo4 at 220 K , suggesting that the phenomenon is probably quite general for transition-metal 7-r-complexes. For the cycloheptadiene compound a second, faster fluxional process involving equilibration of the methylene groups of the organic ligand was also The fluxional character of both Re and Tc complexes (tetraphenylporphyrin - H)M(CO), has been observed in variable temperature 'H n.ii1.r. spectral studies. This fluxional phenomenon was explained by the intramolecular rearrangement of the M(CO)3 group aniong the four ring nitrogen atoms of the porphyrin and concomitant movement of the NH (MeNC)(OC),MnMn(CO),(CNMe), has been examined by variable-temperature 'H n.m.r. spectroscopy. It was shown that the isonitrilc ligands exchange between the two metal atoms at approximately 100 "C. Comparison of these results with those for the complex [(q6-C,H,)Fe(CO)(CNMe)], shows that the activation barriers are very similar and suggests that geometrical variations may not be very important factors in determining the facility by which bridge-terminal co-ordination rearrangements occur.472 Fe, Ru, and 0 s . At - 6 0 "C, the 'H n.m.r. spectrum of (75) shows the terminal hydride at T 20 and the bridge hydride at T 30. On warming, the signals coalesce,

(75)

.

to give AG237* = 12.4 kcal mol-l, while for H20s3(CO)loPMe2PhAG,,,* = 10.9 kcal mo1-1.473 lH N.ni.r. spectroscopy shows exchange in H,Os(CO),(C=CH,) for the CH2 group at 80°C while if HDOs,(CO),(C=CH,) is prepared H-D scrambling only occurs at 100 0C.474 [(~6-C,H,)(~2-olefin)Fe(CO),lf and the indenyl analogue have been examined by lH and 13Cn.m.r. spectroscopies. Signal broadening was used to estimate the 470

472 li3

474

T. H. Whitesidcs and R. A. Budnik, Itiorg. Cliem., 1975, 14, 664. M. Tsutsui. C. P. Hrung, D. Ostfeld, T. S. Srivastava, D. L. Cullen, and E. F. Meyer, jun., J . Amer. Cliem. SOC.,1975, 91, 3952. R. D. Adams and D. F. Chodosh, J . Orgunonrrtallic Chem., 1975, 87, C48. J. R . Shapley, J. B. Keister, M. K. Churchill, and B. G. De Boer, J . Amer. Clzem. Soc,, 1975, 91, 4145. W. C. Jackson, B. F. C. Johnson, and J. Lewis, J . Orgat~ometallicChciti., 1975, 90, C13.

48

Spectroscopic Properties of Inorgntric and Organonletnllic Compounds

barrier to rotation about the Fe-olefin bond as ca. 8 k c a l ~ n o l - ~ .By J~~ use of 13C n.ni.r. spectroscopy i t has been shown that for [Os(CO)(NO)(q2-C2H4)(PPh3),l+ olefin rotation occurs via the nietal-olefin bond with AGT,* = 9.5 0.2 kcal m ~ l - l . Variable-temperature ~~~ l H n.m.r. spectra of [Os(CO)(NO)(q2-HC=CH)L2]+ are consistent with hindered rotation about the metalacetylene bond, with AG7?,* = 11.5 L- 0.2 kcal niol-' (L = PPh3) or 14.4 & 0.5 kcal mol-1 {L = P(CBH11)3}.477 lH and 13C n.m.r. studies on HzM3(C0)9(q2-R1R2C2)(M = Ru, 0s) have shown that at least three separate fluxional processes are occurring. A mechanism involving olefin rotation was considered. For H2Os,(CO),(v2-MeC=CMe), AGTc* = 13 kcal mol-1 (from lH) or 12.3 kcal mol-1 ('T) and for H , O S ( C O ) , ( ~ ~ - C ~ HAGT,* ~ ~ ) , = 16.9 kcal mol-1 (lH) or 17.0 kcal mol-1 (13C).478 The lH n.m.r. spectrum of Fe2(CO),(HC,But),(CO) shows one tert-butyl signal at room temperature and three at low temperature.47Q The 13C0 linewidth of (v5-C5H,)Fe(CO),I is invariant with temperature from 40 to -50 "C at 1.2 Hz but in the presence of 0.079 mol 1-1 Cr(acac), the linewidth changes from 1.1 Hz at 40 "C to 6.4 Hz at - 50 "C. Thus, unless great care is taken, the use of Cr(acac), can introduce significant errors when carrying out lineshape analysis The 'H and 13C n.m.r. spectra of ($-cycleheptadienyl)(~5-cycloheptatrienyl)Ru show the C7H, ring to be fluxional giving seven 13C signals at - 110 "C with A G l B 0 ~ *= 8.1 f 0.2 kcal r n 0 1 - l . ~ ~Both ~ RU,(CO)~(C~H,)(C~H~) and Ru,X(CO),(C,H,) contain cycloheptatrienyl rings which are fluxional down to - 100 "C, while RU,I(CO)~(C~H~R) is fluxional but the spectra are limited at low temperature.482 The three compounds (76) to (78) are fluxional and in the cases of (76) and (77) AG* = 16.0 kcal Similarly fluxionality has been demonstrated for (79) (static at - 127 0C),484 (80) (static at - 1 15 0C),486 and (8 I ) (static at - 30 oC).486 The flipping of CO ligand groups in metal carbonyl compounds has been discussed. For Fe(CO),, the rate is 1 . 1 x 1Olo s-1.487 An extensive l9F n.m.r. study has been made on some (~4-niethyl-substituted b~tadiene)Fe(PF,),,(CO)~-.~ complexes. The results confirm the vibrational analysis and show that the PF, ligand exhibits a strong preference for the apical positions over either of the two basal sites. In the diphosphines of asymmetric dienes, PF3 exhibits a secondary preference for the basal position trarzs to the methyl group on the butadiene ligand. Intramolecular exchange of the PF3 groups occurs in the di- and triJ. W. Faller and B. V. Johnson, J . Organometallic Chem., 1975, 88, 101. J. A. Segal and B. F. G . Johnson, J.C.S. Dalton, 1975, 677. b 7 7 J. A. Segal and B. F. G . Johnson, J.C.S. Dalton, 1975, 1990. 478 J. Evans, B. F. G . Johnson, J. Lewis, and T. W. Matheson, J . Organometallic Chem., 1975, 97, C16. 4 7 ~ 1 E. Sappa, L. Milone, and G. D. Andreetti, Inorg. Chim. Acta, 1975, 13, 67. * 8 0 F. A. Cotton, D. L. Hunter, and A. J. White, Inorg. Chrm., 1975, 14, 703. J. Muller, C. G . Kreiter, B. Mertschenk, and S. Schmitt, Chern. Ber., 1975, 108, 273. 4 F 2 J. C. Burt, S. A . R. Knox, and F. G. A. Stone, J.C.S. Dalron, 1975, 731. p n 3 R. Aumann, Chem. Ber., 1975, 108, 1974. ln4 J. Takats, J. Organornetallic Chem., 1975, 90, 21 I . 4s6 G . Deganello, P. L. Sandrini, R. A. Michelin, and L. Toniolo, J . Organometallic Chem., 1975, 90, C31. R. Goddard, A. P. Humphries, S. A. R. Knox, and P. Woodward, J.C.S. Chem. Cotnnt., 1975, 508. 4n7 R. K . Sheline and H . Mahnke, Angew. Chem. Internat. Edn., 1975, 14, 314.

p76

47u

Nrrclear. Magtietic Resotinrice Spectroscopy

)J

@

(,0(.-)3 RU-R CI( C O ) ,

(79)

(80)

49

I W (OC),Ru---

/

R L:(CO), (81)

phosphines of both asymmetric and symmetric dienes. The limiting spectra are generally well developed by -100°C. Comparison of the limiting and timeaveraged parameters provided information concerning the general nature of the non-rigid process.488 The 'H and 13C n.Ii7.r. spectra of (q4-1-MeO-cyclohexa1,3-diene)Fe(CO), have been reinvestigated. Determination of lJ(lH--13C) and the energy barrier (hGTc* = 7.3 k 0.2 kcal mol-l) for basal-apical CO ligand exchange makes possible the discussion of the stability and lability of the complex in terms of electronic perturbation^.^^^ Variable-temperature 13C n.m.r. studies on (+C5H5),Fe2(CO),(CNR) show that the molecule is fluxional for R = But, which contains a terminally bonded CNR ligand but is static for R = Ph, which contains a bridging CNPh ligand. It was also shown that 13C resonances of isonitrile ligands are diagnostic of the presence of bridging or terminal CNR groups.4eo FluxionaI processes have been examined in (82; M 1 = Co, X absent, M2 = Ge, Sn; M1 = Fe, X = CO, M2 = Si, Sn) by l H n.m.r. spectroscopy. For (MePhSn),Fe,(CO),, a mixture of isomers was found with two exchange processes; one with AG* = 12.7 k 0.3 kcalmol-l and the other with AG* = 22.2 k 0.7 kcal ~ o I - ~ A. number ~ ~ ~ of compounds of the general type (OC)3M(p-ER,)2M(CO)3 (M = Fe, ER, = PMe,, AsMePh, AsMe,, SMe, SEt; M = Co, ER, = GeMe,, SnMe,) 4'19

M. A. Busch and R. J. Clark, Inorg. Chcnt., 1975, 14, 226. J.-Y. Lallemand, P. Laszlo, C. Muzette, and A. Stockis, J . Organonierallic Chcm., 1975, 91,

71. A. S. Howell, T. W. Matheson, and M. J. Mays, J.C.S. Chem. Comm., 1975, 865. T. J. Marks and G . W. Grynkewich, J . Organomefnllic Chem., 1975, 91, C9.

4'0 J. dl'l

50

Spec t 1.0 sc o pic Properties of ltroi*gnti ic mid Organont e tallic Cornpormds Mc \lc

h l c hlc \ /

have been prepared and their dynamical properties studied by lH and n.1n.r. spectroscopy. The RS-bridged compounds shob no evidence of axial-equatorial R-group exchange prior to the onset of irreversible thermolysis. All the phosphinoand arsino-bridged iron compounds show R-group exchange with coalescence temperatures in the range 50 to 100 "C whereas the germylyl- and silylyl-bridged cobalt compounds exhibit R-group exchange with coalescence temperatures around - 55 "C. Interconversion of symmetric and unsymmetric isomers of the AsMePh-bridged iron compound requires a period of many hours at cu. 150" C to attain equilibrium. Rapid exchange of non-equivalent CO groups proceeds at very low temperatures in all cases, with coalescence temperatures of around - 70 " C. Thus there appear to be three essentially independent processes which are, i n order of decreasing rate, (i) CO scrambling, (ii) axiakquatorial R-group exchange in a concerted fashion such that it occurs in both ER2 groups simultaneously, and (iii) axial-equatorial R-group exchange in such a way that isomers of an (83) has been studied ER*Ra-bridgedspecies are i n t e r c ~ n v e r t e d .Compound ~~~ by 13C n.m.r. spectroscopy and is static at -40 "C, with a spectrum which is consistent with the known structure. In the range -40 to +41 "C, the three CO resonances coalesce, possibly by a single averaging process. Compound (84) is static at room temperature. For (85), the spectrum is limiting at - 62 "C. Between -62 and 96 "C, a fluxional process occurs which scrambles the bridging CO groups and four of the six terminal CO groups. In this process, the bridging CO groups appear to be preferentially moving towards the iron atoms with which they have the shortest Fe-C bond.4Q313CN.m.r. spectroscopy has been used to show that the fluxionality of (86) consists of three processes. From - 65 to 8 "Cthere is a 'twitching' process in which the two enantiomorphous forms of the structure interconvert by the minimal movement of the Fe,(CO), group relative to the C,Hlo group without interchanging the two ends of the Fe,(CO), group. Simultaneously the three carbonyl groups on one of the iron atoms are scrambled among themselves. Above 8 "C the remaining two lines of intensity 1 : 2 coalesce to give a high-temperature 13C0 spectrum consisting of two lines.4Q4The 13C n.m.r. spectrum of the iron analogue of (80) shows that the eight-membered ring has four resonances at room temperature which collapse on cooling, but solubility prevented the observation of the limiting low-temperature ( < - 85 "C) spectrum. A 13CO-enriched sample showed six lines at - 120 "C, four lines of which collapse between - 120 and - 88 "C. From - 88 to - 55 "C, these four signals, plus one other, re-form into two signals of relative intensities 498 R. D. Adams, F. A. Cotton, W. R. Cullen, D. L. Hunter, and L. Mihichuk, Inorg. Chern.,

+

1975, 14, 1395.

4@3

494

J. P. Hickey, J. R. Wilkinson, and L. J. Todd, J . Organotnetallic Chem., 1975, 99, 281. F. A. Cotton, D. L. Hunter, and P. Lahuerta, J. Amer. Chein. SOC.,1975, 97, 1046.

Nuclear Magrtetic Resoriarice Spectroscopy

51 P 11

PI1

+

2 : 3. From ca. -50 to 102 "C, the signal of relative intensity 2 and the previously unbroadened signal of relative intensity 1 collapse and re-form as a signal of relative intensity 3. These changes were interpreted in terms of a 'twitching' process of the Fe,(CO), followed by local averaging in one Fe(CO), group followed by averaging in the other Fe(CO),. No gliding motion or internuclear exchange of thc CO group is allowed. By preparing the PEt, derivative it was shown that local scrambling occurs first around the allyl-bound iron a f o n ~ I. n~the ~ ~I3C n.1n.r. spectrum of (acenaphthalene)Fe,(CO),, the CO groups of the Fe(CO), scramble among themselves but do not exchange with those on the Fe(CO), group. In (cycloheptatriene)Fe,(CO), it is also believed that localized scrambling occurs in the (allyl)Fe(CO), The variable-temperature lSC n.ni.r. spectra of M,(CO)12 (M Fe, Ru, 0 s ) have been studied. Fe,(C0)12 and Ru3(C0),, give one sharp resonance down to - 100 "C. Os,(CO),, shows two resonances from - 100 "C to room temperature which coalesce to a single resonance at + 150 'C. Possible mechanisms for carbonyl averaging were considered. The l3C n.ni.r. spectra of the acetylenic complexes HM,(CO),C,But (M = Ru, 0 s ) were also examined and the compounds shown to be stereochemically non-rigid. Both the osmium and ruthenium compounds show axial-equatorial exchange on the metal atom which is cr-bonded to one of the acetylene carbon atoms. Only the ruthenium compound shows exchange between the metal atoms in the temperature range examined.497 13C N.m.r. spectroscopy shows (q5-C5H6)MFe,(CO), (M = Co, Rh) and (87) to be -7

495 WI

OQ7

3

F. A. Cotton and D. L. Hunter, J . Arncr. Chein. Soc., 1975, 97, 5739. F. A. Cotton, D. L. Hunter, and P. Lahuerta, Inorg. Chtw., 1975, 14, 511. S. Aime, 0. Gambino, L. Milone, E. Sappa, and E. Rosenberg, lnorg. Chim. Artrr, 1975, 15, 53.

52

Spectroscopic Properties of Iiiorguriic urrd Orgunometallic Conrpoirrills

0

fluxional but for (~5-C5H,)MFe,(CO), the process could not be stopped. However for (87), at -70 “C, a limiting spectrum was found with a triplet at 6 234.5 and two singlets at 6 190.0 and 6 193.3.4g813C N.m.r. spectra of the cluster complexes HOs,(CO),,(CH=CHR) have been used to show that the 0- and nbonds binding the bridging vinylic group are rapidly interchanged between the bridged osmium at on^^.^^^ Variable-temperature 13C n.1n.r. studies have shown that H,FeRu,(CO),, is undergoing intramolecular carbonyl exchange i n three distinguishable stages; the first localized at the iron atom, the second localized at the three ruthenium atoms, and the third over all the metal centres.6ooThree fluxional processes have been observed for the carbonyl groups in Os,(CO),,, (88).

Local carbonyl group scrambling occurs first at OsA, then at OSU,and finally at Osc, with AG* = 31, 53, and 61 kJ mol-l respectively.501 ‘13 N.m.r. spectroscopy has been used to show that the dithiocarbamate ligand is fluxional in MH(CO)(PPh3)S2CNR2( M = Ru, OS ).~ O13C ~ N.m.r. data and AGc“ for rotation about the C--N bond have been reported for both ions in (89).603 The addition of the shift reagent Eu(fod), to (.l5-C,H5)Fe(C0)(CN)L COC), Fe -C,,N M e,

0

4vn

1-

[H N : Me.] NMe,

+

J. A. S. Howell, T. W. Matheson, and M. J. Mays, J . Organometallic Chem., 1975, 88, 363. J. R. Shapley, S. I. Richter, M. Tachikawa, and J . B. Keister, J . Organoniefallic Cheni., 1975,

94, c43. L. Milone, S. Aime, E. W. Randall, and E. Rosenberg, J.C.S. Chem. Conitti., 1975, 452. w1 C. R. Eady, W. G. Jackson, B. F. G. Johnson, J. Lewis, and T. W. Matheson, J.C.S. Chefti. Conini., 1975, 958. P. €3. Critchlow and S. D. Robinson, J.C.S. Dalton, 1975, 1367. b 0 3 J. Schmetzer, J . Daub, and P. Fischer, Angcw. Clreni. Internat. Edn., 1975, 14, 487.

.so0

53 and to (T~-C,H,)N~(CN)(PP~,) produces downfield shifts, first-order lH and 13C n.1n.r. spectra, and allows the determination of conformational effects and rotational barriers. Evidence for preferred conformations in (y5-C,H,)Fe(CO)(CN)PMe,Ph and (qs-C,H6)Fe(CO)(CN)(PMe2Ph)resulting from rotation about the iron-phosphorus bond was presented. Conformations in which the phenyl rings are orientated adjacent to the (q5-C,H5) ligand appear to be favoured. Maximum barriers to rotation about the Fe-P and P-C bonds were estimated as 8.0 and 7.6 kcal mol-1 respectively. The mechanism of interconversion of right- and left-handed helices in the arylphosphine complexes was discussed and a number of possible pathways were proposed.601 The Tl and T2relaxation times for the methyl protons in tetra-p-tolylporphyrin iron halides have been determined by 'H 1i.m.r. spectroscopy; the Tl : T2ratio for the chloride agreeing with the value predicted by the calculated correlation time. The Tl relaxation was due to dipolar coupling, which was determined by niodulation of the zero-field levels by tumbling of the complex in solution. Proton broadening for certain porphyrin protons by a T2 process reflected the motion of the iron relative to the haein plane, the non-equivalent sides of the molecule being averaged by movement of the iron from side to side through the porphyrin ni01ecule.~~~ At low temperatures, the 31P n.1n.r. spectrum of Fe{P(oR),}, is A2B3, which exchanges on warming, and for R = Me, A H * = 8.6 kcal mol-l and A S * = - 1.5 cal K-l MX2(PPh3), ( M = Ru, 0 s ; X = CI, Br) are square-pyramidal in solution, but undergo an intraniolecular rearrangement which equilibrates the two phosphorus environments. The rearrangement barrier is higher for osmium than ruthenium, and the barrier for the brorno-complex is larger than that of the chloro-analogue. RuCI,(PPh,), is completely dissociated to RuCI,(PPh,), and PPh, in solution and even RuCI2(PPh3), partially dissociates, forming [ RuCI,(PPh,),],. OsX,(PPh,), does not exhibit detectable phosphine dissociation. KuHCI(PPh,), but not RuH(O,CMe)(PPh,) undergoes intramolecular exchange. For RuCI,(PPh,),, A H * = 10.0 kcal mol-l and A S * = 0.9 cal K-l [F~(NO)(O-(M~,AS),C,H,),~~ [ClOJ- is fluxional, showing two methyl groups at room temperature which coalesce o n heating with an activation energy of 12.6 kcal mo1-1.608 Co, Rh, and Ir. IH and 31P n.1n.r. spectroscopies have been used to show that [MeNi(PMe,),]+ is MXL { M = Rh, Ir; L = P[(CH2)nCH=CH2]3, n = 2,3} have been shown to be fluxional due to exchange of bonded and nonbonded olefins.610 (~~-tcne)(RNC)~Rh(acac) have teniperature-dependent 'H n.m.r. spectra which have been interpreted in terms of rotation of tcne around the rhodium-tcne bond accompanying Berry pseudorotation in a trigonal bipyramid."l The temperature-dependent virtual coupling of the POMe 'H n.m .r. signal of [Rh(RCN),( PPh(0 Me),},(y2-fumaronitrile)]+[CIOa]- has been Nircleor- Mognetic Resonance Spectroscopy

J. W. Faller and B. V. Johnson, J . Organometallic Chem., 1975, 96, 99. G. N. La Mar, Pitre A p p f . Chem., 1974, 40, 13. P. Meakin, A. D. English, S. D. Ittel, and J. P. Jesson, J . Amer. Chem. Soc., 1975, 97, 1254. P. R. Hoffman and K. G. Caulton, J. Amer. Chem. Soc., 1975, 97, 4221. T. E. Nappier, R. D. Feltham, J. D. Enemark, A. Kruse, and M. Cooke, Inorg. Chem., 1975, 14, 806.

610

H.-F. Klein and H. H. Karsch, Chem. Ber., 1975, 108, 944. P. W. Clark and G . E. Hartwell, J. Organometallic C h ~ m . 1975, . 97, 117. T. Kaneshima, K. Kawakami, and T. Tanaka, Inorg. Chim. A d a , 1975, 15, 161.

54

Spectroscopic Properties of Inorgnnic and Organometallic Compounds

interpreted as a gradual change of the interaction between fumaronitrile and rhodium with lowering temperature. The temperature dependence of the 'H n.m.r. signals of the fumaronitrile protons of Rh(RNC)2(P(OPh)3}(q2-fumaronitri1e)I at low temperature was interpreted in terms of a restricted rotation of fumaronitrile in a time-averaged square pyramid. At higher temperature both ~ ~ ~ acetylene compounds undergo dissociative exchange of f u n i a r ~ n i t r i l e . The ligand of (q2-PhC=CPh)(q5-C5H5)3Rh3(CO)is fluxional in solution at room temperature but is static at - 87 "C whereas the acetylene ligand of (q2-PhC=CPh)(+C6H,),Rh3 is fluxional even at - 127 "C. The acetylenic carbon signal is very deshielded, and the possibility of carbenoid-type bonding for this ligand was suggested. According to 13C n.m.r. evidence the compound [(qK-C5H,)Rh(+PhC=CPh)], does not have a metallocyclopentadiene structure but an unsymmetrical C4 ligand. The complex [(q5-C5H6)Rh(CO)]2(r]2-CF3C=CCF3 possesses a static bridging acetylene ligand. However, the CO groups appear to be scrambling at room temperature but are static at - 6 0 0C.513 (~ - ~ - T ~ - C ~ H ~ ) C O ( C O and )~P ( I P,2,5,6,7-q5-C8HO)(q4-C8H8)Co ~~ exhibit, in solution, interconversion of their enantiomorphous structures generated by the asymmetric ring-Co bonds. This stereochemical non-rigid behaviour was studied by means of the lH n.m.r. Forskn-Hoffman double-resonance method for evaluating the activation parameters of the interconversion Similarly, 13Cn.m.r. has been used to show that (90) is fluxional, giving a limiting

high-temperature spectrum at 319 K ; on cooling to 259 K the signals corresponding to carbons -1, -5, -2, and -4 'H N.m.r. spectroscopy has been used to show that YCCo3(CO),(q4-norbornadiene) compounds are nonrigid in Site exchange between the single bridging and terminal CO groups in (q5-C6H5)2Rh,(CO),{P(OPh),} has been observed by 13Cn.m.r. spectroscopy. A synchronous mechanism was Variable-temperature i.r. and 'H, 13C, and 31P n.m.r. spectra of some phosphine-substituted methinyl Co,(CO), complexes have been described and interpreted in terms of isomer distribution and intramolecular carbonyl scrambling. Only in the case of the MeCCo,(C0),jP(C6H,,),) complex was it possible to freeze out scrambling at 188 K, and hG* = 41.2 kJ mo1.618 The 13C n.m.r. spectrum of (91 ; R = MeO,C, Ph) shows three 61s

b14 616

b16 617

b18

K. Kawakami, K. Takeuchi. and T. Tanaka, Inorg. Chem., 1975, 14, 877. L. J. Todd, J. R. Wilkinson, M. D . Rausch, S. A. Gardner, and R. S. Dickson, J . Organometallic Chem., 1975, 101, 133. P. V. Rinze, J. Organometallic Chem., 1975, 90, 343. J. Miiller, H . - 0 . Stuhler, and W. Goll, Chem. Ber., 1975, 108, 1074. P. A. Elder, B. H. Robinson, and J. Simpson, J.C.S. Dalton, 1975, 1771. J. Evans, B. F. G . Johnson, J. Lewis, and T. W. Matheson, J.C.S. Cheni. Comm., 1975, 576. T. W. Matheson and B. H. Robinson, J. Organometallic Chem., 1975, 88, 367.

Nuclear Magnetic Resonance Spectroscopy

55

CO resonances at - 9 0 "C, but above -70 "C there is scrambling over all the cobalt atoms. Below -60 "C, three resonances were observed for C O , ( C O ) , , . ~13C ~ ~ N.m.r. studies on the three structurally related carbonyl clusters Rhe(CO)le, [Rh6(C0),,]2-, and [Rh7(C0)16]3-show that Rhs(CO)16is not fluxional at 70 "C, [Rh,(C0)l,]2- readily undergoes intra-carbonyl exchange at - 70 "C, and [Rh,(C0),6]3- is not fluxional at - 70 "C but undergoes partial intra-exchange at 25 0C.520 The 'H n.m.r. spectrum of Co{o-(Me2As),C,H,},(NO) shows two methyl signals at 22 "C which coalesce at 51 "C with an activation energy of 7.5 kcal mol-1.621 The lH n.m.r. spectrum o f {o-C6H,(PPh2)(CH2NMe,)}RhCl(C0) shows two methyl signals at - 36 "C which collapse to a single resonance at 0.5 "C with an activation energy of 8.8 kcal mo1-1.52231P N.m.r. spectroscopy has been used to show that [Ir{Ph2P(CH2)3PPh2}3CO]+C1-and related compounds are fluxional at room temperature but freeze out on cooling, with the CO group equatorial. Activation parameters were determined. Similarly it was found that [Ir{Ph,P(CH,)3PPh,}2HCl]fPFB- is fluxional.622" 'H N.m.r. spectroscopy has been used to show that Ir(NO)(PPh3)(N,{MeC,H,SO,-p),) is fluxional; two methyl signals were obtained at low temperature and one at room temperature; AH* = 8.74 k 0.87 kcal mol-I. and A S * = - 19.7 k 9.5 cal K-' inol-1 were estimated. Unfortunately the rate plot appears to be dominated by the least accurate extreme values, and AH* may be badly ~ n d e r e s t i m a t e d . ~ ~ ~ Ni, Pd, and Pt. Compound (84) is fluxional, with the CH2 group a singlet with lesPt satellites at 40 "C, but AB with lsSPt satellites at -20 "C. This behaviour was attributed to slow inversion of the six-membered ring with AC300' = 15.3 f 'H, 13C, and l*F n.m.r. 0.2 kcal mol-l. 31PN.m.r. spectra were also

+

+

J. Evans, B. F. G . Johnson, J . Lewis, and T. W. Matheson, J . Amrr. Chem. SOC.,1975, 97, 1245. K s o B. T. Heaton, A. D. C. Towl, P. Chini, A. Fumagalli, D. J . A. McCaffrey, and S. Martinengo, J.C.S. Chem. Conitii., 1975, 523. rc* J . H. Enemark, R. D. Feltham, J . Riker-Nappier, and K. F. Bizot, Znorg. Chem., 1975, 14, 624. 623 T. B. Rauchfuss, F. T. Patino, and D. M. Roundhill, Znorg. Chem., 1975, 14, 652. 6 p 3 J . S . Miller and K. G . Caulton, J . Amer. Chem. SOC.,1975, 97, 1067. ~ 2 4S. Cenini, P. Fantucci, M. Pizzotti, and G. La Monica, Znorg. Chim. Acta, 1975, 13, 243. 626 R. ROS,J. Renaud, and R. Roulet, J. Organorzietallic Chetn., 1975, 87, 379.

56

Spectroscopic Properties of Inorganic aiid Organonietullic Comporrrtds

spectroscopies have been used to show fluxional behaviour for (q2-C0H4)2(q2-C2F4)Pt, (norbornadiene),Pt, and (~2-CzH4)2PtP(cyclohexyl),."2G The 'H n.m.r. spectrum of (cyclo-octadiene),NiLi2,4THF is temperature-dependent. At -40 "C, signals due to free and co-ordinated double bonds were observed.s27 'H N.m.r. spectroscopy has been used to show that two conformers exist for (q3-C3H5)2Pd2(pArNCHNAr)2 which interconvert at ca. 100 0C.52R Compounds (92; R = Me, CF,) are fluxional, as shown by lH and 13C n.m.r. spectroscopies,

(acac) (93)

and A H * and A S * were determined.529 'H and 13C n.m.r. spectroscopies have been used to show that three separate fluxional processes occur for (93; M = Pd, Pt). The lowest energy process, where the metal hops from one side to the other of one benzene ring, could not be stopped. The intermediate energy process is where the metal migrates from one ring to another, and the highest energy process involves the exchange of the acetylacetonate methyl groups.SSo The low-temperature 'H n.m.r. spectrum of [(~3-C3H,)Pt(P(cyclohexyl)3)~] [PFJ- shows that the two syn protons of the ally1 group are non-equivalent. This behaviour was attributed to the restricted rotation of the platinumphosphorus 'H N.m.r. spectroscopy has been used to show that for [(dppe)Pt(+2-niethylallyl)]+ the addition of neutral bases leads to s y n - m i exchange but the effectiveness of conversion to a dynamic system is a function of nucleophilicity towards platinum(1r). Good nucleophiles such as PMePh, give stable 1:l adducts which are dynamic in solution at room temperature and appear to have a ql-allyl structure at low temperatures. A mechanism was proposed to account for the base-induced f l ~ x i o n a l i t y .The ~ ~ ~'H n.m.r. spectrum of (q4-norbornadiene)Pt(q1-C,Hs)2indicates that the cyclopentadienyl rings are a-bonded to platinum and that they display fluxional behaviour in solution, but with an activation energy too low to permit 'freezing out' at accessible teniperatures. A H * was estimated to be 2.2 kcal mol-1 and A S * to be - 3 1 12 cal K-I r n 0 1 - I . ~ ~ ~ +

*

sL6

M . Green, J . A. K. Howard, J . L. Spencer, and F. G . A. Stone, J.C.S. C'hcnr. Conitti., 1975, 449.

GJ1 632

G33

K. Jonas, Angew. Chem. Internat. Ecln., 1975, 14, 752. L. Toniolo, T. Boschi, and G . Deganello, J . OrganonretaNic Chcnr., 1975, 93, 405. A. Sonoda, B. E. Mann, and P. M . Maitlis, J . Organonietallir Chem., 1975, 96, C16. A . Sonoda, H. E. Mann, and P. M. Maitlis, J.C.S. Chenr. Comm., 1975, 108. T. G. Attig and H . C. Clark, J . Or~anomrtallicChem., 1975, 94, C49. H . C. Clark and C. K. Jablonski, Innrg. Chent.. 1975, 14, 1518. M. N.S. Hill, B. F. G. Johnson, T. Keating, and J. Lewis, J.C.S. Dalton, 1975, 1197.

Niiclear Magnetic Resonance Spectroscopy

57

For (94), the lH n.m.r. spectrum at low temperatures shows signals in the ratio 27 : 27.9. There are two exchange processes: at 60 "C, bridge-terminal and at lower temperatures terminal-terminal ButNC groups, i.e. at low temperatures the bridge changes faces and then bridge-terminal exchange occurs.534 At - 30 "C, [Pd2(CNMe)J2+shows two methyl signals in the ratio 2 : 1, which at higher temperatures coalesce, apparently via an intramolecular process.635 Variable-temperature IH n.m.r. data have been presented for the square-planar nickel(rr) complexes {Me,M(pz),}Ni (M = B, Ga), and stereochemical nonrigidity for the molecules in solution was invoked to account for the spectral changes observed. The activation energies obtained for the interconversion processes are 46 (M = Ga) and 67 kJ mol-' (M = B).636lH and 13C n.m.r. spectra of trans-PtCl,(diarylsulphurdi-imine)L (L = group V or VI donor ligand) have shown that in solution, in general, only one isomer is formed in which the diarylsulphurdi-imine is very likely in the rrans,rrans-form and co-ordinated to the metal atom via one of the nitrogen atoms. Both intramolecular movements and intramolecular exchange reactions of the sulphurdi-imine ligands were observed. The intramolecular movements involve an N-N migration via a five-co-ordinate intermediate. The rate of this migration is dependent on the type of ligand L and on the aryl ~ u b s t i t u e n t s . ~ ~ ~ Temperature-dependent n.m.r. spectra for the complexes [Ni(edta)12-, [Ni{02CCH2NMeCH2CH2N(CH2C02)2}]-,Ni(edda), [Ni{HN(CH2C0,)2}2]z-, and [Ni(l ,3-pdta)I2- have been reported. Raceniization of [Ni(edta)12- is rapid on the n.m.r. time-scale at 80 "C and of [Ni(l,3-pdta)12- is rapid at 78 "C but racemization is slow up to 105 "C for all other complexes. Activation energies for racemization are AGedh* (80 "C) = 14.2 kcal mol-1 and AGl,spdta* (78 "C) = 14 kcal niolkl. The data were interpreted as indicating predominantly five-co-ordinate edta and 1,3-pdta in nickel(I1) complexes. On the basis of studies of racemization of [Ni(edta)I2- a racemization mechanism similar to the baseracemization of [Co(edta)]- was proposed. In this mechanism a sevenco-ordinate intermediate was proposed. The failure to observe certain peaks in the contact shift spectra of various [Ni(edta)12- type ligands was explained on the basis of kinetic broadening due to rapid attachment and detachment of the free carboxylate of the edta-type ligands. The rate of racemization of [Ni(edta)12634

m5 5:1fl L.17

V. W. Day, R. 0. Day, J. S. Kristoff, F. J. Hirsekorn, and E. L. Muetterties, J . Amer. Chem. SOC.,1975, 97, 2571. D. J . Doonan, A. L. Balch, S. Z. Goldberg, R. Eisenberg, and J. S. Miller, J . Anter. Chem. Soc., 1975, Y7, 1961. F. G . Herring, D. J . I'atrnore, and A. Storr, J.C.S. Dulton, 1975, 711. J . Kuyper and K . Vrieze, J . Otganot?iclullic Chrtn., 1975, 86, 127.

58

Spectroscopic Properties of Inorganic and Organometallic Compounds

is independent of p H from p H 4 to 12. cis-trans Isomerism of [Ni{(O,CCH,),NH),I2- is fast at 48 "C [AG* (48 "C) = ca. 14 kcal mol-'1, implying a rapid twist mechanism which does not lead t o r a c e m i ~ a t i o n . The ~ ~ ~ dynamic stereochemistry of [PhMe,PPd(O,CR1)(O,CR2)1, has been investigated using variabletemperature 'H n.m.r. spectroscopy. Exchange of the stereochemically nonequivalent methyl groups of the co-ordinated PMe,Ph ligand occurs ria a solventassisted process involving ring opening of the Pd(O,CR), bridged structure. For the [CF3C0,]- solution, equilibria between monomer and dimer are readily apparent at low temperature in the 19F n.m.r. spectra. The observed equilibrium constants are a function of solvent and the size of the PR, ligand. A quantitative measure of the ability of a co-ordinated carboxylate t o stabilize intermediate species was obtained from a variable-temperature n.m.r. study of (~~-2-Me-allyl)Pd(OzCR)PMe2Ph.53BVariable-temperature n.m.r. spectra of [MLX]+ [M = Ni, indicate that both Pd, Pt ; L = Me,As(CH,),AsPhCH,CH,AsPh(CH,),AsMe,] axial site interchange and intermolecular exchange can occur by three different bimolecular mechanisms which involve halogen attack of the metal as well as attack by either four- or five-co-ordinate complexes resulting in the formation of d i m e r ~ .At ~ ~ca. ~ 1OO"C, exchange of the N-CH, groups occurs for cis( B u ~ ~ N C S , ) ~ P ~with I , , A H * = 7.2 kcal niol-' and A S * = - 37 cal K-l moI-l. Similar behaviour was found for cis-(MeBzNCS,),PtI,. The experimental data were explained by assuming a slow exchange process up t o 100 "C, then a fast racemization process in which a heteropolar breaking of a Pt-L bond is involved. The isonierization of trans- into cis-(Bu",NCS,),PtI, was also examined, with A H * = 17.2 kcal niol-' and A S * = - 17 cal K-l mol-l. An ionic intermediate was suggested."I Similarly the IH n.m.r. spectrum of (Me,SCH,)Pd(PPh,)(S,CNMe,) shows restricted rotation about the S,C-NMe, bond.542 The lH n,m.r. spectra o f mixtures of trans-(Et,S),PdX, and Et,S show concentrationindependent coalescences at low temperatures which were assigncd t o inversion at sulphur and high-teniperature concentration-dependent coalescences which were assigned to ligand-exchange processes. Similar exchange processes were found in the related selenide and telluride complexes.543 Cu, Ag, and Au. Fluxional poly(pyrazoly1)borate complexes of copper and silver, including Cu(CO)B(pz),, contain co-ordinated and free pyrazolyl groups which interchange rapidly on the 'H n.m.r. time-scale at room temperature. Low-temperature limiting spectra were obtained for some of the copper complexes a t - 100 0C.644 HB(pz),AuCl, is also fluxional but a limiting 'H n.m.r. spectrum is achieved by -20 0C.645 Hg. The 13C n.m.r. spectra of (q1-C5H,)HgCI and (7*-C9H7),Hg have bcen recorded over a temperature range of - 122 to 22 "C. A comparison of the two b3D 640

b42

64s

D. S. Everhart and R. F. Evilia, Inorg. Chem., 1975, 14, 2755. T. R. Jack and J. Powell, Crrtiarl. J . Chcm., 1975, 53,2558. B. Bosnich, W. G . Jackson, and S. T. D. Lo, Inorg. Chetti., 1975, 14, 2998. J. Willernse, F. W. Pijpers, and J . J. M . Backus, Rcc. Trm. chitri., 1975, 94, 185. G. Yoshida, Y . Matsumura, and R . Okawara, J . Organoriietallic Cheni., 1975, 92, C53. R. J. Cross, T. H. Green, R. Keat, arid J. F. Paterson, Inorg. Nuclear Chcni. Lcttcrs, 1975, 11, 145. 0. M. A. Salah and M . I. Bruce, J . Organonictallic Chetw, 1975, 87, C15. N. F. Borkett and M. I. Bruce, Inorg. Chim. Ac,ta, 1975, 12, L33.

Nuclear Magnetic Resonance Spectroscopy 59 low-temperature limiting spectra indicates that ( T ~ - C ~ H , ) H ~rearranges CI uin 1,2-shifts. The activation energy for this rearrangement was found to be 7.7 k 0.7 kcalmol-l. The 13C n.m.r. spectrum of (+C,H,),Hg was also examined, but only a slight line broadening was found at - 120 0C.546 lH N.m.r. spectroscopy has been used to determine E,, A H * , and A S * for Me,ClSi exchange by a second-order process on (Me,SiCl)2Hg.547

B, Al, and TI. Variable-temperature 'H and llB n.m.r. spectra of (95) have been examined. At -20 "C one type of hydrogen is observed but at - 100 "C, a

limiting low-temperature spectrum was found. At - 90 "C the IlB signals due to B1 and B3 are separate but they coalesce to give one signal at -20 "C whereas Bz and B4 are equivalent. For B5HI2,at all teniperatures, two llB signals are observed in the ratio I : 4. At - 5 6 "C the 'H n.m.r. spectruni is a singlet but at - 135 "C three separate signals are observed. For [BBHI1]-the lH n.ii1.r. spectrum is frozen at -25 "C and the l l B n.m r. spectrum at -80 0C.518The IlB n.1n.r. spectrum of B-Me isomers of CB5H7shows a fast bridge-hydrogen tautomerism at ca. 100 0C.549 The 'H n.ni.r. spectrum of Buiz(ButCH=CBut)Al shows two CH signals at - 16 "C and one at 70 "C. Similar behaviour was found for related C O ~ ~ O U ~ ~ Studies S . " ~ of kinetic and activation parameters have been made for intramolecular bridge-terminal exchange for dimers of Me3AI, (p-tol),Al, and (m-tol),AI. The data indicate that the first of these reactions proceeds via a dissociative mechanism, as proposed earlier, but the latter two most likely proceed via a mechanism involving only a partial dissociation of the electron-deficient bridge. This conclusion is supported by the unusually low activation energies of 9.7 i- 1.0 and 8.0 k 1.0 kcal mol-1 respectively as well as negative entropies. The reaction which occurs between Me,AI and Me,Al,(p-tol), to form Me,(p-tol)Al, appears to proceed via a similar mechanism, with a partial dissociation of the tolyl bridges in Me4(p-tol),Al,. The activation parameters are Ea = 11.1 k 1.0 kcal mol-l and A S * = - 11 e.u.551 Variable-temperature lH and l9F 1i.ni.r. spectra of TI(OAc),, TI(OAc), and TI(O,CCF,), have been reported. TI(0Ac) is a singlet at room temperature and a doublet at - 110 0C.652 A total lineshape analysis of exchange-broadened 'H n.1ii.r. spectra for F. A. Cotton, D. L. Hunter, and J. D. Jamerson, fnorg. Chim. Actn, 1975, 15, 245. T. F. Schaaf, R . K . Kao, and J . P. Oliver, Inorg. Chem., 1975, 14, 2288, 6 4 8 R . J. Remmel. H. D. Johnson, jun., 1. S. Jaworiwsky, and S. G . Shore, J . Anicr. C'hetn. Soc., 1975,97, 5395. 6 4 8 J. B. Leach, G. Oates, S. Tang, and T. Onak, J.C.S. Dalton, 1975, 1018. lrSu J. J. Eisch and S. G . Rhee, J . Organonictnllic Cfwtii., 1975, 86, 143. 8 6 1 T. B. Stanford, jun. and K. L. Henold, Inorg. Chem., 1975, 14, 2426. W . R. J. Abraham, G. E. Hawkes, and K. M. Smith, Tetrahedron Letters, 1975, 1999. 547

60

Speclroscopic Proptv-ties of Inorganic and Organonietnllic Compounds

TI(S2CNMe2), has been carried out. The coalescence of the methyl doublet results from a first-order dissociative ligand-exchange reaction, with A H * = 6.2 k 1.0 kcal mol-' and A S * = -28 k 10 e.u.553

Si, Ge, and Sn. The temperature dependence of lineshapes and line intensities of the 'H and 13C n.m.r. spectra of (Me3S&C5H3 and its deuteriated analogue have been used to demonstrate that both metallotropic and prototropic intramolecular rearrangements occur in these compounds. Four possible migration routes were considered. It was shown that the temperature dependence of the 'H and 13C n.ni.r. spectra may be explained only in terms of four successive 1,2-shifts of the metal. Lineshape analysis was also performed on lH{?H}n.ni.r. spectra. The effect of introduction of organometallic groups in the cyclopentadiene ring on the metallotropic rearrangement was discussed. An attempt was made to extend the concept of relative migratory ability of metals so as to include cyclopentadienyl l i g a n d ~ .The ~ ~ ~fluxional molecules (Me,Si),( Me,,Sn)indene, (Me:,Si)(Me,Sn)indene, and (Me,Sn),indene have been studied by IH n.m.r. spectroscopy and the Arrhenius parameters for metallotropic shift of the Me,Si groups have been determined. Although in the case of (Me,,Sn),indene the abundances of the two fluxional isomers were grossly dissimilar (ratio > 20 : l), the very sensitive temperature dependence of the spectra enabled accurate rate parameters to be deduced. The spectral lineshape changes in all were found to be completely compatible with 1,3-metallotropic shifts of the Me,Sn group.555 The fluxional rearrangements and isomerizat ion reactions of a series of methyl-substituted indenyl derivatives of Si and Sn have been examined. Methyl substitution at C-4 and C-7 on the six-membered ring was found to lower the activation energies for both processes, whereas methyl substitution at C-2 on the five-membered ring raised the activation energies relative to the unsubstituted derivatives. The variation in free energies of activation, based on substituent position, occurs in a manner parallel to that predicted from consideration of the n-electron densities in the indenyl group.556 The lH and 13C n.m.r. spectra of (96) show two o-cyclopentadienyl resonances at 40 "C which exchange with AE* = 12.2 kcal m ~ l - ' . ~ The ~ ' stereochemistry of PhCIM(acac), (M = Si, Ge), Ph,Ge(acac),, and MeCISi(acac), complexes has been investigated by lH n.m.r. spectroscopy. The phenylchloro-complexes adopt predominantly a cis-(Ph, CI)

66s 664

65 5

667

H. Abrahamson, J . R . Heiman, and L. H . Pignolet, Inorg. Chem., 1975, 14, 2070. Yu. A. Ustynyuk, Yu. N. Luzikov, V. I. Mstislavsky, A. A. Azizov, and I . M . I'ribytkova, J . Org~itionicftrllicChcm., 1975, 96, 335. K . G . Orrell, V. Sik, M . 0. Dunster, and E. W. Abel, J.C.S. Furtrrfuy I / , 1975, 71, 631. M . N. Andrcws, P. E. Rakita, and G. A. Taylor, Itiorg. Cliint. Acttr, 1975, 13, 191. W. Z . M . Khee and J . J . Zuckerman, J . A t n ~ r .Cheni. SOC.,1975, 97, 2291.

Nuclear Magnetic Kesonunce Spectroscopy 61 structure in solution and the MeClSi(acac), is cis-(Me, C1) in solution. Environmental averaging of the acetylacetonate ring protons in the cis-phenylchlorocomplexes has been studied by total line-broadening techniques. Activation parameters are for PhClGe(acac),, Ea = 12.8 & 1.2 kcal mol-l, AS = - 13 rt 4 e.u., and for PhClSi(acac),, Ea = 6.4 f 1.0 kcal mol-l and A S * = -22 k 5 e.u.668 Similar investigations have been carried out for cis-MeClGe(acac),, with A S * = - 30 _+ 1 e.u. and k = 1.6 x lo2 mol-1 1 s-l. It was thought that the rearrangements go via a five-co-ordinate intermediate resulting from a germanium-oxygen bond The potential barrier to rotation of (ClSiMe,CH,),NCOCI is 8.9 _+ 1 . 3 kcal mol-l, with an Arrhenius frequency factor of lo6 s - ’ . ~ ~ O The 13C n.m.r. spectrum of (97) shows exchange of Me,Si groups with AG* = 16.9 kcal mo1-1.661 A method of using the l17/l19Snsatellites in the lH n.m.r. spectrum of 2,2-disubstituted 1,3,2-dithiastannolans has been

*

(97)

proposed to overcome the difficulties in the conformational analysis arising from rapid interconversion, with A H * = 6.26 kJ mo1-1.662 Variable-temperature ‘H n.m.r. spectra of [(Me,N),Sn], (98), and the cisisomer, indicate exchange of the Me,N groups between the bridge and terminal ’H N.ni.r. spectra and AG* have been determined for C-N bond rotation and N-S migration of the SiMe, group in MeC(S)NRSiMe,.564 ‘H and lQFn.1n.r. spectroscopies have been used to show hindered rotation of the nitrogen-phosphorus bond in P(CF&N(SiMe,),, which has AG* = 15.3 kcal niol-l, while for P(CF,),N(SiMe3)But, A G * = 20.8 kcal mol-I and is large enough for two rotamers to be observed at room t e m p e r a t ~ r e . ” ~Free energies of activation for rotation about the carbon-nitrogen bond in R1,MSC(O)NRZ2(M = Ge, P, As) have also been determined.66s lH N.ni.r. spectra of substituted cyclotrisilazanes have been discussed in terms of conformational analysis. Experimental spectra were consistent with a n equilibrium involving chair conformers, following simulation of the effect of phenjl substituents and the temperature dependence of the methyl lH chemical shifts. The barrier to chair-chair interconversion in (Me,SiNH), was estimated as 3.5-4.0 kcal m01-1.667 hhn G5u

GRZ

5H5 hHM

6ti7

N. Serpone and K. A. Hersh, J . Organonietallic Chem., 1975, 84, 177. K . A. Hersh and N. Scrpone, Canacl. J . Chem., 1975, 53, 448. Y u . A. Strelenko, A. V. Kisin, V. D. Sheludyakov, E. S. Rodionov, and N. V. Aleksecv,

Zhur. srrukt. Kliim., 1974, 15, 935. M . T. Reetz, G . Neurneier, and M. Kaschube, Tetrahedron Letters, 1975, 1295. B. Mathiasch, Z. anorg. Chem., 1975, 412, 71. P. Foley and M. Zeldin, Inorg. Chem., 1975, 14, 2264. W. Walter and H.-W. Luke, Angew. Chrm. Intcvnrit. Edn.. 1975. 14, 427. R. H . Neilson, R . Chung-Yi Lee, and A . fl. Cowlev, .I. Amrr. C h ~ t nSor., . 1975, 97, 5302. W. S. Moore and C. H . Yoder, J . Orgnnotricftillir~C ’ h c i u . , 1975. 87, 389. U. D. Lavrukhin, I(. A. Andrianov, and E. I . Fedin, 01-g.Magn. Resoncmce, 1975, 7, 298.

62

Spectroscopic Properties of Inorganic and Organonietullic Cornpoiitids

The leF n.m.r. spectrum of Sn(hfac), is a singlet at room temperature which splits into four signals at -40 "C.568 P, As, and Sb. Direct measurements at 183 K of the conformers of cis-4-methylcyclohexylphosphine and its PMe, and PCI, derivatives by n.ni.r. spectroscopy and comparison of the averaged 31P shifts at 300K with the shifts for tert-butylhexyl compounds have been used to determine the conformational free energies for phosphorus 1-R-Phosphorinans (99; R = Me,

(9%

Et, Pri, Ph) give a single 31Pn.ni.r. signal at 300 K , but on lowering the temperature separate signals for the axial-R (upfield) and equatorial-R conformers developed. From the variation of the equilibrium constant with temperaturc, AH" values were derived in the range -0.6 to -0.7 kcal n i ~ l - ~revealing , that repulsive non-bonded interactions are considerably smaller than those for similar substituents on the cyclohexane ring. AG* for inversion is 8.3 to 9.3 kcal mol-l.KiO The l H n.m.r. spectrum of MeZAs(q*-CsH5)shows a marked temperature dependence over the range - 1 to + 30 *C,consistent with a sigmatropic rea~rangement."~ Some monocyclopentadienyl stilbenes have been synthesized and found to be fluxional.s77"Rotational barriers have been derived for hindered rotation of acyl-phosphines and - a r ~ i n e s , ~and ' ~ restricted rotation has been found for the C-CHO bond in (loo)."'" The lH and 13Cn.m.r. spectra

Me0

OMc

(100)

of Me,AsOMe shows only one MeAs signal at room temperature but two at The 'H n.m.r. - 100 "C in the ratio 1 : 3, confirming an axial OMe spectra of R,As(OMe),-, (R = Me, Ph; n = 0-3) have been examined down to -100 "C and the results interpreted in terms of pseudorotation processes among structures with trigonal-bipyramidal geoinetries. Ph,As(OMe), was the only compound which showed non-equivalence of the M e 0 groups at low temperat u r e ~ . ~ ~ ~ Lao 670

A. B. Cornwell and P. G . Harrison, J.C.S. Dalton, 1975, 1722. M. D. Gordon and L. D. Quin, J.C.S. Cfzeni. Cot?it?i.,1975, 35.

S. 1. Featherman and L. D. Quin, J . Anwr. Chem. Soc., 1975. 97, 4349. J. Lorberth, J . Organoriictallic Cfieni., 1975, 92, 181. P. Jutzi. M. Kuhn, and F. Herzog, Cfiem. Bcr., 1975, 108, 2439. R. G . Kostyanovskii, Yu. I. El'natanov, K . S. Zakharov, and L. M. Zagurskaya, DoAIudy Akad. Nauk S.S.S.R., 1974, 219, 137. H. H. Pohl and K. Dirnroth, Arigcw. Cficui. Infernat. Edn., 1975, 97, 1 1 1. H. Schmidbaur and W. Richter, Angew. Cfiem. Internat. Edn., 1975, 97, 183. A. J. Dale and P. Freyen, Acta Client. Scarid. ( B ) , 1975, 29, 362.

~.n P. Kronimes and 672

673 674 676

670

Nuclear Magnetic Resonance Spectroscopy

63

lH and 31Pn.m.r. spectroscopies have becn used to show that (101) and related conipounds are dynamic.577 Rut,NPX, (X = F, CI, Br) show restricted rotation about the N - P bond, and AGTc* values were d e r i ~ e d . " ~The 19Fn.ni.r. spectra of RPF,=NC(CF,),N=C(CF,), and RPF,N=C(CF,), show an intermediate

,N-N..

N Mc, (101)

But,

'But

(102)

rate of intramolecular exchange at phosphorus but an apparently fast isomerism at nitr~gen."~For R1R2R3P=NR4, 'H and 31P n.ni.r. spectroscopies have been used to show that the rotational barrier around the P-N bond is below 8 kcal mol-1,G8s0 for (102) the N-But groups coalesce, with AG,* =

1 1.7 kcal mo1-1,G81and intramolecular exchange occurs for F,(Me,P)P-OC(CF,),I

C(CF3)20.K*a A series of 35 monoalkoxyfluorophosphoranes, R1PF30R2,have a dynamic trigonal-bipyramidal structure i n which the exchange of fluorine atoms between apical and equatorial sites is r a ~ i d . ~Pr*,NPF, *~ is also fluxional, and at - 110 "C axial-equatorial fluorine exchange and rotation about the N-C bond are frozen out.584 Dynamic n.m.r. spectra of pentakis(chloroniethy1)cyclopenta-arsine have been interpreted as a combination of low-energy pseudoThe rotational motion and a higher energy arsenic atom inversion conformations and rotational barrier of RAsECR1R2CR3R4E(E = 0, S) have been determined by IH 1i.m.r. spectroscopy.586 The lH n.1n.r. spectrum of Me,NAsNMeCH,CH,O is very sensitive to solvent and temperature. A complete analysis of the spectrum at - 4 8 "C in [eH8]toluene shows that the molecule exists in a preferred conformation in the C-4-C-5 region. The spectrum, corresponding to an A2X2 system in nitrobenzene at +31 "C, indicates free movement around the bond. At higher temperature a new coalescence phenomenon was explained by inversion of the As atom.587 S, Se, and Te. The energetics of ring inversion in E(CH,CH,),O (E = 0, S, Se, Te) have bccn determined, but must be considered to be suspect as A S * = cti. - (50-70) J K-' mol-l,588and AG' has been estimated for the interchange of conformers of ((m-c,, H ,)(CH,),),Se.58g Variable-temperature H n.ii1.r. 677 67n 678

m1 6~

m3 684 6Hs

D. Bernard and R. Burgada. Tetrcrherlron, 1975, 31, 797. 0. J. Scherer and N. Kuhn, Chrrn. Bcr., 1975, 108, 2478. J . A. Gibson and I t . Schrnutzler. Z.anorg. Chrm., 1975, 416, 222. H. Goldwhite, P. Gyscgem, S. Schow, and C. Swykc, J.C.S. Dalton, 1975. 12. I{. Quast, M. lieuschmann, and M. 0. Abdel-Rahman, Angew. Chem. Internat. Edn., 1975, 97, 486. J. A. Gibson, G.-V. Roschenthaler, and K . Schmutzler, J.C.S. Dalton, 1975, 918. J . Ci. Riess and D. U . Robert, Bull. Soc. chini. Frujtce, 1975, 425. A . H . Cowley, R . W . Uraun, and J . W. Gilje, J . Amer. Cheni. Soc., 1975, 91 434. A. L. Rheingold and J. M. Bellama, U.S. NTIS, Ad-A Rep. No. 008111, 1975 (Chem. A h . , 1975, 83, 179 246).

680

Yu. Y u . Samitov, N.K. Taieeva, and N.A. Chadaeva, Zltur. strulct. Khim., 1975, 16, 34. J. Devillers, M . Cornus, J. Navech, and J.-G. Wolf, Org. Mugn. Resonance, 1975, 7, 41 I . J. C. Barne?, G. Hunter, and M . W. Lown, J.C.S. Perkin 11, 1975, 1354. It. H. Mitchell, 7rtruhedron Letters, 1975, 1363.

64

Spectroscqlic Psoperties of ltiorgutiic a i d Orgutiometnllic Conlpourtcls

spectra of MeSeC(Se)NPri, have indicated that internal rotation around both the carbon-nitrogen and Pri-N bonds are restricted below -40 "C, and the compound exists as three rotational isomers with respect to the Pri-N bond, with mole ratios of approximately 0.54 : 0.31 : 0.15.5u0 The lH n.m.r. spectrum of R,NCSe,CH,NR, shows that the N-alkyl groups become magnetically equivalent at unusually low temperatures. The simultaneous disappearance of the "Se satellites for the SeCH, signal indicates that the interchange of N-alkyl groups between diastereotopic positions in the R,NCSe, part occurs through an ionic mechanism rather than rotation around the R,NCSe, bond.591 The temperature dependence of the leF n.m.r. spectrum of SF, has been re-examined and the observed lineshapes in the region of intermediate exchange have been compared with theoretical lineshapes calculated for a number of different methods of permuting axial and equatorial fluorine atoms. Carefully purified SF4 yields experimental spectra in good agreement with those calculated assuming the intramolecular fluorine exchange characteristic of the Berry pseudorotation. The exchange rate in unpurified SF4 is substantially higher than in carefully purified material. The lineshapes observed for unpurified materials can be matched to those calculated by assuming permutations characteristic of several plausible bimolecular mechanisms.5g2 At - 140 "C, in MeF, the lgF n.m.r. spectrum of SeF, shows two triplets with "Se satellites. There is rapid exchange at - 20 0C.6g3 EquiIibria.--Soloafion Studies of Ions. 'H N.1n.r. spectroscopy has been used to investigate the interaction of Group IA and IIA metal cations with model aliphatic a m i d e ~ . ~Experimental ~, techniques, involving spinning side-bands, have been developed and used for determining the chemical shift relative to gaseous methane of the HO and Me protons of pure methanol and methanol i n the presence of strong electrolytes. The strong temperature dependence of the chemical shift of the OH proton is similar to that of water and is consistent with the model developed earlier for aqueous solutions. From these studies, the total 'effective' solvation numbers of Nal, LiN03, CaCl,, LiClO,, LiBr, LiCI, and K1 were determined. The solvation numbers are quite similar to the hydration numbers, and this was taken as evidence that the ions bind water and methanol primarily through the oxygen atom. The methyl 'H n.m.r. shift varies with the concentration of electrolyte but does not vary with temperature.5Q5'H N.m.r. has been used to measure the mobility of water in solutions containing Na+, K+, Cs+, CI-, Br-, and [C104]- at 0-360 "C. The mobility decreased due to hydration. At high temperatures, the hydration numbers of Na+, K+, and C l were determined as 18, 24, and 32 molecules of water.696 6@o

6v1

6a4 696

boa

Y.-I. Takeda and T. Tanaka, Org. Magn. Resonance, 1975, 7 , 107. K. A. Jensen and L. Hendriksen, Acta Cliem. Scand. ( B ) , 1975, 29, 877. W. G . Klemperer, J . K. Krieger, M. D. McCreary, E. L. Muetterties, D. D. Traficante, and G . M. Whitesides, J . Amer. Chem. SOC.( B ) , 1975, 97, 7023. K . Seppelt, 2. anorg. Chem., 1975, 416, 12. D. Balasubramanian and B. C. Misra, Biupolymers, 1975, 14, 1019 (Chem. Abs., 1975, 83, 1 14 864). F. J. Vogrin and E. R. Malinowski, J . Amer. Chem. Soc., 1975, 97, 4876. A. N. Voronovich, L. S. Lilich, and M. K. Khripun, Yad. Magn. Rerun., 1974, 5, 112 (Chem. Abs., 1975, 82, 162 537).

Nirclear. Mrrgtietic Resotmice SpecfroscopJ*

65

For solutions of lithium salts, outside the first hydration sphere, the structure of water is almost the same as in pure water. The nearest protons beyond the first hydration shell are cn. 5 8, from Lit. Compared to pure water, the mobility of water molecules in the first hydration sphere is reduced by ca. 50%.507The values of TI for 7Li and 13,Cs nuclei in aqueous solutions of chlorides have been determined. The magnetic and electronic interaction of the 7Li nucleus with the environment in a 0.326 moll-' solution was averaged by rotation of the water molecules near the Li with an activation energy of 3.8 kcal mol-l. Interionic interactions in 1 and 5 mol I-' solutions of CsCl do not contribute to la3Cs relaxation. The relaxation is determined by the mobility of the water molecules near the Cs+, with an activation energy of 1.26 kcal mol-l. The activation energy for motion of water molecules near Lif or Na+ ions is higher than that for bulk water molecules, whereas the reverse is true for the Cs+ TI of 7Li+ has been measured for solutions of LiCl and LiC10, in a wide range of solvents, both protic and aprotic. The values of (l/Tl)oobtained by extrapolation were discussed i n terms of current theories of magnetic relaxation of ionic nuclei. A linear correlation was found between (1/Tl)" and Gutmann's donor numbers and Kosower's Z-values. These correlations indicated that the relaxation of 7Li+is dominated by donor-acceptor interaction of the cation with the solvent molecules. The concentration dependence of T,-l for LiCl and LiC10, differs on account of specific cation-anion interaction.699 The solvation of Li+ by acetone has been studied in acetone-MeNO, solution by 7Li and 35Cln.m.r. spectroscopy. The Li+ is solvated by four acetone molecules, and stepwise stabilityconstants were calculated. The effect of weak complexing agents on the ion pair Li+[C104]was investigated.600 The 7Li chemical shifts of Et,O, THF, and diniethoxyethane solutions of LiBMe,, LiAIMe,, LiGaMe,, and LiTIMe, have been reported. The observed changes in 7Li chemical shift were discussed in terms of solvation of Li+ and ion-pair formation in solution. The 7Li chemical shift of LiSnMe, in THF was also given.s01 The lH n.m.r. spectra measured in different solvents suggest that indenyl-lithium exists as a solvent-separated species in dimethoxyethane. The charge distribution for the indenyl carbanion as inferred from solution n.m.r. data was presented and compared with INDO results.802 TI of 'Li in the system LiOH-NaOM-H,O has been studied and complex formation was established.s03 The downfield shifts, A s , of the NH proton signals induced by the addition of LiCl to NN-dimethylacetamide solutions of urea and urethane compounds were The interactions which take place between NN-dimethylacetaniide +

m7

6BD

eol

OoS 604

R . K . Mazitov, 0. Ya. Samoilov, N. V. Bryushkova, M. N. Buslaeva, and K . T. Dudnikova, Zhrrr. strukt. Khita, 1975, 16, 564. K . K. Mazitov, 0. Ya. Samoilov, N. V. Bryushkova, M. N. Buslaeva, and K. T. Dudnikova, Tezisy Dok1.- Vses. Soaeshch. Elektrokhim., 5th (1974), 1975, 1, 69 (Chem. A h . , 1975, 83,

185 853). A. I. Mishustin and Yu. M. Kessler, J . Solution Cheur., 1975, 4, 779 (Chem. A h . , 1975, 83, 184 41 1). R. G. Baum and A. I . Popov,J. Solution Chem., 1975,4,441 (Chem. Abs.. 1975,83, 137 813). R . J. Hogan, P. A. Scherr, A. T. Weibel, and J . P. Oliver, J . Organontetullic Chem., 1975, 85, 265. W, E. Rhine and G. D. Stucky, J . Amer. Chem. Sor., 1975, 97, 737. R. K. Mazitov and L. S. Itkina, Zhur. neorg. Khitn., 1974, 19, 3203. Y . Chokki, Take(f0 KmXyirsho Eio, 1975, 34, 43 (Chem. Abs., 1975, 83, 98 851).

66 Spectroscopic Properties of' Inorganic and Organornetallic Compounds and water, aqueous LiCI, or aqueous LiCIO, have been studied using 13Cn.m.r. spectroscopy. The results were interpreted in terms of the transient species (dma),(H,O),, [Li(OHz),(dma)]+C1-, and [Li(OH,)5(dma)]+.605The application of i.r. and 'Li, 23Na,and 3GC1n.m.r. techniques to the study of electrolyte solutions in non-aqueous solvents has been discussed and used to detect contact ion-pair formation and to determine cationic solvation numbers. 23NaChemical shifts in different solvents show a linear relationship with Gutmann's donor numbers for these The self-diffusion coefficients for lH, 'Li, and 23Nahave been measured in solutions of Li-NH3 and Na-NH,. The Li+ and Na+ are solvated by four NH3 molecules over the timescale of molecular diffusion.007 By measuring 'H Tl in aqueous solutions of NaOH and KOH, the hydration numbers n of Na+, K+, and [OH]-, and their mobilities have been determined for various [OH]- concentrations. Values of n = 6 and 18 for Na+ and n = 8 and 24 for K+ were found, depending on [OH]- concentration. The anomalous mobility and chemical shifts of H + and [OH]- were explained in terms of the structure of the hydration complexes of these ions.eo8 Work on the relaxation of 23Na+in polyelectrolytes (J. J . van der Klink, L. H. Zuiderweg, and J. C. Leyte, J . Clzem. Phys., 1974, 60,2391) has previously been criticized on the basis that the closest-approach distance of the Na+ nucleus to the polyion of 2.8 8, is too small to be physically realistic, and the criticism has now been replied to.aoePreferential solvation of the Na+ ion has been studied by determining 23Na chemical shifts for NaBPh, solution in all possible binary solvent mixtures of MeNO,, MeCN, (Me,N),PO, DMSO, pyridine, and (Me,N),CO. Generally these studies reflected the relative donicity of each solvent in a given solvent pair where the solvent of higher donicity was preferentially contained in the inner solvation shell of the Na+ ion. The results were treated quantitatively to yield a geometric equilibrium constant and the free energy of preferential solvation,e10 The lH chemical shifts of water in aqueous solutions of urea and tetramethylurea in the presence of NaCIO, and MgC1, are towards higher and lower magnetic field respectively as the concentrations of NaClO, and MgC1, are increased.611 The values of TIof water in the natural and in the Na, Ca, or A1 forms of kaolinite suspension have been determined.612 3gK, *OK, and 41Kn.m.r. have been recorded for solutions of potassium salts in H 2 0 , D20, MeOH, and ethylenediamine and for the solid halides. The ratio of the Larnior frequency of 3gKand 41K was determined in various samples to be v(~OK)/V(~IK) = 1.821 873 l(9). N o primary isotope effect was detected within the limits of error of 0.5 p.p.m. The concentration dependence of the chemical shift of the 39K resonance frequency was determined, and the ratios of the ao5 Ooa

607 608

ool (lo (11

a'*

G . E. Ellis, R. G . Jones, and A. J . Matheson, J.C.S. Faraday II, 1975, 71, 1823. A. 1. Popov, Pure Appl. Chern., 1975, 41, 275. A. N . Garroway and R. M. Cotts, Electrons Fluids, Nut. Met.-Ammonia Solutions, Cofloq. Weyf,3rd, 1973, 1972, 213, ed. J. Jortner, Springer, New York (Chem. A h . , 1975, 82, 21 877). L. V. Rertyakova. A. 1. Polyakov, and L. G. Romanov, Izoest. Akad. Nuuk Kazakh. S.S.R., Ser. Fiz.-Mat., 1975, 13, 7 (Chem. Abs., 1975, 83. 66401). G. S. Manning, J . Chem. Phys., 1975, 62, 748. M. S. Greenberg and A. I. Popov, Spectrochim. Actu. 1975, 31A, 697. M. Nango, A. Katayama, and N. Kuroki, Sen'i Gakkaishi, 1974, 30, T387 (Chem. Abs., 1975, 82, 8252). F. D. Ovcharenko, A. G. Brekhunets, V. V. Mank, and 1. N. Pereverzeva, Kolloid. Zhur., 1974, 36, 1177 (Chem. A h . , 1975, 82, 64 835).

Nilclear Magnetic Resonance Spectroscopy

67

Larmor frequency of 3DK, *OK, and 41K for infinite dilution relative to the resonance frequency of 2H in D20 were derived. Tl and TLwere also given.013 From lQFn.m.r. studies it has been concluded that the energy of hydrogen bonds between water and F- increases in the order K+F-(H,O), < K+(H20)F-(H2O)Z-n z F-(H,O), < K+(HaO)F-(H20),-1.614 A treatment based on n successive equilibria, where n is the solvation number, has been used to interpret low-temperature lH n.m.r. spectra for solutions of Mg(C104)2 in aqueous acetone of very low water content. No evidence for a change in solvation number from 6.0 +_ 0.4 with increasing acetone : water ratio was found by other workers.s1s The ratios of the Larmor frequencies of 2aMgand s7Cl and of 43Caand ,'Cl have been measured in aqueous solution, and the nuclear magnetic moments were given for these nuclei in the hydrated ions. 2sMg and 43Ca chemical shifts were investigated at natural abundance of these isotopes in solutions of the chlorides, bromides, nitrates, and perchlorates in H 2 0 and D20. The signal intensities are large enough to study, within a reasonable time, these nuclei at natural abundance down to low concentrations (8 x lo-, moll-' for 2SMg). For 25Mg, very small chemical shifts were observed whereas for 43Ca,remarkable shifts to higher frequency were found for halide solutions and to low frequency for oxyanion solution. Linewidths of only a few Hz were observed for both isotopes.616 The effect of Mg2+, Ca2+, and Sr2+on water relaxation rates has been given.617 Longitudinal relaxation rates of ls9La at 8.4 MHz have been reported for aqueous solutions of LaCI, and La(ClO,), in the concentration range 0.1 to 1.7 mol I-'. The effects of added NaCI, LiCI04, and LiNO, were also investigated. I t was found that the 139Larelaxation in aqueous chloride solution is well described by the classical theory of a moving rigid sphere in a viscous mediuni. The relaxation rate at infinite dilution is T1-l := 277 s-l and the quadrupole coupling constant is 3.1 MHz. Departures from the classical theory were observed in the presence of an excess of [C104]-,which was explained by the formation of outer-sphere ion pairs. The effect on the relaxation rate of inner-sphere complex formation with nitrate is much lH N.1n.r. chemical shifts have been used to determine the hydration number of La(CI04),.e1* The concentration dependence of 1i.m.r. relaxation rates in aqueous solutions of La, Ga, In, Hf, Ti, and Zr salts has been studied, and hydration By the use of 'H n.m.r. spectroscopy, the numbers have been number of water molecules in the inner co-ordination sphere of NaNd(edta),8H20 has been determined.621 'H N.m.r. spectra have been used to study the solvation of La(NO,),, Pr(NO,),, Th(N03)4, and U0,(N03)2 by (BuO),PO and related W. Sahm and A. Schwenk, 2. Nuturforsch., 1974, 29a, 1754. W. Kdodziejski and Z . Kecki. J . Mol. Structure. 1975.29,27. A. D. Covington and A. K. Covington, J.C.S. Faradny Z, 1975, 71, 831. 0. Lutz, A. Schwenk, and A. Uhl, 2. Narurforsch., 1975, 30a, 1122. V. B. Kolokol'tsov and V. A. Shcherbakov, Zhur. fir. Khim., 1975, 49, 1214 (Chenr. A h . , 1975, 83, 88 123).

OIB

aal

J. Reuben, J . Phys. Chem., 1975, 79, 2154. Ch. Berger, H.-H. Emons, and D. Pohl. 2. phys. Chent. (Leipzig), 1975, 256, 421. V. B. Kolokol'tsov and V. A. Shcherbakov, Zhur. fir. Khim., 1975,49, 1454. K. I. Popov, V. F. Chuvaev, L. I. Martynenko, and V. I. Spitsyn, Izoest. Akad. Nuuk S.S.S.R., ser. Khim., 1975, 8, 1710.

68

Spectroscopic Properlies of' Inorganic and Organometallic Compounds

At - 93 "C, a solution of [U02(DMF)5]2+[C104]a-i n DMF shows the co-ordinated D M F methyl signals as a singlet while at 280 "C, only a doublet is observed for the co-ordinated and free D M F methyl groups.62:' The 'H n.m.r. spectra of DMSO-[U0J2+ complexes have been measured and two types of complexes determined.624 lH N.m.r. spectroscopy has been used to determine the stability constant of Cr(acac), with CHCI3, CH2C12,or CsHBin cyclohexane, which was correlated with s o l ~ b i l i t y6 2. 6~ ~N.ni.r. ~ ~ relaxation-time measurements have been reported for W o , 61Br,and 35Clfor weak outer-sphere complexes of cobalt(rr1) complex ions. These data were analysed in terms of outer-sphere association constants and line-broadening parameters. It was concluded that the solvent-solute interaction of halide ions in outer-sphere association with [(en)&oI3+ is significantly perturbed. Within experimental errors, both optical and n.m.r. methods gave the same values for equilibrium constants.6z27 A method has been presented for the determination of chemical rate constants from TI. The exchange rate of water molecules between the inner hydration sphere of Ni2+and the bulk has thus been obtained in Ni(NO,), solution. The results indicate a nitrate inner-sphere complex with a stability constant of ca. 0.2 mol-' 1. The ratio of the Ni2+-H,O distances in the first and second hydration layers was estimated. A combined and T, was proposed which improves the accuracy of the measurement of fast chemical reactions.626The effect of acidity on lH n.m.r. relaxation times in Ni2+ salt solutions has been investigated.62B The temperature dependence of the solvent IH n.m.r. spectra has been measured for (103) dissolved in MeOH and MeCN. Rate constants and thermodynamic 2+

(1 03)

parameters were determined for solvent exchange on nickel. The shifts were unusual and attributed to a significant pseudocontact shift of opposite sign to the contact shift.630lsotropic IH n.m.r. chemical shifts have been determined for [ N ~ ( A c O H ) ~ ]and ~ + ,the results indicate some dissociation in ~ o l u t i o n . ~ ~ ~ ma

G. P. Savoskina and E. N. Sventitskii, Yad. hlagn. Rezon., 1974,5,96 (Chem. Abs., 1975,82, 162 535).

824 e26 626

OZ7 888 629

OYo

eJ1

R. P. Bowen, S. F. Lincoln, and E. H. Williams, J. Magn. Resonance, 1975, 19,243. L. E. Nikol'skaya, L. L. Shcherbakova, and S. S. Zelentsov, Kompleksoobrazovanie Ekstr. Aktinoidm Lantanoidov, 1974, 16 (Chem. Abs., 1975, 83, 18 039). V. M. Nekipelov, A. N. Shupik, and K . I. Zamaraev, 2hur.fiz. Khim., 1975, 49, 1061. A. N. Shupik, V. P. Lezina, and V M. Nekipelov, 2hur.fir. Khim., 1975, 49, 1063. K . L. Craighead, P. Jones, and R . G. Bryant, J. Phys. Chem., 1975, 79. 1868. H.Strehlow and J . Frahm, Ber. Bunsengesellschuft phys. Chem., 1975, 79,57. A. A. Popel and A. V. Zakharov, Issled. Po Elektrokhimii, Magnetokhiinii i Elektrokhim. Metodam Analiza, 1974, 4, 114 (Chem. Abs., 1975, 83, 155 227). L. L. Rusnak and R. B. Jordan, Inorg. Chem., 1975, 14, 988. R . E. Cramer, W. Van Doorne, and R. Dubois. fnorg. Chenz., 1975, 14, 2462.

Nitclear Ilfognetic Resonance Spectroscopy

69

The effect of temperature and concentration of ZnC1, on the chemical shift of the OH resonance has been studied for H20,MeOH, and EtOH. The shift of the OH peak towards lower fields was attributed to solvent polarization by ions. With increasing concentration, ion association resulted in screening of cations byanions, thus reducing the polarization of the solvent. The breaking of hydrogen bonds in solutions of higher concentration results in a shift of the OH peak towards higher fields.e32leQHgN.m.r. studies of mercury salts in H 2 0 and D 2 0 or in the appropriate protonated and deuteriated acids have been reported for both [Hg,12+ and Hg2+. A ratio of the Larmor frequency of la9Hgand of in a Hg(NOy), solution of dilute DNO, was given,633 lJ(l1B-l9F) and TI of 7Li nuclei in LiBF4, LiHBF,, and NaBF, in a wide variety of solvents have been measured. 1J(f1B-19F)is solvent- and concentrationdependent but is constant (1.3 Hz) at infinite dilution in all solvents. C('Li) are strongly solvent dependent.63r New n.m.r. data have been reported for the [BFJ anion present at low concentrations in a range of host salt solutions. Host anions appear to have no direct influence on the [BFJ- parameters. Cations have a marked and varied influence on both IJ(11B-19F) and on the 19F chemical shift. If 1J(11B-19F) increases, 6(lgF) may move up- or down-field whereas if lJ(llB-lQF) decreases, only downfield shifts are observed. Changes in 1J(11B-19F)correlate well with changes in electric fields. The nature of the ion pairs was also Separate OH 'H n.ni.r. signals for free and bound MeOH and EtOH molecules have been observed at reduced temperatures for Ga(ClO,),, Al(C104)3, and AICI,. Solvation numbers of ca. 6 for Ga(CIO,), and AI(ClO,), in MeOH; ca. 5 for Al(N03)3in MeOH; ca. 4 for AICI, in MeOH and in EtOH below -45 "C; ca. 7 for Ga(C104)3in MeOH. Rates of exchange, and A H * and A S *, were determined. It was suggested that the exchange was via the SN2 mechanism. However, no allowance appears to have been made for the temperature dependence of broadening by the quadrupolar metal.e36 Tl has been measured for AlCI, lH N.m.r. spectroscopy has been used to derive heats of formation of DMF, DMSO, and MeCN complexes of JnC13.e38 "'Tl N.m.r. spectra have been used to investigate preferential solvation of TI+ by mixed s ~ l v e n t s . ~ ~ ~ The relaxation time, TIP,for 36Cl in [C104]- in aqueous solution is 0.25 s. TIPis insensitive to the presence of most first-row transition metals; however, a weak complex with Mn2+was demonstrated and the exchange rate was estimated. In the absence of Mn2+, the relaxation rate is dominated by the nuclear electric quadrupole interaction while if Mn2+ is present there is also a dipolar contribution.64o wa a3J

6J4 RY6

e37

R:il'

tim

I. Karczewska and 2. Kqcki, Roczniki Chenr., 1974, 48, 1571 (Chem. Abs., 1975, 82, 77 730). H . Krueger, 0. Lutz, A. Nolle, and A. Schwenk, 2.Phys. ( A ) , 1975, 273, 325 (Chem. Abs., 1975, 83. 155 219). R. K. Mazitov, V. V. Evsikov, and M . N. Buslaeva, Teor. i eksp. Khint., 1975, 11, 398. J . W. Akitt, J.C.S. Faraday I, 1975, 71, 1557. D. Richardson and T. D. Alger, J . Phys. Chem., 1975, 79, 1733. A. Takahashi, J. Phys. SOC.Japan, 1975, 38, 1790 (Cheni. Abs., 1975, 83, 123 717). V. V. Skopenko, V. S. Kuts, V. F. Mikitchenko, and L. I. Bondarenko, Ukrain. khirn. Zhur. ( R i m . Erln.), 1974, 40, 1250 (Chem. Abs., 1975, 82, 129 946). 6 . F. Hinton and R. W. Briggs, J . Magn. Resonance, 1975, 19, 393. K. L. Craighead and R. G. Bryant, Mol. Pliys., 1975, 29, 1781.

70

Spectroscopic Properties of Inorganic arid Organometallic Compourrds

Ionic Equilibria. 'H, 2H, and alkali resonances have been measured on alkali naphthalene ion pairs in ethereal solutions. The electron-spin relaxation time is proportional to the inverse of the ion-pair concentration but not to viscosity, T-l, as predicted by the Pake-Tuttle relationship. This behaviour was discussed in terms of ion pairs.641 The metal complexes of an antibiotic drug, monensin, have been investigated by 'H, ?Li, 13C, and 23Na n.m.r, techniques in several non-aqueous solvents. The acidity constants of inonensin and the stability constant for the monensin-Na+ complex were determined in MeOH solution. The order of cation preference is Ag+ > Na+ > K + > Rb+ > Cs+ > Li+ z N H4+. Two sodium complexes of different configuration and stability were found.64z'Li N.ii1.r. studies were performed on Li+ complexes of N{(CH,CH,O),CH,CH,),N (n = 2,2,2; n = 1,2,2; and n = 1,1,2). In the case of the first two cryptands the exchange between the free and complexed Lit was fast on the n.m.r. time-scale. The 21 1 cryptand forms a much more stable lithium complex, and two ?Li resonances were observed for solutions containing an excess of the Li+ The kinetics of complexation reactions of the Lit ion with cryptand 21 1 in a number of solvents have been investigated by temperature-dependent 'Li n.m.r. spectroscopy. The energies of activation for the release of Li+ from Li+ (cryptand 21 1 ) complexes increase with increasing donicity of the solvent as expressed by the Gutmann donor number. Thus the transition state of the complexation reaction must involve substantial ionic ~ o l v a t i o n . From ~ ~ ~ the 2H n.ni.r. spectra of mesophases composed of an anionic amphiphile decanol and D,O, information about the degree of orientation of both water and decanol was obtained. The degree of water orientation is considerably greater with Li' spectroscopy has been rather than other cations as c o u n t e r - i ~ n .'H ~ ~ N.m.r. ~ used to show incomplete dissociation of Li+[3,5-dinitrophenolate]-in D M S 0 , 6 4 e and to follow complexing of ZnC1, and LiCl in aqueous 31PChemical shifts of the middle phosphate groupings of tri- and tetra-metaphosphate and long-chain polyphosphates were measured in aqueous solution in the presence of a series of counter-cations [R,N]+, Li+, Na+, K+, Rb+, Cs+, Mg2+, Ca2+, Sr2+,and Ba2+. The data indicate that to a first approximation, the value of the chemical shift within the middle phosphate group region of the 31P spectrum reflects the conformation of the condensed phosphate backbone.0448The signal widths at half-height of middle-group resonance signals from trimeta-, tripoly-, and long-chain poly-phosphates have been measured in aqueous solution in the presence of [Bu4N]+, Na+, and Mg2+. 31P N.m.r. relaxation times were also measured.s4@ The n.m.r. chemical shift and linewidth have been measured for 23Na- in THF, ethylamine, and niethylamine for 87Rb- in THF and ethylamine and for 133Cs-in THF. In all cases, the counter-ion was the N(CH2CH2(0CH,CH2),}3N,E. de Boer and B. M. P. Hendriks, Pure Appl. Chem., 1974, 40,259. P. G. Gertenbach and A. 1. Popov, J . Amer. Chem. Soc., 1975, 97,4738. a4s Y. M. Cahen, J. L. Dye, and A. I. Popov, J. Phys. Chem., 1975, 79, 1289. Y. M. Cahen, J. L. Dye, and A. I. Popov, J . Phys. Chem., 1975,79,1292. 041 N.-0. Persson and B. Lindman, J . Phys. Chem., 1975, 79, 1410. T. Risanz and P. Szczecinski, Roczniki Chem., 1975, 49,547 (Chem. Abs., 1975, 83, 85 9031. a7 A. J. Easteal, E. J. Sare. C. T. Moynihan, and C. A. Angell, J. Solution Chem., 1974, 3, 807 (Chern. A h . , 1975, 82, 65 142). 64* T. Glonek, R. A. Kleps, E. J . Griffith, and T. C . Myers, Phosphorus, 1975, 5, 157. 64O T. Glonek, R. A. Kleps, E. J. Griflith, and T. C. Myers, Phosphorus, 1975, 5, 165.

841

adz

Nuclear Magnetic Resonance Spectroscopy

71

222 cryptate complex of the corresponding cation. The chemical shift of Na- is, within experimental error, the same as that calculated for the gaseous anion (based upon the measured value for the gaseous atom) and is independent of solvent. Comparison with the solvent-dependent chemical shift of Na+ provides conclusive evidence that Na- is a 'genuine' anion with two electrons in a 3s orbital which shield the 2p electrons from the influence of the solvent. The linewidth increases from THF to ethylamine to methylamine, suggesting either an increasing exchange rate with the cryptated cation or, more probably, the influence of a n increasing concentration of solvated electrons. I n the case of sodium solutions in all solvents, both [Na(222 cryptate)]+ and Na- are detected by their n.m.r. peaks. However, probably because of extreme line broadening, [Rb(cryptate)]+ and [Cs(cryptate)]+ are not observed, but only the relatively narrow line of the corresponding anion. The chemical shifts (diamagnetic shift in p.p.m. from the infinitely dilute aqueous ion) are 185 and 197 for Rb- in ethylamine and THF, respectively, and 292 for Cs- in THF, compared with 212 and 344, respectively, for the gaseous R b and Cs atoms. When 18-crown-6 is used instead of the 222 cryptand complex, it is still possible to obtain solutions which are about 0.4 moll-' in total metal when methylamine is used as the solvent. However, in this case, both the Na- and the [Na(222 cryptate)]+ 1i.m.r. peaks are exchange-broadened, even at - 50 "C, and coalesce as the temperature is raised to about - 15-0 "C,depending upon the concentrations. The variation of the rate of exchange of the sodium nucleus between [Na(222 cryptate)]+ and Na- with concentration should permit determination of the exchange mechanisni. Possible exchange mechanisms and the information obtainable from them are The n.ni.r. relaxation rate of 23Na+in polyelectrolyte solutions containing both univalent and bivalent counter-ions has been investigated to obtain information on the nature of bivalent ion-polyion interaction.651 23Na Nuclear quadrupole relaxation and shielding have been studied for aqueous surfactant systems in order to get information on the mode of interaction between alkali ions and aggregates of anionic amphiphiles. For an aqueous solution of sodium octanoate and sodium octyl sulphate, data can be analysed in terms of a simple two-site model. In this way information was obtained on the association process. From "3Na Tl and chemical shift measurements, it was found that counter-ion binding in aqueous sodium cholate solution changes much more gradually with concentration than is the case in solutions of simple salts. s5Rb and 133Csn.m.r. experiments were also performed.6s2The solution conformation, rate constants, and activation energies for Na and K+ complexes of valinomycin in acetone have been determined.663 T1-l of 23Na+ions in aqueous polyacrylic acid solution increased with increasing neutralization. The dependence of T1-l o n concentration at varying degrees of neutralization decreased sharply at concentrations less than 0.05 equivalents per 1it1-e.~~~ 'H N.m.r. spectra have +

660 661

86 2 653

IJ'O

J. L. Dye, C. W. Andrews, and J. M. Ceraso, J . Phys. Chem., 1975, 79, 3076. J. J . Van Der Klin, D. Y. H. Prins, S . Zwolle, F. Van der TOUW,and J . C. Leyte, Chern. Phys. Letters, 1975, 32, 287. 11. Gustavsson and B. Lindman, J . Anier. Cheni. Soc., 1975, 97, 3923. D. G. Davis and D. C. Tosteson, Biochetnistry, 1975, 14, 3962. J. C. Leyte, L. H . Zuiderweg, and J. J. Van der Klink, Charged React. Polyni. I Polyelectrolyres, Pap. NATO Adu. Study Inst. Charged React. Palym., 1972, 1972, 383 (Cheni. Abs., 1975, 83, 79 767).

72

Spectroscopic Properties of Inorganic and Organonietallic Compounds

been used to investigate the interaction of NaI with various carbohydrate^,^^^ and to examine the complexation of theophylline by sodium benzoate.666 lH and 13C n.1n.r. spectral investigations of the binding of Mg2+,Ca2+, Sr2+, Ba2+,Zn2+,Cd2+,and Hg to cytidine and guanosine show both cation and anion have an effect, and stability constants were Dark-red flavoquinonemetal complexes have been detected by 'H n.ni.r. spectroscopy in aprotic solvents. The stoicheiometry and formation constants were measured by metal-ion titration in acetone with the relative order of stability Cu' > Ni" > Ag', Co" > CU" > Zn" > Cd" > Fe'' B Mn", Mg", Fell'. Stable bidentate chelates were observed corresponding to the octahedral tris complexes (Zn", Cd", Co", Ni", and Fe"), tetrahedral bis complexes (Ag' and Cu') and the squareplanar Cu" bis 13C N.ni.r. spectroscopy has been used to show that Mg2+,La3+,and Nd3+ bind to tetracycline.659 From the lH n.1n.r. spectra of H 2 0 and D 2 0 solutions of KBeH(edta), equilibria between forms with N-Be and N-H bonds were found.66oPhenolic OH and o-H resonances in lH n.m.r. spectra of phenols in [2H6]DMS0 showed downfield shifts on addition of alkaline earth salts. MgClz caused the strongest downfield shifts both for the OH and phenolic ortho-protons.661 The binding of Mgz+ to acetyl phosphate, acetonylphosphonate, and related compounds has been examined by lH and 31Pn.m.r. spectroscopies.662 Similar studies have been carried out on the interaction of Mg2+ with ATP, GTP, CTP, and UTP. Mg2+ only binds to the p-phosphate group, and binds more strongly in neutral than in acidic ~ o l u t i o n s . ~ ~ ~ Complex formation between CaCI, and { RC(0)CH20CHz}a[R = -NMe(CH,)llC02Et, -NPrn,] has been investigated by 1 3 C n.m.r. spectroscopy. In MeOH, the ligands form 1:l and 1:2 complexes (Ca?ligand). In the latter case, apart from solvent molecules, the ligand's two amide CO groups and the two ether atoms probably take part in co-ordination to the metal.664 An n.m.r. relaxation method for studying the diamagnetic ion-ligand equilibrium has been tested for Y 3 +and A13+ with oxalic or sulphosalicylic acids using paramagnetic Fe3+ ions as indicators. The formation constants of the diamagnetic complexes were determined from the known equilibrium constant with the paramagnetic It has been suggested that 139Lacan be used as an n.m.r. probe to molecular dynamics, and applied to bovine serum albumin.666 lH N.m.r. spectroscopy has been used to show that the La3+ complex of edda is labile while the Lu3+ complex is n~n-labile."~ +

A. 13. Haines, K. C . Symes, and A. G . Wells, Carbohyrlratc Res., 1975, 41, 85 (Cheut. A h . , 1975, 83, 97 823). A. L. Thakkar and L. G. Tensmeyer, J . Pharttz. Sci., 1974, 63, 1319. T. Yokono, S. Shimokawa, and J. Sohma, J . Amer. Chem. SOC.,1975, 97,3827. J. Lauterwein, P. Hemmerich, and J.-M. Lhoste, Inorg. Chem., 1975, 14, 2152. J. Gulbis and G. W. Everett, jun., J . Amer. Chem. SOC., 1975, 97,6248. e 6 0 N . I. Voronezheva, A. I . Grigor'ev, and N. M. Dyatlova, Zhur. neorg. Khim., 1974, 19,3232. 6 6 1 H . Yaniaguchi, A. Numata, E. Uemura, H . Kaneto, and A. Yokoyama, Chem. und Pharni. Bull. (Jnpan), 1975, 23, 1169 (Chem. Abs., 1975, 83, 113 185). R. Kluger, P. Wasserstein, and K. Nakaoka, J. Amer. Chem. SOC., 1975, 97,4298. OeS Tran Dinh Son, M. Roux, and M . Ellenberger, Nucleic Acids Res., 1975, 2, 1101 (Chem. A h . , 1975, 83, 143 179). m 4 R. Biichi and E. Pretsch, Helo. Chitit. Acta, 1975, 58, 1573. A. A. Popel, N . L. Kuz'mina, and 0. S. Kudanova, Zhur. neorg. Khim., 1975, 20, 1145. we J. Reuben, J . Atner. Chem. SOC.,1975, 97,3823. N . A. Kostroniina and L. B. Novikova, Zltrrr. neorg. Khim., 1975, 20, 1793.

me

Nuclear Magnetic Resonance Spectroscopy

73

Complex formation between Ti3+ and citric acid has been studied by n.ni.r. spectroscopy.ge8The equilibrium constants of

have been determined for M1 = Coy Ni, Cu; M 2 = Ti, Zr, Hf, using the concentration dependence of the paramagnetic shift of the 19F n.m.r. signals of the [M2F,I2- ion. Complete dissociation was not observed. The formation constants of inner- and outer-sphere complexes of the same cation increase with increasing fluoride exchange rate in the order [TiF,]?- < [ZrF,I2- < [HfF,I2-. 'OF Paramagnetic- shifts of the inner- and outer-sphere associates were calcuIated.u6BB 670 Spin-echo relaxation has been used to investigate the complexation of V" with edta and sulphosalicylic acid, and the nature of the complexes has been deduced.671 The Forsen-Hoffman spin saturation method has been used to show exchange between HF and [ M O ~ O ~ F , ]and - , ~ lgF ~ ~ n.m.r. spectroscopy has been used to show rapid exchange between WF,, [WF,]-, and [WF8]2-.673 'H N.m.r. spectroscopy has been used to determine the order Cu' > Nil' > Ag' Co" > Cu" > Zn" > Cd" > Fe" 9 Mn", Mg", Fe"' for complexes with (104),e74and to investigate antibiotic complexes with Mn" and C U " , ~ and '~

-

CH,(Cl tOC'Ohlc),II

thiamine phosphate complexes of Mn2+and Ni2+.67s The rate of electron exchange between ferrocene and the ferriciniurn ion has been measured in acetonitrile and in methanol by the n.m.r. line-broadening method, activation energies

6eo

e70

*'l 673

874 e76

A. N. Glebov and Yu. I. Sal'nikov, Sb. Aspirantsk. Robot. Kazan. Un-T. Estestu. N . Khinrij,a, 1973, 141 (Chem. Abs., 1975, 82, 160940). B. N. Chernyshov, R . L. Davidovich, T. F. Levchishina, and V. A. Shcherbakov, Fiz. Mat. Metody Koord .Khim., Tezisy Dokl., Vses. Soueshch., 5th, 1974, 1974,96, 'Shtiintsa' Kishinev, U.S.S.K. (Chem. Abs., 1975, 83. 66395). B . N. Chernyshov, R . L. Davidovich, T. F. Levchishina, and V. Ya. Kavun, Koord. Khim., 1975, 1, 185 (Chem. A h . , 1975, 83, 66341). V. M. Zyatkovskii and A. P. Filippov, Fiz. Mat. Metody Koord. Khim., Tezisy Dokl. Vses. Soueshch., 5rh, 1974, 1974, 86, 'Shtiintsa' Kishinev, U.S.S.R. (Chem., Abs., 1975.82, 162 552). R. Bourgon, T. Bui Huy, and P. Charpin, Inorg. Chem., 1975, 14, 1822. I . D. MacLeod, D. Millington, A. Prescott, and D. W. A. Sharp, Inorg. Nuclear Chem. Letters, 1975, 11, 447. J. Lauterwein, P. Hemmerich, and J.-M. Lhoste, Inorg. Chem., 1975, 14, 2153. G. V. Fazakcrley and G . E. Jackson, J . Inorg. h'uclcur Cliern., 1975 37, 2371. A. A. Gallo and H. 2. Henry, J . B i d . Chem., 1975, 250, 4986.

74

Spectroscopic Properties of Inorganic and OrganometaIIic Compounds

have been derived,677and the equilibrium constant for [(f"C5H5)Fe(CO),],

+

+ H2S04

[(~6-C,H5>,Fe,H(CO)z]2 [HSO,]-

was calculated.678 Stability constants for the formation of cyanide complexes of ferriprotoporphyrin have been A study of the 'H n.m.r. spectra of the photolysis product of Fe2+in 5.6 mol I-' H 2 S 0 4failed to indicate complex The 'H n.m.r. spectra of [Ph,As]+[H,(CO),,Ru]- at low temperatures reveal the presence in nearly equal concentration of two isomers, one of C2or CZvand one of C,,symmetry, which are rapidly interconverting. Equilibrium constants and both equilibrium and activation thermodynamic parameters were determined.@jl IH, 2H, and I3C n.m.r. spectra have been used to determine the rotational correlation time for [Co(en),13+. From the change in the correlation time on ion-pair formation with phosphate ion it was concluded that the partners in the ion pair rotate as a unit in water.68z The rate of N H exchange has been determined by 'H n.m.r. spectra for compounds such as [Co(trien)(gly0)12+ and [C~(trien)(glyOEt)Cl]~+.~~~ The lH n.m.r. spectra of Co", Ni", and Zn" complexes of some adenine derivatives indicated the existence of N-9 binding of Co" i n 3-Me-adenine while in 3-benzyladenine-ZnC1(H20)N-7co-ordination of Zn" occurred.s8a The temperature dependence of the lH n.m.r. spectra of trans[ C ~ ( d i a r s ) ~ H ( H ~ Oin) ]CF3COzH ~+ has been attributed 686 to the equilibrium trans-[Co(di ars), H( H,O)] 2+

+ CF,C02H

+

truns-[Co(diar~)~H(CF~CO,H]~+ H,O

The concentration dependence of 14Nshifts in acetone solution of Co(N03),,9Hz0 was assigned to the equilibrium [Co(H,0)J2+

+ [NO,]-

-

[Co(H,O),(NO,)]+

+ H,O

with an equilibrium constant of ca. 1.5 k 0.2 mol 1-1.sa6 Correlations of exchange on nickel have been investigated by n.1n.r. spectros c ~ p y .The ~ ~ complex ~ formation reaction between Ni" and acetate ions in aqueous solution has been studied by Fourier-transforin 13Cn.m.r. spectroscopy. Equilibrium quotients for the formation of monoacetatonickel(I1) complexes were calculated from the relative areas of the distinct co-ordinated and bulk acetate signals over the temperature range - 5 to + 2 0 "C and were found to be 677

L78

87B RnO 6~

RH3

R04

ass

887

E. S. Yang, M.-S. Chan, and A. C. Wahl, J . Phys. Chem., 1975, 79, 2049. D. C. Harris and H . B. Gray, Inorg. Chetpt., 1975. 14, 1215. J. T. Wang, H . J. C. Yeh, and D . F. Johnson, J . Amer. Chem. SOC.,1975, 97, 1969. V. V. Korolev and N. M. Bazhin, Zhur. neorg. Khim., 1975, 20, 701. J . W. Koepke, J . R . Johnson, S. A. R. Knox, and H. D. Kaesz, J. Amer. Chem. SOC.,1975, 97, 3947. K . L. Craighead. P. Jones, and R. G. Bryant, J . Chem. Phys., 1975, 63, 1586. D. A. Buckingham, M. Dwyer, G. J . Gainsford, V. J . Ho, L. G . Marzilli, W. T. Robinson, A. M. Sargeson, and K . R. Turnbull, Inorg. Chem., 1975, 14, 1739. T. Sakaguchi and M . lshino, Nippon Kagnku Knishi, 1974, 8, 1480 (Chcm. Abs., 1975, 82, I69 555). 13. Rosnich, W. G. Jackson, and S. T. D. Lo, fnorg. Chetn., 1975, 14, 1460. V. V. Matveev, Yu. G . Gladkii, G . I. Skubnevskaya, and Yu. N. Molin, Zhur. strukt. Khim., 1974, 15, 93 I . C. H. Langford, J. P. K. Tong, and A. Merbach, Canad. J. Chern., 1975, 53, 702.

Nuclear Magnetic Resonance Spectroscopy 75 constant over this range. Equilibrium quotients determined over the ionic strength range 1.2 to 4.0 mol 1-1 were found to be smaller than the previously reported values. A niinimuni in the equilibrium quotient was observed at approximately 2 niol 1-1 ionic strength.6s8 Equilibria between tetrahedral, square planar, and octahedral complexes of nickel@) with thiourea have been studied and it was concluded that the charge o n the metal ion has the predominant influence in determining Five-co-ordinate complexes [MLJn+ ( M = Co', Rh', Nil'; L = phosphorus ligands) are in equilibrium in solution with a four co-ordinate complex and free ligand, and rates of ligand exchange were determined.6u0 The temperature dependence of the [1J3C]acetate line broadening and chemical-shift data for monoacetatonickel(i1) have been investigated and rate constants and A H * derived.6Q1For a-amino-acid-Ni2+ complexes there is a linear correlation between the metal-ion concentration and linewidth, which was used to study c ~ r n p l e x a t i o n .lH ~ ~ N.m.r. ~ spectra of [Pt(NH3)2L2]2+ C1-2 (L = acetoxime) have been used to determine the successive stability constants K1 and K2 of acid dissociation of cis- and trans-isomers. The hydrogen signals of the methyl groups of the acetoxime ligand shift towards higher fields with increasing pH.6s3 The stability constant for Cu'-isoprene has been determined as a function of t e r n p e r a t ~ r e696 . ~ ~13C ~ ~and 31Pn.m.r. spectroscopies have been used to show that Cu" binds to the purine ring and the phosphate in the spermine-Cu'I-AMP complex.6QsThe proton exchange rate constants of Cu" amino-acid complexes have been determined. The thermodynamic and kinetic stability of the complexes containing OH, NH,, or CO groups in axially co-ordinating positions was higher than for other complexes. Donor groups in the y- or &position had no effect.6Q7 lH and 13C n.m.r. spectroscopies have been used to investigate the binding of Cu2+and Cd2+ to PheA~pAlaSerVal,~~~ and to show that Cu2-1-is preferentially ~ ~ ~amide bound to the N-7 of the purine ring of AMP in aqueous ~ 0 1 u t i o n .The groups of [(acetylhistamine),Cu]+and [(acetyl-~-histidine)~Cu]+ do not complex Cu but the carboxylate and imidazole groups Rate-constants for IH n.m.r. exchange reactions in aqueous solutions of complexes of Cu2+with amino-acids have been determined at 28 "C by an n.m.r. method.701 The initial bonding of Cu2+ to L-lysine, L-histidine, glycylglycine, and histidylglycine in aqueous

Rol

OQ3 MU

fiu4

OD5

Boi

7U*

K. Fuentes, jun., L. 0. Morgan, and N. A. Matwiyoff, fnorg. Chem., 1975, 14, 1837. D. R. Eaton and K. Zaw, Canad. J . Chem., 1975, 53, 633. E. J. Lukosius and K. J. Cookran, Inorg. Chem., 1975. 14, 1926. R. Fuentes, jun., L. 0. Morgan, and N . A. Matwiyoff, Inorg. Chenr., 1975, 14, 2774. L. Gelbaum and R. Engel, J . fnorg. Nuclear Chem., 1975, 37, 793. A. 1. Stetsenko, N. K . Skvortsov, and B. S. Lipner, Zhur. obshchei Khim., 1975, 45, 1783. 0. P. Yablonskii, S. Yu. Pavlov, L. A. Bolkhova, N. M. Rodionova, and L. F. Lapuka, Z h u r . 3 ~Khim., . 1975, 49, 1413. S. Yu. Pavlov, 0. P. Yablonskii, E. G . Chekalova, and S. G. Kuznetsov, Z h u r . 3 ~ Khim., . 1975,49, 1409. U. Weser, G. J. Strobel, H. Kupp, and W. Voelter, European J . Biochcm., 1974, 50, 91. I . Nagypal, E. Farkas, and A. Gergely, Magyar. KPiii. Folyoirat., 1974. 80, 545 (Chern. Abs., 1975,82, 90 559). 11. Warren and J. H. Bradbury, J . Polynier Sci., Part C, Polymer Syntposia, 1975, 49, 65 (Chrni. Abs., 1975, 83, 93 271). U. Seser, G. J. Strobel, and W. Voelter, F.E.B.S. Letters, 1974, 41, 243 (Chern. Abs., 1975, 83, 54 772). P. A. Temussi and A. Vitagliano, J. Amer. Chem. SOC.,1975, 97, 1572. 1. NaypAI, E. Farkas, and A. Gergely, J . Iiiorg. Nicclear Cheiti., 1975, 37, 2145.

76

Spectroscopic Properties o j inorganic and Organometallic Corripoirnds

solution has been examined by 13Cn.m.r. spectroscopy. The histidine derivatives are ambidentate, with an equilibrium between the two possible cornple~es.~~2 From the pH dependence of the n.m.r. relaxation time, four complexes have been found for the system Cu"-edta. For [Cu(edta)OHI3-, the proton exchange rate and the contact interaction constants were determined. In the presence of en at pH 9, [Cu(edta)(en)12-is f o r n - ~ e d13C . ~ ~N.m.r. ~ spectroscopy has been used to show that uracil binds to Ag+ weakly, with NCO as the binding A study of the pH dependence of the lH n.ni.r. [MeHg]+ signal shows that MeHgOH predominates at pH > 9, and that thestabilityconstant of [(MeHg),O]+ is 0.7 for the equilibrium ? 0 5 MeHgOH

+ [(MeHg),OH]+ 7[(MeH&O]+ +

H,O

The interaction of metal chlorides with adenine in DMSO has been shown to decrease in the order Hg2+ > Zn2 > Cd2+ > Pb2+and some stability constants Metal-nitrogen were derived. The effect of added C1- was also bond lability in Zn", Cd", and Hg" complexes of (HO,CCH,),N(CH,),,N(CH2C02H),has been investigated and the relative lability of the M-N bonds in each series established as a function of n.707 The rate of [cytaI4- exchange in [M(cyta)I2- (M = Zn, Cd) has been determined.?08 N.m.r. spectroscopic and light-scattering investigations on a supersaturated zincate solution show that the zinc is present as {Zn(OH)4]2-.70913CN.ni.r. spectroscopy has been used to identify Hg2+ binding sites on nucleosides, especially thiolated n u c l e ~ s i d e s . ~ ~ ~ The binding of MeHg" by cysteine, penicillamine, and glutathione has been investigated by IH and 13C n.m.r. spectroscopy. The binding sites and kinetics of ligand exchange were estabIished.?l1 Halide exchange on MeHgX has been investigated and A H * and A S * were derived.'12 Formation constants for [MeHgCI,]- and [MeHgBr,]- have been derived from variation of the la9Hg n.m.r. chemical shift as LiX is added,713and the binding of MeHgOH to inosine has been investigated.?14 19F N.m.r. spectra have been used to examine the co-ordination of PF, to [HgJ2+ and evidence was found for 1:l and 1 2 [Hg,I2+PF3 complexes. No J(lgF-lgQHg)was observed, and this was attributed to exchange.71635Cl and 81Brn.m.r. relaxation-time measurements have been used to determine equilibrium positions of anion-exchange reactions of RSMgX, and ratios of equilibrium constants have been derived.71s +

?Oa ?OS

?04

?O6 ?07

?09

?ll 712

?13

ilfi

W. Voelter, G . Sokolowski, U . Weber, and U. Weser, European J . Biochem., 1975, 58, 159. M. S. Shapnik, A. N. Gil'manov, T. P. Petrova, and F. F. Gubaidullin, Zhur. ncorg. Khim., 1975, 20, 2148 (Chem. Abs., 1975, 83, 169 175). J . R. DeMember and F. A. Wallace, J . Amer. Chem. Suc., 1975, 97, 6240. D . L. Rabenstein, C. A. Evans, M. C. Tourangeau, and M. T. Fairhurst, Analyr. Chetn., 1975, 47, 338. S. J. Bevcridge and W. R. Walker, Austral. J . Chein., 1974, 27, 2563. D . L. Rabenstein, G. Blakney, and B. J. Fuhr, Canad. J . Chem., 1975, 53, 787. J. G. Kloosterboer, Inorg. Chem., 1975, 14, 536. W. Van Doorne and T. P. Dirkse, J . EZecrrochetn. SOC.,1975, 122, 1 (Chem. Abs., 1975, 82, 90 859). K. W. Jennette, S. J. Lippard, and D. A. Ucko, Biochim. Biophys. A d a , 1975, 402, 403. D . L. Rabenstein and M. T. Fairhurst, J . Amer. Chem. SOC.,1975, 97, 2086. R. D. Bach and A. T. Weibel, J . Atner. Chew. SOC.,1975, 97, 2575. V. Lucchini and P. R . Wells, J . Oi~gnnoincfrtllicChem., 1975, 92, 283. S. Mansy a n d I NCS > CI > Br > H20.751Stability constants for outer-sphere adducts of Co(acac),-B complexes with CHC13, CH2CI,, CeHs, and PhMe depend on the nature of the B ligand, and distances between the cobalt atom and the nearest hydrogen atom of the outer-sphere ligand were 4.0 -t 0.1 lH and lSF n.m.r. spectroscopies have been used to demonstrate the equili b r i ~ m . ~ ~ ~

Ar A l4N study has been reported for the exchange of pyridine on Ni(Bzac),(py), and the lability of the pyridine was found to decrease as the electron-withdrawing power (assessed from Taft parameters) of the p-alkanedionato-ligand increases.7G4 i

7

((p-t~l)~P},N~OC(p-tol)=NNC(O)p-tol shows a marked solvent effect in the Il-1 n.m.r. spectrum which was attributed to a square-planar-tetrahedral equilibrium, and in all cases the tolyl groups are exchanging.755 The solution behaviour of Pd(PK,), complexes has been studied by 'H, 13C, and 31Pn.1n.r. spectroscopies, and A H * and A S * were derived for PR, exchange. I t was found that Pd(PBz,), . ~ ~Variable-temperature ~~ 19F exchanges PBz, via a dissociative m e c h a n i ~ m 757 n.m.r. studies on {Ph2(CF3)P}3Ptoshow that rapid phosphine exchange which occurs at room temperature is frozen out at ca. - 5 0 "C, and that at lower temperatures a further dynamic process, possibly associated with rotation about the platinum-phosphorus bond, is reduced in rate. Addition of free phosphine shows the formation of the tetrakis species and another unknown species.75* Equilibriuni thermodynamics for the cis-trans isomerism of ((p-ZC,H,).PMe,-,),PdX, have been determined by variable-temperature lH n.1ii.r. spectroscopy, and a linear correlation of both A H and AS with the Hamniett u constant of Z was found and 31PN.m.r. spectroscopy has been used to show that complexes of the type PdPtC14L1L2are formed when equiniolar amounts of Pd2C14L12and Pt2C14L2,are mixed, and activation energies were determined for 760

761

pb2. 7b3

H . E. Hosseini and J. F. Nixon, J . Organometallic Chem., 1975, 97, C24. A. P. Gulya, V. A. Shcherbakov, 0. A. Bolga, and A. V. Ablov, Fir. M a t . Met0d.v Koord. Khim., Trzisy Dokl. VSPS.Soueshch., 5th, 1974, 1974, 83 (Chem. Abs., 1975, 82, 129 989). V. M. Nekipelov, A. N. Shupik, and K. I. Zamaraev, Zhur.Jiz. Khim., 1975, 49, 1028. P.-T. Cheng, T. K. Jack, C. J . May, S. C. Nyburg, and J. Powell, J . Organometallic C h ~ n i . , 1975, 369.

764 76s

7b7 7LB

7b9

J . Crea and S. F. Lincoln, Austral. J . Chmi., 1975, 28, 1523. S. D. Ittel and J. A. Ibers, Inorg. Chem., 1975, 14, 1183. W. Kuran and A. MUSCO,Inorg. Chitn. Acru, 1975, 12, 187. B. E. Mann and A. Musco, J.C.S. Dulton, 1975, 1673. T. G. Attig, M . A. A. Beg, and H . C. Clark, Inorg. Chem., 1975, 14, 2986. A. W. Verstuyft and J. H . Nelson, Inorg. Chem., 1975, 14, 1501.

Niiclear Magnetic Resouatice Spectroscopy

81

exchange via a tetrameric intermediate involving four metal centres. For Pt,CI4(PBuX~,),zJ(1e5Pt-1D5Pt)= 199 Hz and for Pt2T,(PBun3), zJ(195Pt-195Pt)= 380 HZ.'~O A H * and A S * for pyridine exchange and unpaired spin density have been determined for pyridine complexes of ( R,NCS,)2Ni.7s1 Complexes of 1,3-butadiene and isoprene with CuCl and Cu2SO, have been studied in the solid phase and in several solvents by n.m.r. spectroscopy. The enthalpy of formation of the complexes was calculated and the stability constants were given.762 'H and 13C n.m.r. spectroscopy have been used to investigate the complexation of acetylene and ethylene by CuCl and the shifts were and 'H n.1n.r. spectroscopy indicates that (R~3P),Cu,{EC(0)NK1z},(E = S, Se) dissociates at room temperature, while an excess of R2,P breaks the bridge.7B4 IH N.ni.r. spectroscopy has been used to show that there is Me,NN=NNMe, exchange on ( M ~ , N N = N M ~ , ) Z ~ A I - , .The ' ~ ~ effect of X1 on the exchange equilibrium PhSX'

+ 2,6-Me,C6H,SX2 7PhSX2 + 2,6-Me,C,H,SX1

where X' = X2 = H, PhHg, Ph,Sn, or Ph,Pb, have been studied by IH n.m.r. spectroscopy in CHCI,. For orrlro-substituted thiophenols and organometallic derivatives the stability of the chelate rings in most cases increases in the order Ph,Sn < PhBPb -= H < PhHg for five-membered rings and Ph,Sn < Ph,Pb < PhHg < H for six-membered rings.76B Subsequently the work was extended to the exchange of 2,6-Me,CsHSSSbPhz and RSPh (R = H, SnMe,, PhHg) and of Ph,SbSC,,H,Me-o with RSC6H,Me-o (R = H, HgPh, SnPh,, PbPh3).7s7 'H and llB n.ni.r. spectroscopies have been used to show that isonierization to the 1,7,2,4-derivative is via the isolatable of 1 ,7,2,3-(q6-C5H5)Co2C2B3H5 1,2,4,5- and 1,2,3,5intermediates, see Scheme 1 . The equilibrium constant for the reversible rearrangement of Scheme 2 was determined as a function of 'H and llB n.m.r. spectroscopies have been used to investigate exchange reactions of ($-allylic group),B with (MeO),B and BC13,76gand to demonstrate the equilibrium between PhB(OH), and (HOC2H,),E to form PhB(OCH2CH2)& (E = 0, S).770 Adducts of the type PhMe,NBX, have 3J(1H-C-N-11B) = 3 Hz at room temperature, which collapses on warming. Rates of exchange and quadrupole-induced relaxation were measured and mechanisms for exchange 13C N.ni.r. spectra of BF, adducts of '0°

7e1 70a

764

A. A. Kiffen, C. Masters, and J. P. Visser, J.C.S. Dalton, 1975, 1311. G. S. Vigee and C. L. Watkins, J. Inorg. Nuclear Chem., 1975, 37, 1739.

0. P. Yablonskii, S. Yu. Pavlov, N . M . Rodionova, V. A. Stepanova, and E. G . Chekalova, Zhur. obshchei Khirn., 1975, 45, 186. A. Borg, T. Lindblom, and R. Vestin, A d a Chem. Scand. ( A ) , 1975, 29, 475. €4.Nakajima, K. Matsumoto, K. Tanaka, and T. Tanaka, J. Inorg. Nuclear Chmi., 1975, 37, 2463.

71i5

707

76R 760 770

771

V. W. Day, D. H. Campbell, and C. J . Michejda, J.C.S. Chem. Comni., 1975, 118. A. S. Peregudov, L. A. Fedorov, D. N . Kravtsov, and E. M. Rokhlina, Izocst. Akad. Nauk S.S.S.R., Ser. khim., 1975, 2045. L. A. Fedorov, D. N. Kravtsov, A. S. Peregudov, S. I. Pombrik, and E. M. Rokhlina, Izuest. Akad. Nauk S.S.S.R., Scr. khim., 1975, 1512. V. R. Miller and R. N. Grimes, J . Amer. Chem. SOC.,1975, 97, 4213. B. M. Mikhailov, Yu. N . Bubnov, and V. S. Bogdanov, Zhur. obshchei Khinr., 1975, 45, 333. U. W. Gerwarth and W. Weber, Syn. React. Inorg. Metal-Org. Chem., 1975, 5 , 175. J . R . Blackborrow, J . Magn. Resonance, 1975, 18, 107.

82

Spectroscopic Properties of' Iiiorgariic and Orgairoinetaffic Compounds

aCH

CO (Cc,Hc,)

OBH

Scheme 1

ketones and ethers show conformational changes, and AG* (T,)were derived.772 'H, 13C,and 19Fn.m.r. spectroscopies have been used to investigate the complexing of BF, to 'H and ISF n.m.r. spectroscopies have been used to investigate halogen redistribution in adducts of PMe,, PMe,O, and Me,PS with

O B H

C H .

Scheme 2 773

J . S. Hartman, P. Stibbs, and S. ForsCn, Tetrahedron Letters, 1975, 3497. A. Fratiello and C. S. Stover, J . Org. Cheni., 1975, 40, 1244.

83 BX3. Only small proportions of the fluorine-containing mixed boron trihalide adducts are present at equilibrium in the Me,PS adduct system, in accord with previous studies of adducts of other sulphur donors. The effects of the donor on F, CI and F, Br halogen redistribution were discussed.774 The 19F n.m.r. spectra of F3P,B(BF2NMe3),(BF2),-, at - 90 "C show the presence of all four species. As the temperature is raised, exchange occurs, and F3PB(BF2NMe3),BF2 becomes ?he predominant species.775 Dissociation of Et3AIL has been studied by n.1n.r. spectroscopy and a donorstrength order Et,N > THF > Et,O > Et,S established.576 [Me,AI(NMePh)], exists in solution as a mixture of cis- and irons-isomers, and thermodynamic parameters for isonierization were determined. The isomerization is catalysed by 4-Me-pyridine or THF.777Me,AINEtC,H,NMe, exists in equilibrium between the monomer and dinier, and A H " and A S " were determined.778 Exchange of R,P in 1:l and 2:1 adducts with AICI, has bcen confirmed by IH and n.m.r. spect r osco p ies,77g and complex fort na t ion between A1C1 and acet op hen on e,7H0 and All, and K2E (E = 0,S) has been observed.7R1Complex formation between Me,Ga and a r e n e ~ , 'NR3,7d3 ~~ AsMe,, and SbMe,784has been investigated by *H n.m.r. spectroscopy and activation parameters have been determined for ligand exchange. SbMe, exchange is very slow. N.m.r. data indicate that alkyl and aryl hydrides of silicon, germanium, and tin are weakly associated. Aprotic electron-donor solvents form labile complexes with these hydrides, the stability increasing in the order Si < C e < Sn; the central atom being five- or s i x - c o - ~ r d i n a t e . The ~ ~ ~ lH n.ni.r. spectra of 22 silanamines, e.g. Me3SiNHMe, have been determined and correlated with structure. Hydrogen-hydrogen exchange between the NH groups of these compounds was significantly slower than in organosilylamines owing to the weaker intermolecular hydrogen 'H and 31P n.m.r. spectroscopies have been used to demonstrate an equilibrium mixture between Et3P=CHCH2CH2SiMe, and Et2P(=CHMe)CH2CH,CH,SiMe,,787 and between RIC(S)NR2SiMe3and R1C(SSiMe3)=NR2 (lH n.m.r. spectra Determination of the concentrations of pyridine required to cause coalescence of the neophylic Nuclear Mcrgnetic Resononce Spectroscopy

774 776 770

777 770

77D 780

781

7L)a 783

7n4

785

7136 787 788

M. J . Bula, J. S. Hartman, and C. V. Raman, Cunad. J . Clietn., 1975, 53, 326. J . S. Hartman and P. L. Timms, J.C.S. Dalton, 1975, 1373. V. M . Denisov, E. B. Toporkova, L. V. Alferova, and A. I. Kol'tsov, Izaest. Akad. Nauk S.S.S.R., Ser. khinr., 1975, 157. K. Wakatsuki and T. Tanaka, Bull. Chem. Soc. Jupun, 1975, 48. 1475. 0. T. Beachley, jun. and K. C. Racette, Inorg. Chem., 1975, 14, 2534. J.-P. Laussac, J.-P. Laurent, and G. Commenges, Org. Magn. Resonance, 1975, 7 , 7 2 . K . B. Starowieyski, S. Pasynkiewicz, A. Sporzyriski, and A. Chwojnowski, J . Organontetallic Chem., 1975, 94, 361. P. J. Ogen, L. Steenhoek, K . S. Greve. and W. C. Hutton, J . Inorg. Nuclear Chem., 1975, 37, 293. G . M. Gusakov and B. I. Kozyrkin, Zhur. strukt. Khitn., 1975, 16, 202. G. M. Gusakov, B. G. Gribov, B. I. Kozyrkin, N. E. Kulagin, and G. K . Chirkin, Dokhdy Akad. Nauk S . S . S . R . , 1975, 220, 358. G . M . Gusakov, V. I . Bregadze, B. G . Gribov, and B. I. Kozyrkin, Izaest. Akad. Nauk S.S.S.R., Ser. khitn., 1974, 2116. V. A. Ivanov, V. 0. Reikhfel'd, and I. E. Saratov, Zhur. obsltchei Khim., 1975, 45, 2036. K. A. Andrianov, V. V. Yastrebov, A. I. Chernyshev, V. M. Kopylov, and Zh. S. Syrtsova, Zhur. obshchei Khittz., 1975, 45. 802. H . Schmidbaur and W. Wolf, Chem. Bcr., 1975, 108, 2834. W. Walter, H.-W. Luke, and J. Voss, Annalen, 1975, 1808.

4

Spectroscopic Properties of Inorganic and Organonietallic Compounds

84

methyl groups has shown that the racemization of methylneophyl-t-butyltin halide is second-order in the n u c l e ~ p h i l e .The ~ ~ ~kinetics of halogen exchange in binary mixtures of Me,SnX in solution have been investigated by total lineshape analysis, and it was concluded that ionization does play a part in the kinetics;790 dissociation of Bun2SnC12and Et,N to Bu,N aiid SnCl,NBu, has been cis-trans Isomerism of SnC1,.2(Me2RPO) occurs, and activation parameters for pseudorotation of the tetragonal-bipyramidal structure were determined.7g2 The self-diffusion coefficient in liquid PH3 and PD, has been determined from lH, *H, and ,lP spin-echo measurements. It was found that the molecules move by large reorientational and translational From the 13Cand 31Pn.m.r. spectra of RP(X)(CH,CH,),CO (X = lone pair, Me+, 0, S) some evidence was found for the equilibrium :794

-

1

N.m.r. spectra of OR12CsH2N=PR22indicate an equilibrium between two valence t a u t o m e r ~ .Thermodynamic ~~~ parameters for self-association of R2PS2H, determined from 'H n.m.r. data, indicate that the acids exist as cyclic diniers with S-H-S bonding.79s The 31P spin-echo diffusion coefficient of aqueous H3P04 has been determined and decreases as (concentration)i. The calculated radius of 3.2 -t 0.4 A for the H3P04molecule at a concentration of 1.00 equiv. 1-' showed one hydration shell associated with the molecules. In aqueous solutions of sodium polyphosphates, the experimental decrease of polyphosphate anion diffusion coefficient with increasing n was reproduced by D values calculated using the theory of Brownian motion of ellipsoids in 31P N.m,r. Tl and Tlpvalues have been reported for an equimolar mixture of PBr, and PCI,. The lock-field dependent TIPtechnique was shown to be inadequate for exact determinations of scalar spin-spin coupling constants. For PBr,_,Cl,, the values of activation energies and frequency factors for chemical exchange and molecular reorientation, and Tl for bromine and chlorine, were determined from TIPnieasurements when the exchange rates are of the order of lo3 to lo5 s-l. Using known values for quadrupolar coupling constants, the temperature dependence of the reorientation correlation time was derived; this was used for a complete analysis of the temperature-dependent Tl measurements, and contributions to TI were 789

7Q0 791 798

708 791

7Qa

M. Gielen and H. Mokhtar-Jamar, J. Organometallic Chem., 1975, 91, C33. J. A. Ladd and B. R. Glasberg, J.C.S. Dalton, 1975, 2378. Y. Farhangi and D. P. Graddon, J. Organornetallic Chem., 1975, 87, 67. A. V. Aganov, A. A. Musina, I. Ya. Kuramshin, E. G . Yarkova, Yu. Yu. Samitov, and A. A. Muratova, Zhur. strukt. Khim., 1974, 15, 779. K. Krynicki, D . W. Sawyer, and J. G. Powles, Magn. Reson. Relat. Phenom., Proc. Congr. Ampdre, 18th (1974), 2, 51 1 (Chem. Abs., 1975, 83, 197 955). J. J. Breen, S. 0. Lee. and L. D. Quin. J . Org. Chem., 1975, 40, 2245. H. B. Stegmann, G. Bauer, E. Breitmaier, E. Herrmann, aiid K. Schemer, Phosphorus, 1975, 5, 207.

794 797

V. K. Pogorelyi, I. I. Kukhtenko, and T. F. Dwnich, Teor. i eksp. Khim., 1975, 11, 242. H. S. Kielman and J. C. Leyte, Magn. Reson. Relat. Phenom., Proc. Congr. ArnpPre, 18th (1974), 1975, 2, 515 (Chem. Abs., 1975, 83, 197956).

Nuclear Magnetic Resotiawe Spectroscopy

85

identified.798The rate constant, A H *, and A S * were determined for ligandexchange reactions of Me,SbL(X-Y). Most of the ligand-exchange reactions were found to proceed through a bridged intermediate and are entropy controlled.799 Exchange reactions in the antimony(III)--cysteine and 3,3-dimethylD-cysteine systems have also been investigated.*OO The temperature dependence of the 'H n.m.r. X2-I on the 180" pulse spacing has been measured for pure water, enriched at 4% 1 7 0 , to obtain the protonexchange time. At 58 "C, the dispersion of the proton Tlp was explained by a comparable proton-exchange time.so1 The equilibrium between Te(OH),F,-, species has been studied by 19Fn.m.r. spectroscopy, and products u p to n = 3 have been identified in the solvolysis of Te(OH), in HF, while in the hydrolysis of TeF,, products with tz = 0 to 5 were observed. Solvolysis of selenic acid in H F leads to pentafluoro-orthoselenic acid and two other products, one of which is probably HSe03F.s02 Course of Reactions. Li and Mg. The cis-trans isomerization of (E)- and (2)-1-lithio-1-phenyl-1-butenehas been followed by IH n.m.r. spectroscopy as a function of solvent, and evidence found for isomerization via an ion-pair intermediate.*03 Dynamic nuclear polarization parameters have been reported for 7Li ions in collision with several radical anions and with one radical cation. All the systems show a large negative 'Li n.m.r. enhancement indicative of weak scalar relaxation, Radical-induced relaxation rates derived from 7Li relaxationtime measurements suggest stronger complexing of Li+ with radical anions rather than with the radical lSF N.m.r. spectra of the reaction of C,F,Br and Mg show the formation of RMgX and then R2Mg.soa Ti, Zr, Nb, Ta, Mo, W, Mn, and Re. lH N.m.r. spectroscopy has been used to follow reactions such as that between Bz3AI and Bz,Ti, eliminating toluene to give catalytic systems,*06and to follow exchange between M(0213CNMe,), and 12C02,where M = Zr, Ti, Nb, Ta, W, and activation parameters were deter* 0 8 (qs-C7Hs)Mo(CO), reacts with HBF4 or HCI to give [(C,H,)Mo(CO),]+[BF,]- and C,H,Mo(CO),CI respectively. [(C,H,)Mo(CO),]+ reacts with PPh3 to give [C,H,PPh3]+ (13C n.m.r.).80glH N.m.r. spectroscopy has been used to monitor reaction of BzCOMn(CO), with PPh3,810and the kinetics of the isomerization below and A H * were determined.s11

'*

'08

*02

803 804

ao8

T. K. Leipert, W. J. Freeman, and J. H. Noggle, J . Chem. Phys., 1975, 63, 4177. Y. Kawasaki and K. Hashimoto, J. Organotnetallic Chem., 1975, 99, 107. S. 0. Wandiga, J.C.S. Dalton, 1975, 1894. R. R. Knispel and M. M. Pintar, Chem. Phys. Letters, 1975, 32, 238 (Chem. Abs., 1975, 83, 48 893). U. Elgad and H. Selig, Inorg. Chem., 1975, 14, 140. E. J. Panek, B. L. Neff, H. Chu, and M. G. Panek, J . Amer. Chem. Soc., 1975, 97, 3996. J . A. Potenza, J. W. Linowski, E. H. Poindexter, B. E. Wagner, and R. D. Bates, jun., Mol. Phys., 1975, 29, 1597. H. W. H. J. Bodewitz, C. Blomberg, and F. Bickelhaupt, Tetrahedron Letters, 1975, 2003. P. Pino, G . Consiglio, and H. J. Ringger, Annafen, 1975, 509. M . H. Chisholm and M. Extine, J.C.S. Chem. Comm., 1975, 438. M . H. Chisholm and M. Extine, J . Amer. Chem. SOC.,1975, 97, 1623. A. Salzer and H. Werner. J . Organometallic Chem., 1975. 87, 101. D. Drew, M. Y . Darensbourg, and D. J. Darensbourg, J . Organometallic Chem., 1975, 85, 73. W. R. Cullen and F. L. €IOU,Canad. J . Chanr., 1975, 53, 1735.

Spectroscopic Properties of Inorgartic and Organometallic Compounds

86

(OC),y?M '(CO), \

(OC),MLAs Me, M e2A&MC0)4 / \

'F

F

Fe, Ru, and 0s. Thermolysis of (y4-cyc1openfadiene)Fe(CO), in a sealed n.ii1.r. tube to give [(+C,H,)Fe(CO),],, cyclopentane, and cyclopentene does not obey a simple rate law.812 Extensive use has been made of variable-temperature 31P n.m.r. spectroscopy to investigate the reaction of RuC12(PPh3)*with several PR,-type ligands,*13and IH n.m.r. spectroscopy has been used to demonstrate deuteriation of H,Os,(CO),(C= CH2).B14 Co. Photolysis of (y6-C5H,)Co(CO), to give (q5-C,Ha)oCo,(CO), and ~ ~rate ~ p y . [(y6-C6H5)Co(C0)I3has been followed by 'I3 n.m.r. ~ p e ~ t r ~ The of hydrogen exchange measured for cobalt(ri1) ammines reflects the trans-effect. Large inductive effects of [CNI- and in some cases [NO,]- offset the effect of the magnetic anisotropy of cobalt which accounts for ammine lH chemical shifts in most complexes.s16 Similar exchange rates have been determined for [C~(tren)(NH,)Cl]~+'.*~~ Each malonato-group in [Co(en)(mal),]- has inequivalent methylene protons, one in the Hs position between the malonato-rings and the other in the HA position near the ethylenediamine group. In D20-D2S04 mixtures these protons undergo exchange with deuterons, and the protons in the HB position are replaced first; A H * and AS* were derived.818 A transient intermediate has been detected by stopped-flow pulse Fourier-transform 'H n.m.r. spectroscopy during the reaction between an excess of Co(acac), with N-chlorosuccinimide. The intermediate is believed to be [(acac),CoOCMe-

I

CHCICMeO]+.sls IH N.m.r. spectroscopy has been used to follow the stereoselective hydrogen exchange at the methylene group of glycine in the A-R(N-benzylglycinato)bis(ethylenediamine)Co"l ion,82oand I3C n.m.r. spectroscopy has been used to follow the biosynthesis of vitamin B12.821The rate of formation of Ph(MeO)P(O)Co(dmg),L has been determined.822 Rh and Ir. The displacement of ethylene from (q6-C6H,)Rh(y2-C2H4)2 823 and CO from Rh2C12(CO)4824 by phosphorus compounds has been studied by lH n.m.r. spectroscopy. An n.m.r. study of the reaction of [MC1(y4-cyclo-octadiene)l, T. H. Whitesides and J. Shelly, J. Organonietallic Chem., 1975, 92, 215. P. W. Armit, A. S. F. Boyd, and T. A. Stephenson, J.C.S. Dalton, 1975, 1663. W. G. Jackson, B. F. G . Johnson, and J. Lewis, J . Organometallic Chenz., 1975, 90, C13. K. P. C. Vollhardt, J. E. Bercaw, and R. G . Bergman, J . Organoriietallic Chern., 1975, 97, 283.

816

H. Yoneda, U. Sakaguchi, and K. Maeda, Cheni. Letters, 1 9 7 5 2 , 107 (Chem. Abs., 1975, 82, 13 1 679).

817

8ao

D. A. Buckingham, P. J. Cresswell. and A. M. Sargeson, Inorg. Chem., 1975, 14, 1485. M. E. Farago and M. A. R. Smith, Inorg. Chim. Acta, 1975, 14, 21. D. A. Couch, 0. W. Howarth, and P. Moore, J.C.S. Chem. Comm., 1975. 822. B. T. Golding, G. J. Gainsford, A. J. Herlt, and A. M. Sargeson, Angew. Chem. Internat. Edn., 1975, 14, 495. A. I. Scott, Tetrahedron, 1975, 31, 2639. W. C. Trogler, L. A. Epps, and L. G. Marzilli, Inorg. Chem., 1975. 14, 2748. R. Crarner and L. P. Seiwell, J . Orgunometallic Client., 1975, 92, 245. A. J. Deeming and P. J. Sharratt, J . Organomerallic Chem., 1975, 99, 447.

87 (M = Rh, Ir) with the ligands PCInPh3-n has shown that MC1(~4-cyclo-octadiene)PCInPh3-, is first forlned and then MCI(PClnPh3-n)3.S25 Hydride transfer from JrH,L, to Pt,Cl4L2or Pd,CI4L2(L = PPr,) has been investigated by and 31P n.m.r. spectroscopies and shown to involve ~istrans-H,(Pr~P)~Ir(p-H)(p-Cl)PtClPPry.s28 Ni. lH and 31Pn.m.r. spectra have been used to determine the rate of reductive elimination of toluene from (Et3P)2NiMeAr.827Thermal decomposition reactions of (q6-C,H,)Ni(PPh3)R have been studied in aromatic solvents using lH n.m.r. spectroscopy. Compounds containing a @-hydrogen atom decompose via a @-eliminationreaction and the others via a unimolecular reaction which does not involve free radicals. The order of stabilities is Me3SiCH, > PhCH, > Me 3 Et x Bu* > Prn > Bu* z B U . ~ , *lH N.m.r. spectroscopy has also been used to determine the rate of deuterium exchange with Ni", Pb", and Zn" complexes of [(H02CCH,)2NCHPhC0,]-.s2G The interchange between co-ordinated and unco-ordinated acetyl groups in (107) has been followed by 'H n.1n.r. spectroNuclear Magnetic Resonance Spectroscopy

(107)

scopy with some of the hydrogen atoms of the unco-ordinated acetyl groups replaced by deuterium for the purpose of 'labelling'. The process follows firsts. The order kinetics with rate constant k (at 35 T ) = (0.81 ? 0.05) x activation energy for the isonierization was calculated as 17.4 k 0.7 kcal mol-1 and AS,,,* = -20.9 & 2 e.u. It was concluded that a CO group has a significant lifetime co-ordinated to the nickel(i1) ion. The implications of this conclusion, which relate to a possible mechanism for reaction of this compound with amines to give a macrocyclic complex, were d i ~ c u s ~ e d . ~ ~ ~ Pd, Pt, nnd Au. 'H N,m.r. spectroscopy has been used to follow the oligomerization of ButC=CH by PdC1,(PhCN),,831 and to study the rearrangements B. Denise and G . Pannetier, J. Organometullic Chem., 1975, 99, 455. J. P. C. M. van Dongen, C. Masters, and J. P. Visser, J . Organometallic Chem., 1975, 94, C29.

D. G . Morrell and J . K. Kochi. J . A m w . Clzern. Soc., 1975. 97, 7262. J . Thonison and M . C. Baird, Inorg. Chin?. Actm, 1975, 12. 105. L. G . Stadtherr and R . J. Angelici, Inorg. Chem., 1975. 14, 925. w U L. A. Funke and G . A. Mclson, Inorg. Chetjt., 1975, 14, 306. R:'l B. E, Mann, P. M. Bailey, and P. M. Maitlis, J . Amer. Chem. Soc., 1975, 97. 1275. bda D J. Mabbott, P. M. Bailey, and P. M. Maitlis, J C.S. Chem. Comm., 1975, 521.

R27

88

Spectroscopic Properties of Inorganic and Organometallic Compounci~~

From 'H, 13C(*H), and 31P(1H) n.m.r. data for (Ph2PMe)2Pd(N3)2 and (Me2PPh),Pd(N3), it was concluded that the magnitude of 2J(31P-31P)is greater for the azido-complexes than for the corresponding chloro-complexes. The energetics for cis + trans isomerization were determined. Evidence was found for non-ionic and five-co-ordinate intermediates in solutions containing the complexes and amines or p h o ~ p h i n e s .The ~ ~ ~reaction of Pd(PPh3)4, Pt(PPh,),, and Pt(PPh3)4 in DCl to give MCI2(PPh3),, which in the case of palladium goes on to [Pd2C16]2-,has been monitored by 31P n.m.r. spectroscopy, and a Pt-D intermediate was detected.834 'H N.m.r. spectroscopy has been used to follow methyl or halogen exchange between Au', Au"', Pd", and Pt", and it was proposed that exchange proceeds uia a S E cyclic ~ The reaction of cis-PtMe,(PMe,Ph), with cis-Pt(NO,),(PMe,Ph), has been shown to give cis-PtMe(NO,)(PMe,Ph),, which then isomerizes to the more stable t r a n ~ - i s o i n e r . The ~ ~ ~ rate of allene insertion into the Pt-Me bond in [Pt Me(-q2-C3H4)(PMezPh)J+837 and of the exchange between Pt,Cl,(+deuteriated3,3-dimethyl-pent-l-ene), and the free alkene have been determined. 13C N.ni.r. spectroscopy has been used to show that alkenes of the type RCMe,CH=CH2 undergo H-D exchange with D20-HOAc (containing perchloric acid) in the presence of a homogeneous Pt" Crown ethers have been used to take KPtCI3(C2H,) into CDCI3 and the process was followed by lH n.ni.r. spectroscopy. The 13C n.m.r. spectra were also noted.840 The reactions between K2PtC14and 2-propenol, 2-butenol, and 3-buten-2-01 have been followed by 'H n.m.r. spectroscopy, and [PtCl,(olefin)]- is first formed, followed by a rearrangement into ci~-PtCl,(diolefin).~~~ 'H N.m.r. spectroscopy has also been used to monitor the replacement of nitrogen by DMSO in L2Pt [L = (108)],842 and the deuteriation of Pt2C14(PR3)2.843

Hg. The reactions of Me,Sn2 and HgC12 and MeHgC1, which give evidence for Me8SnHgMe,844~ 845 and between (dpm),Hg and HgX2 to give (dpm)HgX, where equilibrium constants and AGO were determined,84s have been followed by *H *3s

836

nss 840 841 84a

n43 844

D. A. Redfield, L. W. Cary, and J. H . Nelson, Inorg. Chem., 1975, 14, 50. K. B. Dillon, T. C. Waddington, and D. Younger, J.C.S. Dalton, 1975, 790. R. J. Puddephatt and P. J. Thompson, J.C.S. Dalton, 1975, 1810. P. J. Thompson and R. J. Puddephatt, J.C.S. Chem. Comm., 1975, 841. M. H . Chisholm and W. S. Johns, Inorg. Chem., 1975, 14, 1189. C. Masters and P. A. Kramer, Rec. Trav. chim., 1975, 94, 25. P. A. Kramer and C. Masters, J.C.S. Dalton, 1975, 849. R . T. Gray and D. N. Reinhoudt, Tetrahedron Letters, 1975, 2109. J. Hubert and T. Theophanides, J. Organometallic Chem., 1975, 93, 265. N . Hadjiliadis and T. Theophanides, Inorg. Chim. Acta, 1975, 15. 167. A. A. Kiffen, C. Masters, and L. Raynand, J.C.S. Dalton, 1975, 853. D. C. McWilliam and P. R. Wells, J. Organometallic Chem., 1975, 85, 335. D. C, McWilliam and P. R. Wells, J . Organometallic Chem., 1975, 85, 347. R. H. Fish, R . E. Lundin, and C. G. Salentine, J . Organometallic Chem., 1975, 84, 281.

Nu clear Magnetic Resonance Spectroscopy

89

OH OH

( 108)

n.m.r. spectroscopy. The reaction of MeCH(OH)CH,HgClO, with NaNO, to give MeCH(N02)CH2HgC104has been followed by lH n.m.r. spectroscopy and the amount of mercurial co-ordinated by the nitrite ions was evaluated by analysing the geminal J(lH-lsDHg). Thus rate constants and activation IH N.m.r. parameters were derived for both the aquo- and nitrito-mercurial~.~~~ ClDNP has been observed in reactions between photolysed (Me,Ge),Hg and Bu~CI.~~* B and Al. IlB N.m.r. spectroscopy has been used to follow the hydrolysis of [BH,]- to boric acid in DMSO by acidic and to investigate the reaction of (Me2NBH& with LiAIH, to give [Me,NBH,]- and [Me.LNBH2NMe2BH3]-.860 In T H F solution, [Al(BH4)4--nBrn]-decomposes to [B,H,]-, [AlBrJ-, and a butoxy-derivative of Al(BH4),. 27Al N.m.r. spectra indicate the formation of [A1(BH4),]-, [AI(BH4),Br2]-, and [Al(BH,)Br,]- as intermediate IlB N.m.r. spectroscopy has been used to monitor the reaction of LiNMe, with [Me2NBH212to form B(NMe,), and LiH,852 and to follow the alkolysis of 1,5-B3C2H6.853lH and IlB n.m.r. spectroscopies have been used to study the reaction of B6Hll with ethers at low temperatures, and products such as R2S,BH3, R2S,B4Hs,and [H2B(THF),]+[B,HD]- were The llB n.m.r. spectrum of paramagnetic (q5-C5H6),Fe,C2B6H8shows two resonances of equal intensity at +346 and +700 p.p.m. (cot = 500 Hz) relative to BF,OEt,. This species slowly isomerizes to (log), which has signals at 6 - 142.9, -36.8, -28.1, - 18.1, - 1.8, and + 8.5.856 lH N.m.r. spectroscopy has been used to follow the kinetics of the reaction of BI0Hl2(Me2S), with various acetylenes. AH* and A S * correlate well with the Taft polar-substituent constants for acetylene s ~ b s t i t u e n t s .A~ ~study ~ by llB n.m.r. spectroscopy of the system Prn,B-B,O, shows that scrambling reactions occur between the alkylborane and its oxidation products. This involves a redistribution of the monofunctional (Pr”) and difunctional (-00-) substituents attached to boron, leading to molecules of 847 R48

RSo RBI

Ega R53

RK4 865

S. Shinoda and Y. Saito, J . Organometallic Chem., 1975, 90, 1. M. Lehnig, F. Werner, and W. P. Neumann, J . Organometallic Chem., 1975, 97, 375. L. M. Abts, J. T. Langland, and M. M. Kreevoy, J . Am1.r. Chem. SOC.,1975, 97, 3181. P. C. Keller, Inorg. Chem., 1975, 14, 440. L. V. Titov, E. R. Eremin, and L. N . Erofeev, Fiz. Mat. Metody Koord. Khim., Tezisy Doklady Vses. Soueshch., 5th, 1974, 1974, 101 (Chem. Abs., 1975, 82, 164 353). P. C. Keller Inorg. Chenz., 1975, 14, 438. R. C. Dobbie, E. Wan, and T. Onak, J.C.S. Dalton, 1975, 2603. G. Kodama and D. J. Satumino, Inorg. Chem., 1975, 14, 2243. K . P. Callahan, W. J. Evans, F. Y. Lo, C. E. Strouse, and M. F. Hawthorne, J . Amer. Chem. SOC.,1975, 97, 296. W. E. Hill, F. A . Johnson, and R. W. Novak, Inorg. Chem., 1975, 14, 1244.

90

Spectroscopic Properties of Iizorgariic arid Organoinetaliic Compounds

*c

ou

@Fc

( 109)

varying size and Redistribution reactions for PhBX,-PhBY, and for PhBX2-BY3 have been investigated, principally by llB n.1ii.r. spectroscopy, and A H " and ASo values were Si, Ge, Sn, and Pb. lH N.ni.r. spectroscopy has been used to follow the isomerization of M e 2 S i C H 2 C ( 0 ) o , I to Me,&OC(= CH2)(CH2),J,859and the chlorination of Me,+,Si, and Me,Ge by SbC15,880while 31P n.m.r. spectroscopy was used to follow the reaction between Me,M(OMe),-, and MePC1,,861 and 18F n.m.r. spectroscopy to follow the pyrolysis of MeCF,SiCl, and related compounds.8s2The rapid redistribution of phosphino-groups (PH,) and hydrogen atoms on germanium in phosphinohyridogernianes has been followed by l H n.m.r. spectroscopy and evidence found for GeH2(PH2)2and GeH(PH,), as redistribution products of GeH,PH,. The Me,Ge(PH,),,H,-, system reaches a statistical distribution of H atoms and PH, groups on germanium.863 The ll9Sn nuclei of Me,Sn, formed during the photochemical reaction of Me,SnH with But02But or dibenzyl ketone or during the thermal decomposition of azodi-isobutyronitrile with Me,SnH exhibit CIDNP. The data were fully interpreted and a positive sign was found for a~~~ (h4e,Sn).884 Pair-substitution CIDNP effects have been utilized to study reactions of benzoyloxyl radicals at the metal centres of Pb, Sn, and transition-metal a l k y l ~ .'H ~ ~N.1n.r. ~ spectroscopy has been used to follow the reaction of Bu",SnCH,CH=CH, with CCI, to give C13CCH2CH=CH2 and B U ~ , S ~ CCIDNP I . ~ ~ ~studies have shown that alkyl-lead compounds, when reacting with reactive organic halides, produce lead chlorides and a radical pair in a singlet G. Cros, J. Costes, and J.-P. Laurent, Org. Magn. Resonance, 1975, 7, 78. S. S. Krishnamurthy, M. F. Lappert, and J. B. I'edley, J.C.S. Chem. Comrn., 1975, 1214. 860 A. G. Brook, D. M. MacRae, and A. R. Bassindale, J. Organometallic Chem., 1975, 86, 185. 8 6 0 E. Carberry, T. Keene, and J. Johnson, J. Inorg. Nuclear Chem., 1975, 37, 839. K. M. Abraham and J. R. van Wazer, J. Inorg. Nuclear Chem., 1975, 37,541. 862 W. I. Bevan, R. N. Haszeldine, J. Middleton, and A. E. Tipping, J.C.S. Dalton, 1975, 252. 863 A. R. Dahl, C. A. Heil, and A. D. Norman, Inorg. Chem., 1975, 14, 1095. * a p M. Lehnig, Chem. Phys., 1975, 8, 419. 865 R. Kaptcin, P. W. N. M. van Leeuwen, and R . Huis, J.C.S. Cheni. Conim.,1975, 568. J. Grignon, C. Servens, and M. Pereyre, J. Orgunoinetnllic Chem., 1975, 96, 225. 887 P. W. N. M. Van Leeuwen, R. Kaptein, R. Huis, and W. I. Kalisvaart, J. Organornetullic Chem., 1975, 93, C5.

867 858

Nitclear Magnetic Resonance Spectroscopy

91

P. 31P N.m.r. spectroscopy has been used to monitor the intramolecular cyclization of alkenyl-substituted phosphonium ions such as [Pb,Bz(CH,=CH(CH,),)P]+X-.8ss Direct evidence from 31P n.m.r. spectroscopy has been presented for the formation of a five-co-ordinate intermediate in the Arbuzov reaction : (RIO),P

+

with C12, Br,, or benzenesulphenyl The 31P CIDNP in fourco-ordinate phosphorus-containing radicals has been quantitatively studied by n.m.r. spectroscopy. The greater the lifetime of the ROP(OEt), radical, the greater the coefficient ?f the nuclear polarization amplification. The rate of oxidation of RO(EtO),P to RO(EtO),PO, is 1.4 x lo6 1 mol-ls-l .870 ‘H, 13C, and 31P n.1n.r. spectra of bCH,CH,ObPhX (X == lone pair, S) show that it slowly isomerizes to two isomers XPhP(OCH2CH,0)2PXPh.87119F N.m.r. spectroscopy has been used to follow the isomerization of (1 10) to (CF,),-thiophen

catalysed by PhnPCI3-,; ‘@Fand 31Pn.m.r. spectra were used to provide evidence for LPPb2CI [L = (1 lo)] as an inter~nediate.~~, 4 Paramagnetic Complexes

I n this section, compounds of the d-block transition elements will be considered first and then those of the lanthanide and actinide elements. Papers concerning the use of paramagnetic complexes as ‘shift reagents’ are usually omitted. A number of paramagnetic complexes have been referred to in the references 505, 538, 622, 625, 626, 628-630, 658, 659, 665, 668-671, 674-677, 679, 684, 686689, 691, 692, 696--699, 701---703, 752, 754, 755, 761, 1009, 1018, 1020, 1022, 1031, 1034, 1036--1038, 1041, 1042, 1109-1120, 1129, 1131-1138, 1140, 1141, 1143, 1152, 1165, 1167, 1174-1176, 1182, 1183, 1193, and 1205. A number of reviews have appeared including ‘Recent Results on Paramagnetic Spin-Lattice Relaxation in Hydrated Cobalt, Manganese, and Chromium 869

no0 870

Bil R72

ti73

W. R. Purdum, G . A. Dilbeck, and K . D. Berlin, J . Org. Cheni., 1975, 40, 3763. A. Skowronska, J . Mikoiajczak, and J. Michalski, J.C.S. Chent. Comm., 1975, 791. D . G. Pobedimskii, V. A. Kurbatov, and 1. D . Ternyachev. Fiz. Mat. Metody Koord. Khirn., Tezisy Dokl., Vsrs. S o w ~ l i t h .j, t h , 1974, 1974, 94, ‘Shtiintsa’, Kishinev, U.S.S.R., (Chem. Abs., 1975, 83, 16 355). J. P. Dutasta, A. C. Guimaraes, J. Martin, and J. €3. Robert, Tetrahedron Letters, 1975, 1519. Y . Kobayashi, I. Kumadaki, A. Ohsawa, and Y . Sekine, Tetruhcdron Letters, 1975, 1639. C . J. Gortcr and A. J. Van Duyneveldt, Rev. Mex. Fis., 1974, 23, 343 (Cheni. Abs., 1975, 82, 79 578).

92

Spectroscopic Properties of Inorganic and Organometnllic Compounds

'Application of Paramagnetic Probes in Biological 'Nuclear Magnetic Resonance and the Electronic Structure of the Actinides',875and several reviews of shift reagent~.~'~-88'J Compounds of d-Block Transition Elements.-The effect of an electric field on the relaxation of a spin-4 nucleus by a paramagnetic ion has been calculated. In an optimum case the value of T, may be changed by 50% with electric field strengths of less than 10 MV ~ i i - ' . ~'H ~ ' N.m.r. relaxation has been used to investigate the interaction between transition-metal ions and Bu'COMe. The effect of the paramagnetic ions on the transverse relaxation rate of the But protons was measured as a function of M2+ concentration in water and other 13C Isotropic shifts and linewidths have been measured for a series of paramagnetic transition-metal acetylacetonates. The relaxation pathway of the I3C nuclei is controlled by hyperfine interactions with unpaired electron spin and in cases where the 'H n.m.r. linewidth is dominated by the hyperfine mechanism, good agreement was obtained between the experimental 13C: lH linewidth ratio and that calculated on the basis of the contact shift. Pseudo-contact interactions can be important in determining the total isotropic shift for both 'H and 13Cnuclei and, contrary to previous studies, such effects are also important for V(acac), and M n ( a c a ~ ) , .An ~ ~ investigation ~ of the site of Nd3+,Tb3+,V3+, , Ca3+, and Mg2+ complexation to tetracycline has been Cu2+, Mn2+,C o 2 + La3+, carried out, and isotropic shifts and broadening of certain tetracycline 'H n.m.r. signals were 13C N.m.r. spectra of selected phenyl- and ethyl-substituted metallocenes (M = V, Cr, Co, Ni) have been recorded. Instrumental methods were discussed. It was shown that selective off-resonance experiments can be used to assign the spectra.88S The work was extended to (Bu'C,H,),V and dipolar and contact contributions to the linewidth were separated and the electron-spin relaxation time determined. The zero-field splitting did not affect the electron-spin relaxation. Except for the ring carbon atoms of nickelocenes, the I3C signals of paramagnetic metallocenes should be observed easily.88s 'H N.m.r. spectroscopy has been used to show that VO(acac)dma has unequal broadening of the N-Me 874

875

878 87a 88O

883

88s 884

xn7

R. A. Dwek, R. J. P. Williams, and A. V. Xavier, Metal Ions in Biol. Systems, 1974, 4, 61 Chem. Abs., 1975, 83, 39 577). F. Y. Fradin, Actinides: Efecfron.Sfruct. Relat. Prop., 1974, 1, 181, ed. A. J. Freeman and J. B. Darby, Academic Press, New York (Chem. Abs., 1975, 83, 17 787). D. H. Williams, Pure Appl. Chem., 1974, 40, 25. R. E. Sievers, J. A. Cunningham, and W. E. Rhine, Proc. Rare Earth Res. Con$, l l t h , 1974, 2, 846, ed. J. M . Haschke and H. A. Eick, NTIS, Springfield, Virginia (Chem. Abs., 1975, 83, 90 026). M. Hajek and Z. Ksandr, Chem. fisry, 1975, 69, 225 (Chmr. Abs.. 1975, 82, 177 746). K. Tori, Kagaku (Kyoto), Zokan, 1975, 66, 43 (Chem. Abs., 1975, 83, 185 558). B. A. Levine and R. J. P. Williams, Proc. Roy. Soc., 1975, A345 5. P. W. Atkins and M. J. Clugston, Adv. Mol. Relaxation Processes, 1975, 7 , I (Chem. Abs., 1975, 83, 68 708). C. Jolicoeur and P. Bernier, Chem. Phys. Aqueous Gas Solutions (Proc. Symp.), 1975, 135, ed. W. A. Adams, G. Greer, and J. E. Desnoyers, Electrochemical Society, Princeton, New Jersey (Chem. Abs., 1975, 83, 85 906). D. M. Doddrell and A. K. Gregson, Chem. Phys. Letters, 1974, 29, 512. D. E. Williamson and G. W. Everett, jun., J . Amer. Chem. Soc., 1975, 97, 23Y7. F. H. Kohler, J. Organometallic Chem., 1975, 91, 57. F. H. Kohler, 2. Naturforsch., 1974, 29b, 708. E. Kwiatkowski and J. Trojanowski, J . Inorg. Nuclear Chetti., 1975, 37, 979.

Nuclear Magnetic Resonance Spectroscopy

93

(C,H,)Cr(C,H8) is paramagnetic but the lines are well-enough resolved to indicate that the C8H8 ring undergoes rapid rotation.888 The solvation of inert low-spin Cr‘ complexes by n.m.r. active species in the second co-ordination sphere has been investigated by dynamic nuclear polarization. Only dipolar coupling was observed for [Cr(CN),N0I3- and the nuclear test probes octafluoronaphthalene, P(OMe),, Li+, and [BFJ-. There is little unpaired spin density at the periphery of the nitrosyl complex. With [Cr(bipy),]+, moderate scalar coupling was observed for C ~ Oand F ~P(OMe),, indicating the presence of unpaired spin-density in the plane of the bipy ring at the periphery of the complex. For [Cr(C,H,),]+ strong scalar coupling by transient bonding interaction was observed for P(OMe), and [BFJ-. The absence of scalar coupling with CloF8 was taken as showing a lack of unpaired density above the v-benzene rings, and the small molecules probably penetrate into the The so-called ‘shiftless’ relaxation reagent Cr(acac), has received considerable attention. It can produce shifts, e.g. 0.64 p.p.m., in chloroform however, Cr(dpm), is more soluble and less liable to co-ordinate.8a1 As a reagent for removal of 13C-lH nuclear Overhauser effect, Cr(acac), is not very efficient in medium and large organic molecules, leaving a variable residual enhancement and consequently can even degrade the spectra The outer-sphere adducts of Co(acac),L, and Cr(acac), with CHCI,, CH2C12, PhMe, and PhH have been detected and stability constants determined. The contact and pseudocontact components of the paramagnetic shifts were separated and the Co-N(L) bond-length which was determined agreed with X-ray structural data. The determination of the pseudocontact shift helped to establish the most probable structure of the adducts. The thermodynamic parameters of the external-sphere adducts depended markedly on the nature of the inner-sphere ligands, indicating that the structure of the complex changes on outer-sphere complex The l9F n.m.r. spectrum of Cr(SO,F), is a singlet at -36 p.p.m. (with respect to CFC13).89a By use of the concentration- and temperature-dependence of the n.1n.r. line shifts and broadening, the hyperfine interaction constants, ionligand distances, the lifetime of the complexes, the heat of complex formation, and the activation energy of complex decomposition were calculated for p-tert-butyl benzoate and related complexes of Mo(acac),, MoCI,, WCls, Zn2+, Mn2+, and Ni2+.8e5 The 13C relaxation (TI and T2) and the 13C isotropic contact shift of histidine in aqueous solution at pH 10.5, caused by the presence of Mn2+ ions in low concentrations, have been measured. For all six histidine carbons the TI relaxation times were measured at least at two temperatures (310 and 343 K) and the temperature variation of the T2 relaxation times of the same atoms, as

8Ba

8Q3 894

J. Muller and H . Menig, J . Orgcmometallic Chem., 1975, 96, 83. B. E. Wagner, R. D. Bates, jun., and E. H . Poindexter, Inorg. Chem., 1975, 14, 256. P. M. Henrichs and S. Gross, J . Magn. Resonance, 1975, 17, 399. G. C. Levy, U. Edlund, and J. G. Hexem, J . Magn. Resonance, 1975, 19, 259. G . C. Levy and U. Edlund, J . Amer. Chem. Soc., 1975, 97, 4482, V. M. Nekipelov, A. N. Shupik, and K . I . Zamaraev, Fir. Mat. Metody Koord. Khim., Tezisy Dokl. Vses. Soreshch., 5th, 1974, 1974, 113 (Chem. Abs.. 1975, 82, 148 013). S. D. Brown and G . L. Gard, Inorg. Nuclear Chetn. Letters, 1975, 11, 19. R. B. Svitych, A. L. Buchachenko, 0. P. Yablonskii, A. A. Petukhov, V. A. Belyaev, and A. K . Kobyakov, Kinerika i Kataliz, 1974, 15, 1300.

94 Spectroscopic Properties of Iiiorgnnic aiid Organometnllic Conlpourds well as the isotropic contact shift for five of the histidine carbons and the water protons, were measured over a temperature range of 70-80 "C. From thesc results the number of histidine molecules i n the co-ordination sphere of the metal ions and the coupling constants for the hyperfine interaction between the unpaired electrons and the individual 13C nuclei in these molecules have been evaluated, as well as the kinetic parameters for the exchange of the histidine ligands between the co-ordination sphere and the bulk histidine solution. Furthermore, it is found that the experimental results can be interpreted in terms of the model of Bloembergen and Morgan, according to which the electronic relaxation is caused by collision modulation of a transient zero-field splitting interaction. Thus, the experimental results have yielded information about the zero-field splitting interaction and the electronic relaxation and its temperature dependence. Likewise, estimated values of the correlation time for the molecular diffusional rotation and its activation energy have been obtained. Based on these results, i t has been concluded that, whereas the spin-lattice relaxation of the 13Cnuclei caused by the unpaired electrons is due to the dipolar interaction only, the paramagnetic contribution to the 13C spin-spin relaxation is primarily controlled by scalar interaction. Finally, it was found that the distances between the Mn2+ion and the individual carbon atoms in the ligand evaluated from the dipolar relaxation terms are in agreement with an octahedrally co-ordinated Mn2+complex and correspond, with a single exception, closely to the distances expected from the crystal structure of the bis(histidin0)-nickel(i1) complex. The experimental accuracy of the structural parameters obtained by this method for a metal complex in solution is found to be comparable to the accuracy of X-ray structures of similar compounds in the crystal phase.8Bs The temperature- and concentration-dependence of TI and T2 for 'H nuclei in solutions of Mn2+in HCI (0-8 11101 1-l) have been investigated. Addition of HCI to the Mn2+solution did not affect the dipole relaxation of the water protons and thus C1- does not enter the inner co-ordination sphere of Mn2+, which retained the form [Mn(OH2)6]2+ for < 4.5 M-HCI. In contrast to T,-', the T2-' was highly sensitive to the change in HCI concentration. For 1.5 M HCI, [ M I ~ ( H ~ O ) ~and ] ~ +the - outer-sphere [Mn(l-l,0)6]2tC1- complex are present in amounts of 60 and 40% respectively in solution. The dependence of the H i relaxation rate on M n 2 +concentration in 5 M-HCl was examined. With increasing Mn2+ concentration, the equilibrium shifted to the formation of the outersphere complexes. In 8-10 M HCI, a neutral inner-sphere complex of Mn2+ with 2C1- occurs.8g7 Relaxation times of aqueous Mn(NO,), solutions vary from 1.5 x 10-lO to 2.0 x s for concentrations 5 4 . 5 mol l-1,89Rand these measurements were then applied to aqueous glycerine and aqueous sugar The paramagnetic contribution to the lH and 13C n.m.r. relaxation rates in the EtOH-Mn2+ system has been calculated, and correlation times for the dipolar and scalar parts have been discussed and evaluated.g00 From 13C n.ni.r. studies on pyridine solutions containing Mn(acac),, Ni(acac),, Co(acac),, 806

*@'

88LI

8pB @O0

J. J. Led and D. M . Grant, J . Amer. Chcnr. SOC.,1975, 97, 6962. V. A. Glebov and T. M . Nikitina. Koord. Khitiz., 1975, 1 , 1106. G . P. Vishnevskaya, F. M. Gumerov, and €3. M . Kozyrev, Teor. ic.hsp. Khim., 1975, 11, 199. G. P. Vishnevskaya, F. M . Gumerov, and €3. M . Kozyrev, Tc.or. i rksp. Khini., 1975, 11, 205. E. Tiezzi and G. Valensin, Org. Mogn. Resonance, 1975, 7, 602.

Nuclenr. Mognetic Kesonunce Spectroscopy 95 and Cu(acac),, the induced chemical shift, the linewidth, and T, due to the paramagnetic metals have been derived. The origin of the paramagnetic effects on the 13C n.ni.r. spectra induced by Co(acac),, Ni(acac),, or Cu(acac), is mainly the contact interaction, whilc the 13C n.m.r. spectra of the pyridine-Mn(acac), system cannot be similarly interpreted.gu0'The 'H n.1n.r. spectra of a series of Mn-porphyrin derivatives have been analysed and assigned. The isotropic shifts were shown to be predominantly contact in origin, reflecting extensive porphyrin to metal n-bonding. This spin-transfer mechanism is consistent with the decrease in the extent of spin transfer with increasing n-donor properties of the axial halogen, while nitrogeneous bases have no effect * 0 2 The binding of Mn2+to peptides and amino-acids has been examined.903 lH N.1n.r. studies have been carried out o n flavoquinone complexes of Mn", Fe2+,Co2+,Ni", and Cu2+. The paraniagnctic contribution to the linewidth of the ligand resonances was analysed in order to estiniate the value of the correlation times involved in the relaxation processes. The isotropic shifts were analysed in terms of contact and pseudocontact interactions and structural information derived. The mechanisni of the contact delocalizalion was discussed.SoJ 'H N.ni.r. spectra were used to investigate the binding of Mn2+,Co2+,Ni2+,and C h 2 + to adenosine and ~ y t i d i n e . ~ ~ ~ The 13C n.m.r. spectra of cytidine, deoxycytidine, and related conipounds have been recorded in the presence of Mn2+ and Cu". The primary binding site of Mn2+ was the phosphate group while Cuzt interacts with the base residues.goa However, similar work on the binding of Mn2+ to inosine 5'-triphosphate indicates that the Mn2+ interacts at two distinct sites, namely C=O and N-7, and lifetimes were deterniined.*07 31PN.m.r. studies on the Mn2+-ATP system indicate that two n.m.r. exchange mechanisms are present in solution; namely the Eigen-Tanim mechanism and the direct ligand-exchange mechanism. Their respective contributions to the observed n.1n.r. linewidths and hence to the n.ni.r. exchange-rate depend upon the concentration of the ligand ATP. Equations were developed to prove what n.ni.r. 'sees' for the Eigen-Tamm mechanism, and these equations were applied.g08 The calculation of n.ni.r. relaxation rates due to electron-nuclear dipolar interaction in paramagnetic complexes has been extended to include the distribution of the electronic unpaired spin density on the metal and the ligand orbitals. The numerical values are in good agreement with the available experimental data.g0g 'H N.ni.r. isotropic shifts have been measured for the high-spin [CIO,],- (M = Fe2+, Co2+, Ni2+). The octahedral complexes [M(i~nidazole),]~-' isotropic shifts were interpreted as being primarily contact in nature, being 95% contact for M = Co. Possible spin-delocalization mechanisms were discussed.*'O Bu3 u04 *06

807

Oo8

K. Hayamizu, M. Murata, and 0. Yamamoto, Bull. Chern. Soc. Japan, 1975, 48, 1842. G . N . La Mar and F. A. Walker, J . Amcr. Chem. Soc .. 1975, 97, 5103. R. Basosi, E. Tiezzi, and G . Valensin, J . Phys. Chem., 1975, 79, 1725. J . Lauterwein, P. Hemmerich, and J.-M. Lhoste, Inorg. Chem., 1975, 14, 2161. L. G. Marzilli, W. C. Trogler, D. P. Hollis, T. J. Kristenmacher, C.-H. Chang, and B. E. Hanson, Inorg. Cheni., 1975, 14, 2568. H. Fritzsche, K. Arnold, and R. Krusche, Stud. Biophys., 1974, 45, 131 (Chem. A h . , 1975, 82. 125 554). G. P. P. Kuntz and G. Kotowycz, Biochemis/ry, 1975, 14, 4144. G . P. P. Kuntz, Y.-F. Lam, and G . Kotowycz, Canad. J . Chem., 1975, 53, 926. D. Waysbort and G . Navon, J . Chem. Phys., 1975, 62, 1021. M. Wicholas, R. Mustacich, B. Johnson, T. Smedley, and J. May, J. Amer. Chem. Soc., 1975,97,2113.

96

Spectroscopic Properties of itiorgatiic and Orgatiometallic Cornpourids

Binding sites and structure of complexes of Fe(NO), to carbazides, thiocarbazides, amino-acids, and related compounds have been elucidated using 'H and 13C n.m.r. ~ p e c t r o ~ c o p i e The ~ . ~ ~'H ~ n.m.r. spectra of solutions of oxidized glutathione have been studied in the presence of Fez+, Ni2+, and Cu2+.912 Specific assignments of the paramagnetically shifted porphyrin ring proton resonances in the n.m.r. spectrum of iron(m) protoporphyrin IX dicyanide have been made by consideration of the perturbations induced in the spectrum by paramagnetic shift and relaxation The solvent shifts for dicyanoferric porphyrin parallel the hydrogen-bonding donor-strength of the ~ 0 1 v e n t . ~ ~ * 'H N.m.r. relaxation times have been used to characterize some dynamic properties of Paramagnetic model haem complexes. Tl Relaxation of the porphyrin methyl protons in high-spin ferric complexes was shown to arise from dipolar coupling where the correlation time is the electron spin-lattice relaxation time T ~ T~ ; is in turn determined by modulation of the zero-field levels by the tumbling of the complex in solution. The 'H line broadening for certain porphyrins was shown to reflect the motion of the iron atom relative to the haem plane.g15 The 'H n.m.r. spectra of dicyanodeuteriohaeinin show a significant and characteristic concentration dependence in the range 1-1 00 x moll-' typical of associative effects, and the dimerization parameters were determined.g16~917 13C N.m.r. shifts have been measured for a range of paramagnetic iron salicylideniminato-complexes of the type {(N-R-Xsal),Fe},O. In one case the shifts were determined over the temperature range 320--225 K and the carbon hyperfine-coupling and exchange-coupling constants have been obtained. It was concluded that a n-delocalization mechanism is dominant though a-paths to certain nuclei are probably l H and 13C isotropic shifts have been measured for Fe(S,CNR,),. The 13C isotropic shifts were interpreted as arising solely from contact hyperfine coupling and also demonstrate that as the low-spin state of the metal is favoured there is an increase in metal-ligand n-bonding. o-Delocalization of unpaired spin density is more important in determining the 13C isotropic shifts than those of the contiguous For 'H n.1n.r. investigations of (Et2NCS,),FeX there is a marked effect of the T - , term in the iodo-derivative, and this was rationalized in terms of the large ground-state zero-field splitting of the ferric ion. The variable-temperature study has revealed a conformational change in these molecules which has been ascribed to a hindered S2C-N rotation, and thermodynamic parameters have been Although complexes of the type G. Martini, N. Niccolai, and E. Tiezzi, J . Phys. Cliem., 1975, 79, 1721. R. Jezowska-Trzebiatowska, L. Latos-Grazynski, H. Kozlowski, G. Formicka-Kozlowska, and T. Kowalik, Bull. Acad. polon. Sci., SPr. Sci. chim., 1974, 22, 1075 (Chem. Abs., 1975, 83, 21 091). 013 J. B. Brassington, R . J. P. Williams, and P. E. Wright, J.C.S. Chcnr. Comm., 1975, 338. p14 J. S. Frye and G. N. La Mar, J . Amer. Chcmi. SOL.,1975, 97, 3561. G. N. La Mar, Pure Appl. Cltem., 1974, 40, 13. W. Schoessler, J. Fischer, E. Winkler, and R . Hintsche, F.E.B.S. Letters, 1975, 55, 249. u7 W. Schoessler, K. Gerisch, R . Hintsche, K . Pommerening, and P. Mohr, Actu Biol. Mcd. Ger., 1975, 34, 345 (Chem. A h . , 1975, 83, 104 204). K. S. Murray, J.C.S. Dalton, 1975, 1538. A. K . Cregson and D . M . Doddrell, Chmi. Phys. Lctrers, 1975, 31, 125. OZo M. M. Dhingra, P. Ganguli, V. R . Marathe S. Mitra, and R. L. Martin, J . Mrrgrr. Rcsonancr, 1975, 20, 133. 912

Nirclear Magnetic Resonance Spectroscopy

97

OsC12(4-R1CsH4NzCOR')(PPh,), are apparently diamagnetic, the 'H and 13C n.m.r. shifts are paramagnetic in character, but the anomalies were restricted to certain positions of the diazene ligand. Variable-temperature lH n.m.r. spectra suggest that a second-order paramagnetic effect may be responsible.921 New cobal t(IiI)-alkyl complexes of the type Co(CloH14N8)LRhave anomalous n.m.r. spectra which have been ascribed to paramagnetic contact shifts arising from a thermally populated triplet lH N.m.r. spectra of paramagnetic compounds are frequently disturbed by side-bands, which can be avoided, as shown for (q5-EtC5H4)zC~.g23 The effect of some Co2+,Ni2+,and Zn2+salts on the positions of 'H and 14Nresonances in MeCN, Me2C0, ROH, and D M F has been studied, and isotropic shifts of the order lo-lo4 Hz and coupling constants of 104-106 Hz were determined. The decisive factor in spin-density transfer was the symmetry of the complex and the nature of the bonding = acetone, MeOH, The composition and structure of [ C O ( H ~ O ) ~ L ~ - (L ~]'+ MeCN, DMSO, DMF) have been studied as a function of anion, solvent, concentration, and temperature. The electron density is transferred from the central atom to the ligand through 7-r-bonds for water, o-bonds for D M F and DMSO, and by a 7-r-cr interaction in MeCN and Me2C0.g26The paramagnetic shifts in the lH n.1n.r. spectrum of y-picoline in the presence of Ni" and Co" complexes and thiodibenzoylmethane and N-Ph-/%mercaptocinnamamide confirm complex formation.926The use, applicability limits, and precision of n.m.r. spectroscopy for the quantitative determination of geometric parameters of complexes in solution have been investigated. The lH n.m.r. shifts of pyridine, co-ordinated with different nickel(1r) complexes, differ according to the degree of delocalization of spin density onto the pyridine molecule; the symmetry of the ligand fields was compared. The bond length between the metal and the co-ordinating-ligand atom and the angle between this bond and the axis of the complex symmetry were determined for some labile pyridine complexes with Coil and Cu" chelates. The proportionality of contact shifts in Co" and Ni" complexes is correct only for axial ligands. The absolute values of the shifts as well as the bond length between the metal and co-ordinating ligand were affected by the solvent mixture.u27Some octahedral complexes of the type ML4Xz and ML2X2 (M = Co", Ni"; L = y-picoline) have been studied by lH and 19F n.ni.r. spectroscopy. Both cis- and trans-isomers were found and there was a 7-contact interaction of the X(RfC0,-) ligands, particularly when they act as bidentate l i g a n d ~ The . ~ ~ complexation ~ of N-vinyl2-methylimidazole by CoCl, or NiCla has been investigated and it was found that the introduction of the 2-methyl group had increased the rate of exchange.B2g J . Chatt, J . R . Dilworth, and T. Ito, J.C.S. Dalton, 1975, 2348. V. L. Goedken and S . - M . Pcng. J.C.S. Chent. Comrn., 1975, 258. F. H . Kiihlcr, Z.Nuturforsc,/i., 1975, 30b, 649. M. Olczak-Kobza and Z . Kecki, Roczniki Chent., 1974, 48, 2225 (Chem. Abs., 1975, 82, 177 721). A. P. Gulya and V. A . Shcherbakov, Fiz. Mat. hfetody Kourd. Khim., Tezisy Dokl., V s m . (Chem. A h . , 1975, 83, Suveshch., 5th, 1974, 1974, 106, 'Shtiintsa', Kishinev, U.S.S.R., 18 443). M. Chikuma, A. Yokogama, and 11. Tanaka J . Inorg. Nuclear Cliem., 1975, 37 199. V. M . Nekipelov, A. N.Shupik, and K. 1. Zamaraev, Koord. Kliim., 1975, 1, 956. K . G . Orrcll, Inorg. Chim. Actu, 1975, 12, 2 5 5 . V. K . Voronov, E. S. Domnina. N. P. Glazkova, and C;. Ci. Skvortsova, Izocsf. Aknd. Nuuli S.S.S.R., Sor. lihitll., 1974, 2598.

98

Spectroscopic Properties of'Imrguiric und Organonietullic Compounds

The pseudocontact shifts for tetragonal high-spin Co" complexes were calculated using a crystal-field model. The calculated results for the dipolar field strength and its variation with temperature were compared with values derived from ~ +was . experimental measurements on complexes of the type [ C O ( M ~ O H ) ~ L ]It shown that good numerical agreement can be obtained with experimental results for the dipole-field strength and its temperature dependence. However, the calculations show that the linearity found when pseudocontact shifts are plotted against T-l is only apparent, making simple interpretations or extrapolation of the plots so obtained nicaningless.y"o For these complexes the question of how to separate the observed shifts into their respective Fernii-contact and dipolar contributions has been examined, with the result that a new procedure was introduced, and it was found that the mechanism depends on L.931The surfactant Triton X-I 00 interacts with CO(NO,),.~"~ Hyperfine interactions are revealed i n the asymmetric 'H n.1n.r. signal for cobalt and nickel t e t r a - a c e t a t e ~ .l~H~N.m.r. ~ contact shifts have been measured for octahedral cobalt(rr) and nickel(r1) complexes of ketones. Upfield shifts were observed for the methyl and methylene groups directly bound to the carbon group and all the other protons niove downfield. These results were explained in terms of spin-density distribution in the CO group.g34The 'H n.ii1.r. spectra of Co"(bae) and Co"(F,bae) are strikingly different from other low-spin cobalt(i1) derivatives. There is a substantial contact contribution to the isotropic shifts. The pattern of contact shifts was interpreted with the help of CNINDO M O calculations. I t was concluded that a-spin density delocalized into the ligand HOMO. The pattern and magnitude of the contact shifts are surprisingly insensitive to the presence or absence of axial bases. However, the linewidth and therefore the electron-relaxation time are quite dependent on axial ligation and on the nature of the solvent. The temperature dependence of the shifts was Isotropic 'H n.m.r. shifts have been measured for low-spin salicylaldehyde Schiff-base complexes of cobalt(ii), and were shown to arise from both dipolar and contact interaction of comparable magnitude. The contact shift was attributed to spin delocalization involving M L n-charge transfer out of the highest filled n molecular orbital, and it was concluded that the complexes have an electronic ground state with the The previously reported data which were unpaired electrons in the d,, interpreted as evidence of ambidentate metal co-ordination of imidazole and pyrazole have been re-examined. In contradiction to the previous report, the true paramagnetic 'H n.1n.r. shift of the N-1 proton of imidarole was shown to be downfield when this base is co-ordinated eilher to Ni(sa1oph) or to Co(sa1oph). The lH n.m.r. data which were taken as evidence for the existence of two different 1:l adducts between Co(sa1oph) and either imidazole or pyrazole have been shown to be either erroneous or m i ~ i n t e r p r e t e d . ~ ~ ~

--

Q30 981

933 939 03'

938 p37

J. Goodisman, J . Phys. Chmi., 1975, 79, 1206. J . R . Vriesenga and J. Goodisman, J . Magn. Resonance, 1975, 20, 102. L. F. Malysheva and E. E. Zaev, Izcest. bibirsk. Otdel. Altad, Nauh- S.S.S.K., Scr. khinr. Nauk, 1974, 5, 75 (Chetn. Abs., 1975, 82, 74798). A. C. Padmanabhan, G . Rangarajan, and R. Srinivasan, Proc. Nut. Acud. Sci., India ( A ) , 1975, 40, 247 (Chem. Abs., 1975, 83, 211 042). K. Jackowski and Z . Kecki, Magn. Reson. Relat. Phenoni., Proc. Congr. Aniptre, 18th (1974), 1975, 2 , 529 (Cheni. Abs., 1975, 83, 185 882). C. Srivanavit and D. G . Brown, Itiorg. Cheim, 1975, 14, 2950. K. Migita, M. Iwaizumi, and T. Isobe, J . Attier. Chetn. SOC.,1975, 97, 4228. D. J. Doonan and A. L. Batch, J . Artier. Chcm. Sor., 1975, 97, 1403.

Nuclear Magrretic Resotiatice Spectroscopy

99

Comparison of the 'H n.m.r. shifts of the K-- and Ni'+ salts of [tl,B(niethylpyrazole),]- has been used to determine if the methyl group is at C-3 or C-5.938 'H N.ni.r. data for [Ni(6-Me-pyridine),(pyridine),Jtre1i)]~ have been The spin-density distribution in Ni(acac),L, (L. = amine) has been studied by 'H and 13C n.m.r. spectroscopy. For RNH,, the trans conformation of the K chain with respect to the N-C, bond is prevalent while for R,NH this conformation is less important. I n each case the trans-configuration with respect to the C,-CB bond is prevalent.oao K2 and correlation times of complexes of Ni(acac), with aniincs have been determined by l.'C and 14Nn.m.r. spectroscopies. T, is affected by the type of ligand and its length.Da1 The mechanism of delocalization of unpaired electrons in the carbon chain has been determined from 13C n.ni.r. spectra of Ni(acac), complexes with alcohols, amines, and pyridine. The unsymnietric distribution of the spin density in the a-Me derivatives indicated that the Ni-N bonding i n the complex was not orthogonal t o the equatorial plane. Eu and Pr complexes were also The electronspin distribution of some aniline derivatives complexed to Ni(acac), has been deduced from 'H, 13C, and "N contact shifts. The nitrogen hybridization statc was given by the experimental values of uN#/aN and compared to the results of an INDO calculation. An Ni-N distance of 2 A and an electron Tl of s were estimated.g43Similar studies on fluoroaniline (including 19F n.m.r. spectroscopy) have been carried out and similar results obtained. I t was suggested that the CNH, fragment is pyramidal, with an angle of 13--15" between the perpendicular of the C-N bond and the axis of the p-like orbital centred at The effect of frequency o n the effectiveness of Ni(acac), on removing J(1H-31P) has been examined. For PIr1derivatives, the concentration of Ni(acac), at which spin decoupling occurs is proportional to the resonance frequency while the reverse is true for Pv derivatives. For PI'' compounds the governing process is dipole-dipole relaxation while for Pv compounds it is contact r e l a ~ a t i o n946 . ~ ~The ~ ~ isotropic 'El n.ri1.r. shifts in adducts of y-picoline with Nil1 nionothio-/3-diketones have been analysed in terms of theoretical spin densities calculated using INDO theory. For axial ligands, the spin transfer involves 0-,d)-, and n*-orbitals while for equatorial ligands the spin transmission through 0- and &-orbitals suffices to explain the observed shifts.947 There is a correlation between the isotropic contact shifts of the H2 and H3 protons of the +

938 938

940

041

942

B 43

944 94G

946

947

W. H. McCurdy, jun., fnorg. Cheni., 1975, 14, 2292. L. J. Wilson, D. Georges, and M. A. Hoselton, Inorg. C h m i . , 1975, 14, 2968. A. A. Obynochnyi, R. Z. Sagdeev, Yu. N. Molin, and A. I . Rezvukhin, Koorrl. Khitii., 1975, 1 , 817. R. Z. Sagdeev, A. A. Obynochnyi, and Yu. N. Molin, Koord. Khirn., 1975, 1, 897. Yu. N. Molin, Fiz. M at . Metody Koord. Khini., Tezisy Dokl. Vses. Soceshch., 5th, 1974, 1974, 6 (Chml. Abs., 1975, 82, 162549). C. Chachaty, A. Forchioni, J . Virlet, and J . C. Ronfard-Haret, Chem. Phys. Letters, 1974, 29, 436. C. Chachaty, A. Forchioni, and J. Virlet, Canurl. J . Chem., 1975, 53, 648. Yu. Yu. Samitov, T. A. Zyahlikova, and V. K. Kurpnov, Doklady Akad. Nauk S.S.S.N., 1975, 220, 1137. T. A. Zyablikova, E. 1. Zoroatskaya, and Yu. Yu. Samitov, Fiz. Mat. Mctodj- Koorcl. Khim., Tezisy Dokl., Vses. Soveshch., Sill, 1974, 1974, 99, 'Shtiintsa', Kishinev, U.S.S.R. (Chrni. Abs., 1975, 83, 5 3 256). M. M . Dhingra, B. Maiti, and R. M. Sathe, Inrliun J . Chem., 1975, 13, 359 (Chenr. Abs., 1975, 83, 18 557).

100

Spectroscopic Properties of Inorganic and Organometnllic Compounds

co-ordinated pyridine bases and the Taft ci* values of the substituent group R in Ni(S,COR),. An explanation based on a detailed study of the change in energy levels of the individual metal d-orbitals was proposed for the observed correlation which implies that the relative strength of the Lewis acid-base interaction can be inferred from contact shift studies.y4* l H N.m.r. contact shifts and isotropic electron spin-nuclear spin hyperfine coupling constants have been given for amine adducts of (RpNCSg)2Ni.ygg Electron-nuclear spin-spin hyperfine interaction constants and spin densities have been derived for (R2NCS2)2N i@-pic~line),.~~~ g3CuN.1n.r. transitions of Cu2+ions have been detected in Zeelnan-perturbed quadrupole levels in the exchange-coupled pair Cu,(OAc),(OH,),. The electric quadrupole coupling tensor at the copper nuclear site was determined. The temperature dependence of the T, rate along the x-axis is proportional to the triplet-spin population, which is compatible with the model that the relaxation is brought about by the fluctuation of the hyperfine coupling via triplet spins. The second-order perturbation of the static part of the hyperfine coupling results in indirect nuclear spin coupling in the exchange-coupled pair.g51 The demagnetization and chemical shifts of glycerol containing water and Cu2 have been The ‘H n.m.r. spectra of a series of bis(N-alkylsalicylaldiminato)copper(ir) complexes have been recorded and the isotropic shifts factorized into dipolar and contact contributions. The lH n.ni.r. linewidth as well as the contact shift values were found to increase along the series from N-Me to N - B u ~ . ~ ~ ~ The Evans method has been used to determine the magnetic susceptibility of [M(Bu-salen)H,0]+[CI0,]-,@54 Mn, Co, Ni, and Cu derivatives of some b i l i v e r d i n ~ ,and ~ ~ ~ Fe derivatives of ligands such as N(CH,CH2N=CH-2pyridyl),.g5s +

Compounds of the Lanthanides and Actinides. -A discussion of the use of the lanthanides purely as ‘shift reagents’ is not included in this Report. Bleaney’s theory of dipolar shifts or ‘contact-free’ ‘H n.m.r. shifts and Golding’s theory of contact shifts provide bases for the separation of the contribution each makes to experimentally observed n.ni.r. shifts. This treatment makes use of shifts obtained with several selected lanthanides but does not require a prior knowledge of the structure of the ligand adduct other than effective axial symmetry around the l a n t h a r ~ i d e . The ~ ~ ~ temperature dependence of the paramagnetic shifts induced by Eu(fod), i n lH n.ni.r. spectra of ethylene oxide can be described 948 OP9

OS1

OL2

8 ~

964

OS6 956 957

Y. Y. Lim and K. L. Chua J.C.S. Dalton, 1975, 1917. H. J. McCormick and D. L. Greene, J. Co-ordination Cheni., 1974, 4, 125 (Chcrrz. A h . ,

1975, 82, 79 875). A. T. Pilipenko, N. V. Mel’nikova, and N. M. Pashkova, Zhur. nmrg. Klzim., 1975, 20, 155. A. Kawamori and G. Soda, Mol. Phys., 1975, 29, 1085. Z. Frait and D. Fraitova, Prac. Konf. Crsk. Fyz. (Pr.), 3 r , 1973, 141, ed. M. Matyas, Academia, Prague, 1974 (Cheni. A h . , 1975, 83, 52 151). y I. Bertini, A. Dei, and A. Scozzafava, Inorg. Chem., 1975, 14, 1526. L. J. Boucher and C. G. Coe, fnorg. Chrm., 1975, 14, 1289. J.-H. Fuhrhop, A. Salek, J. Sabramanian, C. Mengersen, and S. Besecke, Annalen, 1975, 1131. M. A. Hoselton, L. J. Wilson, and R. S. Drago, J. Amer. Chern. Sac., 1975, 97, 1722. C. N. Reilley, I3. W. Good, and J. F. Desreux, Ana/.vt. Cheni., 1975, 47, 2110.

Nuclecir Magnetic Resortaitc*eSpectroscopy

101

using a modified Swift-Connick equation. The upper limits of the mean lifetimes of the Eu(fod),-ethylene oxide adduct were estimated and the activation energy is 13.7 kcal mol-1.9581959 I t has been shown that the 13C chemical shift of a mixture of Me,CO and Yb(fod), is very temperature-dependent, changing by 15 p.p.ni. over a temperature range of 200-310 K, and can therefore be used as an n.m.r. thermometer. The tetramethylsilane signal was also temperaturedependent, varying over a range of 0.3 p . p . ~ n . ~Equimolar ~O mixtures of Ln(fod), and C3F7C0,Ag act as shift reagents for alkenes in CCI, or CDCI, solution.961 Eu(dpm),-induced shifts of aliphatic aniines, alcohols, and pyridines have been examined with respect to steric, electronic, and solvent effects and can be expressed as an exponential function of these three Oe3 Appreciable lanthanide-induced shifts are observed in the lH n.m.r. spectra of organic and inorganic thiocyanates on addition of Eu(fod), but not in the spectra of isothiocyanates; thus a method is provided for distinguishing between 'H N.m.r. shifts in D Y ( C I O ~aqueous )~ solutions have been measured as a function of temperature and Dy3+ concentration. The contact and pseudocontact shifts were separated by means of a least-squares method based on their different temperature variations (as T-' and T - 2 respectively). The hyperfine coupling constant between the Dy unpaired electrons and the proton nuclei and the spin density at the proton nuclei were calculated, and compared with those obtained for other lanthanides. Linewidth measurements yielded an estimation for the water-exchange rate. The electronic relaxation times were calculated and the activation energies for the relaxation processes present in solution were A new method to separate lanthanide-induced shifts into contact, pseudocontact, and complex formation contributions has been described. I t was proposed that Gd(fod),-induced 13C shifts are a versatile measure of the contact contributions for shifts induced by lanthanide shift reagents other than Gd(fod),. Complex formation contributions were discussed.*66 n-Spin densities have been derived for Ln(fod),-induced shifts of aniline and n i - t ~ l u i d i n e . ~ ~ ~ Measurements of solvent TI-' in an aqueous solution of GdCI,, pH 5 . 5 , have been reported as a function of magnetic field and temperature. The data were compared with theory and it was shown that a satisfactory fit may be obtained for a range of values of the parameters of the theory. The interpretation of the results is ambiguous, depending on the unknown relative magnitudes of the residence lifetime, T M , of a proton in the first hydration sphere of the [Gd(rrq)13 ion and the of the proton on the ion. It was pointed out that many workers refer to T M but no experiments have been published that report values of T M for the protons on the [Gd(aq)13+."* Fortunately it was later shown that ThZ 9 TIM, Yu. Yu. Saniitov and Sh. S. Bikeev, Org. Magn. Resonance, 1975, 7 , 467. Yu. Yu. Saniitov and Sh. S. Bikeev, Doklady Akad. N ~ i i hS.S.S.R., 1974, 218, 145. ti. J. Schneider, W. Freitag, and M. Schommer, J . Mogn. Resonance, 1975, 18, 393. D. F. Evans, J. N. Tucker, and G. C. de Villardi, J.C.S. Cheni. Conun., 1975, 205. 8u2 Y. Sasaki, H . Kawaki, and Y. Okazaki, Chcm. and Phorni. Bull. (Jopun), 1975, 23. 1899. Oo3 Y. Sasaki, H . Kawaki, and Y . Okazaki, Chem. and Pharni. Birll. (Jupan), 1975, 23, 1905. S. J. Anderson and A. H . Norbury, J.C.S. Cheni. Cunilri., 1975, 48. 986 J. Granot and D. Fiat, J . Magn. Resorianw, 1975, 19. 372. K . Ajisaka and M. Kainosho, J . Amcr. Clirni. Soc.. 1975. 97, 330. m 7 M. Hirayama, N . Sato. M . Takeuchi, and M. Saito. 81~11. Cficni. Soc. J q w t i , 1975, 48, 2690. OBN S. H . Koenig and M . Epstein, J . Chcni. f.'hj.s., 1975. 63, 1779. 06n

OKB

102

Spectroscopic Ptwperrics of Inorganic and Organonietallic Conipaimds

as this condition must be met for the ratio of T,-* for 'H and 2H to be the

theoretical 42.4. For aqueous Gd3+solutions the ratio was measured as 45.3.Dfi9 Eu(fod), has little effect on TI of however, [Gd(edta)]- is a 13C n.m.r. T, reagent for some functional surfactants in aqueous ~ o l u t i o n .N.m.r. ~ ~ ~ studies of differential relaxation and isotropic shifts of various hydrogen atoms in monocarboxylates containing additional 0 or S binding sites for Gd:'t- and Tb31 indicate chelation by 2-hydroxy- and 2-alkoxy-monocarboxylates, whereas 4-hydroxy, 3-alkoxy-, 2-mercapto-, and 2-, 3-, and 5-alkylniercapto-monocarboxylates are primarily ~ n i d e n t a t e . ~ ~ ~ There have been many applications of lanthanide-induced shifts to determine the geometrical structure of ligands in and details of a computer program for the analysis of lanthanide-induced shifts have been However, the warning that differences i n K factors of less than 3:; are not significant has been given.983 Thc i1.m.r. spectra of a series of paramagnetic anionic lant hanide-nitrato-complexes containing N-alkyl-lutidini um cat ions reveal that 3,5-methyl-substitution of the pyridine ring alters the structure o f the ion pair compared to the previously studied 4-substituted case, although the interionic distance (7 A) appears to remain the samega4 1:1, 1:2, and 1:3 Complex formations, and in some cases stability constants, have been determined for the interaction of some lanthanide compounds with various l i g a n d ~ . ~ ~ ~ - ~ ~ ~ 06* g70

O7l 972

B7J 974

07b

s76

g77 978

979

1x13 084 88K

086 OS7 OM8

gR9 90°

gS1

J. Reuben, J. Chcm. Phys., 1975, 63, 5063. J. Wooten, G. B. Savitsky, and J. Jacobus, J. Amrr. Client. Suc., 1975, 97, 5027. J. M. Brown and J. D. Schofield, J.C.S. C'hcvn. Comrn., 1975, 434. M. R. Harrison, B. E. Moulds, and F. J. C. Rossotti, K. Tek. Hoegsk. Handl. (Contrib. Coord. Chem. Solution), 1972, 261 (Client. Abs., 1975, 82, 162 543). P. Tanswell, J. M. Thornton, V. Korda, and R. J. P. Williams, Europcun J . Biockcm., 1975, 57, 135 (Chein. A h . , 1975, 83, 159373). M. Yu. Kornilov. A. V. Turov, and V. I. Zamkovei, Ukrain. khim. Zhur. (Rirss. Edn.), 1975, 41, 796 (Chcm. Abs., 1975, 83, 139 102). V. V. Yastrebov and A. I. Chernyshev, Tr. Mosk. In-Ta Tonkoi Khini. Tdihnol,, 1974, 4, 7 (Chem. Abs., 1975, 83, 88 202). D. K. Lavallee and A. H. Zeltmann, Prod. R w e Earth Res. Con$, Ilrh, 1974, 1, 218, ed. J. M. Haschke and H. A. Eick, NTIS, Springfield, Virginia (Chem. A h . , 1975, 83, 54 782). K. L. Servis and D. J. Patel, Tetrahedron, 1975, 31, 1359. C.-Y. Lee and M. J. Raszka, J. Magn. Resonance, 1975, 17, 151. R. E. Cramer, C. K. Furuike, and R. Dubois, J. Magn. Resonance, 1975, 19, 382. F. Inagaki, S. Takahashi, M. Tasumi, and T. bliyazawa, Bull. Chem. Soc. Japun, 1975, 48,

1590. C. M. Dobson, L. 0. Ford, S. E. Summers, and R. J. P. Williams, J.C.S. Faraday I I , 1975, 71, 1143. R. H. Newman and G. Neal, N.Z. Dept. Sci. Ind. Res., Chem. Dic., Rep. Report N o . C . D . 2171, 1974 (Chcnl. Abs., 1975, 82, 36 939). H.-J. Schneider and E. F. Weigand, Tetrrihedron, 1975, 31, 2125. M. S. Quereshi and 1. M. Walker, Inorg. Chem., 1975, 14, 2187. V. A. Bidzilya, N. K. Davidenko, L. P. Golovkova, and K. 9. Yatsimirskii, 7cor. i e l i s p . Khiin., 1975, 11, 388 (Chem. Abs., 1975, 83, 121 747). S. J. Angyal and R. J. Hickman, Austral. J . Chem., 1975, 28, 1279. Y. Sasaki, H. Kawaki, and Y . Okazaki, Chem. and Pharm. Bull. (Japon), 1975, 23, 2432. F. Inagaki, S. Takahashi, M. Tasumi, and T. Miyazawa, Bull. Chetn. Soc. Japan, 1975, 48, 853. R. E. Cratner, R. Dubois, and C. K. Furuike, Inorg. Chenz., 1975, 14, 1005. K. Ajisaka and M. Kainosho, J. Amer. Chem. Soc., 1975, 97, 1761. H. Grasdalen, T. Anthonsen, B. Larsen, and 0. Smidsrrad, Acfa Chem. Scand. ( B ) , 1975, 29, 17. H. Grasdalen, T. Anthonsen, B. Larsen, and 0. Smidsrerd, Acta. Chem. Scand. ( B ) , 1975, 29, 99.

Nuclear Magnetic Resonance Spectroscopy

103

The ’H n.1n.r. signals of the paramagnetic [IJ(CHzSiMe3)e]2-are at r 11.2 (SiMe,) and T 19.6 (CH,),993and (C,H,),UR also shows contact shifts.0°4 For (C,H,),UH,BR,, large isotropic shifts were observed. It was possible to separate contact and dipolar contributions. The mechanism of unpaired spin distribution involves negative spin-density on the protons bound directly to uranium. The lH{l’B} n.m.r. spectrum of the fluxional molecule (C,H,),UBHI exhibits collapse of the BH4 resonance at low temperatures. This indicates that the paramagnetism induces sufficient energy separation between the exchanging sites (bridge and terminal hydrogen atoms) for the dynamic intramolecular rearrangement process to be observed. At the estimated coalescence point (-140 ? 20°C) 6w = 15 000 to 36 000 Hz and AG* = 5.0 A 0.6 kcal mo1-1.995 The l H n.m.r. spectrum of U(H,,B(~Z),-~}, has also been From the results of both ‘H n.m.r. spectra and magnetic susceptibility in solution it was concluded that the structure of U’v-fi-diketonate in solution is a square antiprism with higher symmetry than a d o d e c a h e d r ~ n . ~The ~ ’ uranyl ion has been found to enhance the chemical-shift difference between the non-equivalent methylene protons adjacent to the sulphur atom in s ~ l p h o x i d e s . ~ ~ ~

5 Solid-state N.M.R. Spectroscopy This section consists of three parts: ‘Motions in Solids’, ‘Structure of Solids’, and ‘Molecules Sorbed onto Solids’. A number of reviews on aspects of solid-state n.m.r. spectroscopy have appeared and include ‘High-resolution N.m.r. in Solids’,g9g‘Nuclear Double Resonance Spectroscopy of Solids’,looO‘Proton Magnetic Resonance Spectra of Heterogeneous Systems. Applications of Magic-angle Rotation’,lool ‘Pulsed N.m.r. in Static Solids’,loo’ ‘Magnetic Resonance Spectra in Polycrystalline Solids’,loo3 ‘Detection of Weak Interactions in Multiple Pulse N.m.r. ‘Reference List of Inorganic and Organic Solids Studied by Wide-line N.ni.r.’,loo5 ‘N.m.r. Studies on Fine Powders, and Related Current Topics’,1ooe‘N.m.r. in Magnetically Ordered Solids’,1007‘Nuclear Spin Energy Exchange in Solids’,loo8 R. Andersen, E. Carmona-Guzman, K. Mertis, E. Sigurdson, and G. Wilkinson, J. Organometallic Chrm., 1975, 99, C19. OR4 M. Tsutsui, N. Ely, and A. Gebala, Inorg. Chern., 1975, 14, 78. B86 T. J. Marks and J. R . Kolb, J . Amrr. Chenr. Soc., 1975, 97, 27. B B R K. W. Bagnall, J. Edwards, J . G . H. du Preez, and R . F. Warren, J.C.S. Dalton, 1975, 140. C. Miyake, H. Sakurai, and S. Imoto, Chrni. Phys. Lcttws, 1975, 30, 273. 8 9 8 M. M. Dhingra and M. S. Subramanian, Chem. Phys. Letters, 1975, 30, 83. Pep T. Fujito, Nippon Butsrrri Gahkaishi, 1974, 29, 935 (Chem. Abs., 1975, 82, 78 543). l o o 0 €I. Ernst, Wiss. Z., Karl-Mars-Univ., Leipzig, Alnth.-Naturwiss, Reihr, 1974, 23, 449 (Chem. Abs., 1975, 82, 147 224). lnol B. Schneider, D. Doskocilova, and H. Pivcova, in ref. 17, p. 127 (Chem. Abs., 1975, 83, 139 057).

P. Mansfield, Atoniic Energy Rev., 1974, 12, 727 (Chem. Abs., 1975, 83, 17 821). l o o 3 P. C. Taylor, J. F. Baugher, and H. M. Kriz, Chem. Rev., 1975, 75, 203. l o a d M. Mehring, H. Raber, and G. Sinning, in ref. 18, Vol. I , p. 35 (Chem. Abs., 1975, 83, looa

185 548). Ganapathy and R. Srinivasan, J. Sci. Ind. Res., India, 1975, 34, 134 (Chem. Abs., 1975,

l o o S S.

83, 185 542).

Y. Masuda, Nippon Butsirri Gakkaishi, 1975, 30, 536 (Chem. Abs., 1975, 83, 105 500). W. Zinn, Atomic. Energy Rco., 1974, 12, 709 (Cfirn~.A h . , 1975, 83, 34 841). l o o a G. Parry-Jones, in ‘Transfer Storage Energy Molecules’, ed. G. M. Burnett, A. M. North, and J. N. Sherwood, Wiley, New York, 1974, p. 471 (Chem. A h . , 1975,83, 34826).

looO loo7

104

Spectroscopic Properties of Inorganic and Orgarlometallic Compounds

‘Thermodynamics of Spin Systems in Paramagnetic Crystals’,1000‘Nuclear Magnetic Resonance Studies on the Structure of Glass’,1o1o‘Nuclear Magneticand Electron Spin-resonance Spectroscopy of ‘Nuclear Magnetic Resonance [of Polymers]’,1o12‘N.ni.r. of Solid Polymers’,1o13‘Measurement of Moisture Content in Agricultural Products by Proton Magnetic Re~onance’,’~’~ ‘N.m.r. Studies of Surface and ‘Application of N.ni.r. to Certain Surface The application of dipolar proton ( I ) spin-lattice relaxation time measurements for the determination of fast quadrupolar spin-lattice relaxation rates on non-resonant ( S ) spins, the signals of which are too weak to be measured directly, is discussed in the limit of strong I-S dipolar coupling. The spin-lattice relaxation of the common 1H-75As dipolar reservoir in KH,AsO, and the common 1H-1271dipolar reservoir in Ag,H,IO, were used to illustrate the above te~hnique.’~’’ The variations of the first moments of the n.m.r. absorption lines have been studied experimentally and theoretically as a function o f nuclear polarkation in solid samples containing several spin species. The first moments, which describe quantitatively the ‘shift’ of the lines with respect to their Larnior frequencies, are linear combinations of the polarizations with a coefficient dependent on the shape of the sample. The experiments were performed on rectangular samples of LiF and CaF, doped with paramagnetic impurities, and the results were in very good agreement with theory.1018 The experimental deterniination of the gradient-elastic constant connecting the electric field gradient at the given nucleus to the electric stress was performed for strongly distorted solids, and values were determined for ”Rb and 12’1 in RbI single crystals.1o1BThe relaxation of a two-spin-state paramagnetic ion embedded in an ionic lattice has been treated theoretically, using the assumption that the decay mechanism is due to the vibrational modulation of the crystalline electric field.Io2O N.m.r. dipolar echoes have been observed for solids, e.g. CaS0,,2H20, containing spin-4 pairs.1o21A calculation has been given which shows how the n.m.r. absorption can be used to monitor the time-dependent diffusion of hydrogen gas into a metal. The result was given in the form of the deviation of the absorption from that of a honiogeneous distribution of hydrogen. The calculation was made by solving Maxwell’s equations with a susceptibility derived from the tiniedependent solution of the diffusion equation.1022 An atlas of the ‘H n.ni.r. W. T h . Wenckebach, T. J. R. Swanenburg, and N . J. Poulis, Phps. Rvp., 1974, 14, C , 181 (Chrnr. A h . , 1975, 82. 79 582). P. J . Bray, Internnt. Congr. Glass (Pup.), loth, 1974, 13, 1 (Chem. Abs., 1975, 83, 6 4 777). l o l l I I . Dutz and W. Poch, Fachausschussber. Dtsch. Glastech. Ges., 1974, 70, 219 (Chem. Abs., 1975, 82, 49 336). l o l a A. Pidcock, P o l j ~ m Sci. . ( U . S . S . R . ) , 1972, 2, 1383 (Chem. A h . , 1975, 83, 131 945). l0ls V. J. McBrierty. Polpnrrr, 1974, 15, 503 ( c h ~ n rAbs., . 1975, 82, 43 750). lo1‘ A. L. Skripko, Kontr. Vlzahnosti Radiiospcktrosk. Diel’Kometricheshirii Mctod., 1973, 3 (Chem. A h . , 1975, 82, 2680). l 0 l 6 H . Pfeifer, in ref. 18, Vol. 1 , p. 51 (Chem. Abs.. 1975, 83, 183 944). 1016 W. E. E. Stone, Silicates lnd., 1974. 39, 255 (Chem. Abs., 1975, 82, 77 370). lo1’ R. Blinc and S. Turner, J . Chem. Phys., 1975, 62, 3118. l 0 l 8 Y . Roinel and V. Bouffard, J . Magn. Resonance. 1975, 18, 304. l o l 9 H . J . Hackeloer and 0. Kanert, J . Magn. Resonance, 1975, 17, 367. 1020 R. S. Wilson, A . J. Fedro, and D. C. Knauss, A.I.P. Con5 Proc., 1975, 24, 524 (Chcrtt. Ahs., 1975, 83, 105 891). l 0 2 1 N. Boden, Y . K . Levine, D. Lightowlers, and R. T. Squires, Mol. Phys., 1975, 29, 1877. loZ2 J. I. Kaplan, J . Mngn. Rcsonancc, 1975, 20, 110.

loo0 lolo

Nuclear Magnetic Resonance Spectroscopy

105

spectra of crystal hydrates calculated by computer has been prepared. The calculation was performed for different interprotonic distances R (1.561.65 A) in water molecules and for broadening parameters /3 (1-2.2 Oe) responsible for intermolecular interactions. It is possible to derive R and ,f3 to ? 0.02 and k 0.02 Oe respe~tive1y.l~~~

Motions in Solids.-The earlier hypothesis (1970) that the narrow component of the n.m.r. signal of ice corresponds to the mobile water molecules on the ice surface whereas the wide component corresponds to the mobile water niolecules in the ice lattice has been Pulse 1i.m.r. studies of ,H n.m.r. linewidth, interbond jump time, and Tl were made between - 106 and 0 "C on one zone-refined and two less uniform crystals of D 2 0 ice. The time constant required for deuterons originally in bonds parallel to the c-axis to mix with non-c deuterons was measured directly below -45 0C.1025N.ni.r. studies of clathrate ices show that the lH resonances of water molecules begin to narrow at a temperature where the dielectric relaxation time has reached s. Rotational and diffusional narrowing seem to be intimately connected. The spectra of molecules encaged in D 2 0 lattices show low-temperature linewidth transitions which are very broad for large polar molecules but narrow for such encaged species as SF,. Fine structure was observed at low temperatures.1020 The motion of sodium ions in single crystals of p-alumina has been studied via its effect on n.m.r. linewidth and electric quadrupole interaction. A single line was seen between - 160 and +220 "C, and this is indicative of rapid ionic motion. The average coupling constant remains almost constant over the temperature range. The average asymmetry parameter decreases with teniperature, reflecting the change in off-axis site population. An activation energy of about 0.1 7 eV was estimated from linewidth changes.1027 The temperature dependence of the 87Rb T, and TIPrelaxation times has been measured in RbH2P04. The relaxation rates are determined by two competing effects: a 'fast' relaxation mode near the ferroelectric transition and a 'slow' highBy single-crystal n.ni.r. temperature motion mechanism above 220 K.1028 spectroscopy, the temperature dependence of the n.q.r. coupling constants in the P-alum CsAI(SO,),,l 2 H 2 0 has been investigated. The temperature coeficient is positive for 27Aland negative for 133Cs.Similarly, the temperature coefficient of 87Rb in the a-alum RbGa(S04)2,12H,0 is negative, and these signs were explained. The nuclear quadrupole coupling constants of 14N in NH4AI(SO,),,I 2 H 2 0 , N,H,AI(SO,),, 12 H z 0 , and MeN H3AI(S04)2,12 H 2 0 have been explained by the rotational motions of the ions M+, and the direction of the rotational axes of [N,H,]+ and [MeNH,]+ with respect to the molecular and crystal axes has been determined.102Q

r,,

1023 1024

1026

1026 1027

iozn

1029

R . N. Pletnev, Zhur. fiz. Khim., 1974. 48, 2882. V. I. Kvlividze, V. F. Kiselev, and L. A. Ushakova, Vesfnik.Moskoii. Univ., Fiz., Astronomiya, 1974, 15, 736 (Chem. A h . , 1975, 82, 145 634). V. H. Schmidt, Phys. Chem. Ice, Pap. Symp., 1973, 1972, 212 (Chem. Abs., 1975,82,49 665). S. K. Garg and D . W. Davidson, Phys. Cheni. Ice, Pap. Symp., 1973, 1972, 56 (Chem. Abs., 1975, 82, 49 663). I. Chung, H . S, Story, and W. L. Roth, J . Cheni. Phys., 1975, 63, 4903. I 2 kcal mol-l for both tops. The moments was of inertia, together with a measured dipole moment component of pc = 0.0 D, implied that the molecule has a plane of symmetry. On making various assumptions, a structure was obtained in which r(P-B) = 1.841(20) A. The overall dipole moment was 3.94(5) D. The barrier to internal rotation in PH3BFS was detetmined4l by measuring the intensities of the torsional state satellites, giving torsional frequencies of 190(20) cm-l in PH3BF3and 141(15) cm-l 8'

39 4"

T. C. Bartke, A. Bjoerseth, A. Haaland, K. M. Marstokk, and H. Moellenda1,J. Organornetaffic Chem., 1975,85, 271. P. Cassoux, R. L. Kuczkowski, P. S. Bryan, anti R. C. Taylor, Inorg. Chem., 1975, 14, 126. J. R. Durig, V. F. Kalasinsky, Y. S. Li, and J. D. Odom, J. Phys. Chem., 1975, 79, 468. R. A. Creswell, R. A. Elzaro, and R. H. Schwendemann, Inorg. Chem., 1975, 14, 2256. J. D. Odom, V. F. Kalasinsky, and J. R. Durig, Inorg. Client., 1975, 14, 2837.

Microwave Spectroscopy

187

in PD8BF3; these gave V, = 3.34(35) and 3.44(30) kcal mol-l, respectively. Assuming the PH3 group geometry enabled the authors to determine the rest of the structure, in which r(P-B) = 1.921(17) A. This is shorter than in PH3BH3 but longer than in PF3BH3, showing the familiar lack of correlation of bond length with stability. A sensitive i.r.-radiofrequency double-resonance technique, in which the gas cell was placed inside the cavity of a CO, or NzO laser, was employed to observe 42 the 'forbidden' AJ = 0 rotational transitions in SiIJ,. Four rotational lines were assigned, three others also being observed. A detailed rotational assignment was performed 43 on many vibrational states of SiH3CN, giving rotational constants and various other parameters. In Me,SiHCN, several assumptions were made in order to obtain structural information from the of the one isotopic species observed. The distance between the cyanide carbon atom and the silicon atom was determined as 1.840 A, which is shorter than the Si-C bond in SiH,Me,, probably because of the sp hybridization of the carbon atom, since a similar difference occurs between Me,CH, and Me,CHCN. The dipole moment of 3.8(1) D is similar to that of SiH3CN, indicating that the inductive effect of the methyl groups has little effect on the dipole, in contrast to the corresponding carbon compounds. An analysis45of the rotational spectra of six isotopic species of MeSiH,Cl gave rotational, centrifugal distortion, and nuclear quadrupole coupling constants. The determination of the structure was deferred until further information is obtained on other isotopic species. The splitting of the rotational transitions in PhSiH3 enabled Caminati et to determine V, = 17.78(2) cal mol-l. This precise value shows that the value of 35(10) from i.r. bandshapes was rather unreliable. The observed value is much greater than in PhMe, possibly due t o p -+ d n-bonding since less steric hindrance is expected. The rotational constants and dipole moment were also determined. From the rotational constants derived from the microwave spectrum 4 7 of the recently synthesized SiH3SiF3, the substitution distance r,(Si-Si) = 2.320(5) 8, was derived, a little shorter than the 2.34(3) A of Si2H6. Bond lengths were transferred from Si2H6(Si-H) and SiHF3 (Si-F) to give LSiSiH = 108.7(20)" and LSiSiF = 112(2)". The dipole moment was 2.03(7) D. Although several vibrational states were observed, no progression due to torsional states could be discerned, so that the barrier to internal rotation was not calculated. I n SiH,PH2, however, the barrier of 1.535(40) kcal mol-l was obtained from an analysis 48 of the splitting of the transitions; this is less than in the corresponding carbon compound, as is usual. Bond lengths were transferred from analogous niolecules to give r(Si-P) = 2.25 A, LHPH = 93.85" and LSiPH = 92.8", implying very little p -+ d .rr-bonding. 43 64

G' 4e

O7 4n

W. A. Kreiner and T. Oka, Cunad. J . Phys., 1975, 53, 2000. A. J. Careless and H. W. Kroto, J . Mol. Spectroscopy, 1975, 57, 198. J. R. Durig, V. F. Kalasinsky, and M. J. Flanagan, Inorg. Chem., 1975, 14, 2845. W. Zeil, W. Braun, B. Haas, H . Knehr, F. Riickert, and M. Dakkouri, Z . Naturforxh., 1975, 30a, 1441. W. Caminati, G. Cazzoli, and A. M. Mirri, Chem. Phys. Letters, 1975, 35, 475. J. Pasinski, S. A. McMahon, and R. A. Beaudet, J . Mol. Spectroscopy, 1975, 55, 88. R . Varma, K . R. Ramaprasad, and J. F. Nelson, J . Cheni. Phys., 1975, 63, 915.

188

Spectroscopic Properties of Inorganic arid Organometailic Compounds

Several organogermanium chlorides have been investigated. In CH,CIGeH3, five isotopic species were giving rotational and nuclear quadrupole coupling constants. A complete structure could not be obtained, but the transference of some parameters from CH2ClSiH, gave r(Ge-C) = 1.961 A, r(Ge-H) = 1.517 A, LClCGe = 110.2' and LCGeH = 107.7'. Using this structure and the xaa values in inertial axes, the quadrupole coupling constants in a bond axis system for the main species was xzz = -74.5 MHz, xzz - xvv = -0.2 MHz, showing almost cylindrical symmetry around the C-CI bond. From the intensity of the first torsional satellite, the barrier of 1.733(30) kcal mol-1 was obtained; this is considerably higher than in CH,FGeH,, CH,GeH,, or CH,GeH,F. The microwave spectra of trichloromethylgermane 5 0 and chlorotrimethylgermane 61 both yield substitution values for r(Ge-Cl), but these are quite different, being 2.135(6) and 2.170(1) A, respectively. Both are considerably shorter than the sum of the covalent radii (2.21 A), indicating possible double-bond character in the Ge-Cl bond. The r(Ge-C) value of 1.940 8, in Me,GeCI is similar to that in the Me,GeH,-, compounds, although shorter than those found in Me,Ge and Me,GeCN. In MeGeC1, the CGeCl angle is 106.0(7)", implying considerable CI- - -Cl repulsion but little C- - -C1 repulsion owing to the large Ge-C distance. The ground-state rotational spectrum 6 2 of the main isotopic species of arsabenzene gave some information on the electronic and molecular structure. The C,, symmetry expected is confirmed by the presence of only one dipole moment component, and the small positive inertia defect shows the molecule to be planar. The dipole moment i s 1.10(4) D, compared with 1.54 D for C6H6P ~ quadrupole coupling constants were and 2.24 D for C6H5N. The 7 6 Anuclear xaa = - 186.4(1) MHz, X b b = 43.5 MHz, and xcC= 142.9(2) MHz, giving orbital population differences of n, - nb = 0.387, n, - n, = 0.553, and nb - no = 0.166. Since n, is largest this orbital is involved in the lone pair. By measuring the spectra of molecules containing 13C or 2D,Walls et aZ.63 have determined an r, structure for MeHgX (X = CI, Br, 1). Although the lines were broad due to the quadrupole structure, the Bo values were accurate enough to obtain the bond lengths shown in Table 2. The values are as expected from

Table 2 Substitution structure of the niethyimercury halides r(C-H)/A r(Hg-X)/A Molecule r(C-Hg)/A 1.090 2.283 2.055 CHsHgCl 1.095 2.072 2.406 CH,HgBr 1.092 2.077 2.571 CH3HgI a

L HCH/deg 109.5" 109.5" 109.5"

Assumed.

Me,Hg and HgX, compounds, being close to the sums of the covalent radii, although there is a slight trend of increasing Hg-C bond length with decreasing electronegativity of X. as 6o 61 62

63

J. Nakagawa and M. Hayashi, CIimi. Letters, 1974, 1379. J. R. Durig, P. J. Copper, and Y. S. Li, J . Mol. Spectroscopy, 1975, 57, 169. J. R. Durig, and K . L. Hellams J . M d . Structrire, 1975, 29, 349. R. P. Latimer, R. L. Kuczkowski, A. J. Ashe, and A. L. Meinzer, J . Mol. Spectroscopy, 1975, 57, 428. C. Walls, D. G. Lister, and J. Sheridan, J.C.S. Fciruduy 11, 1975, 71, 1091.

Microwave Spectroscopy 189 The microwave spectra of hydrogen-bonded 5 5 and charge-transfer complexes 58 have been obtained. In a 1 : 1 mixture of H F and H,O at 0.8 Torr, rotational transitions near 14.4 and 28.8 GHz were assigned 6 4 to the J = 1 +- 0 and 2 + 1 transitions of H,O,HF, giving ( B C) = 14402 MHz. Of the three C), whence likely structures (1)-(3), only (1) gave a reasonable value for ( B 64p

+

+

r ( 0 - - -F) = 2.72 A. This conclusion that the structure is (1) is strengthened by the evident 3 : 1 intensity alternation of the rotational transitions, implying either a planar C,, structure or a non-planar structure with a low barrier to inversion. Three vibrational states were observed, at ca. 198, 94, and 180 cm-l, these being assigned to the H-bond stretch, out-of-plane, and in-plane bending modes, respectively. The relatively large out-of-plane bending frequency (which could be positively identified because of the reversal of the 3 : 1 intensity alternation) again implied a planar molecule or a low barrier. The dipole moment of = 3.82(2) D is quite close to the 3.68 D calculated from ~ H F p ~ , o . Similarly, spectra were also observed 6 5 for MeCN,HF, where r(N- - -F) = 2.741 8, if there is no change in the MeCN and H F geometries. The H-bond stretching and bending frequencies of 18 l(20) and 45( 15) cm-l are consistent with those obtained from the far-i.r. spectra. At temperatures less than 250 K and pressures ca. 2.5 Torr, a 1 : 1 mixture of Me,N and CFJ gave56 broad peaks due to a new symmetric top with f,, -- 431.95(20) MHz. This was assigned to the charge-transfer complex Me3N-TCF8, and r(N-I) = 2.932 A if the parent molecule geometries are unchanged on complexing. This distance is much greater than in Me,N-I, (2.27 A) or Me3N-ICl (2.30 A) but similar to that in (CH&N4-I8CH, these three distances having been determined by diffraction methods.

+

64 66

J. W. Bevan, A. C. Legon, D. J. Millen, and S. C. Rogers, J.C.S. Chem. Comm., 1975, 341. J. W. Bevan, A. C. Legon, D. J. Millen, and S. C. Rogers, J.C.S. Chem. Comm., 1975, 130. A. C. Legon, D. J. Millen, and S. C. Rogers, J.C.S. Chem. Comm., 1975, 580.

~.IJ

4

Vibrational Spectra of Small Symmetric Species and of Single Crystals ~

~

~~~

BY D. M. A D A M S AND P. G A N S

1 General Introduction By D . M . Adams

The year 1975 bore witness to two established truths:’ ‘of making many books there is no end, and much abstracting is a weariness of the flesh’. There was an unusually heavy crop of books,”17 soine of value; a welcome emphasis upon the vibrational spectra of and a plethora of reviews of Raman spectroscopy;”-31 not to mention two new journals :I3 and another review 321

Ecclesiastes 12, v. 12 (marginal reading). N. N. Greenwood and E. J. F. Ross, ‘Index of Vibrational Spectra of Inorganic and Organometallic Compounds, Vol. II’, Butterworth, London, 1975. P. S. Braterman, ‘Metal Carbonyl Spectra’, Academic Press, London, 1975. L. J . Bellarny, ‘The Infrared Spectra of Complex Molecules, Vol. I’, 3rd etln., Chapman and Hall, 1975. P. R. Griffths, ‘Chemical Infrared Fourier Transform Spectroscopy’, Wiley Intcrscience. New York, 1975. ti N. B. Colthup, L. H . Daly, and S. E. Wiberly, ‘Introduction to Infrared and Raman Spectroscopy’, 2nd edn., Academic Press, New York, 1975. I. N. Levine, ‘Molecular Spectroscopy’, Wiley, New York, 1975. R. C. Denney, ‘A Dictionary of Spectroscopy’, Macmillan, London, 1973. J. W. Robinson, ‘Handbook of Spectroscopy, Vol. 2’, C.R.C. Press, Cleveland, Ohio, 1975. l o L. May, ‘Spectroscopic Tricks, Vol. 3’, Plenum, London, 1975. ‘Vibrational Spectra and Structure, Vol. 3’, ed. J . R . Durig, Dekker, New York, 1975. l a M. Horak and D. Papousek, ‘Infrared Spectra and Molecular Structure. Use of Vibrational Spectroscopy in Determining Molecular Structure’, Academia, Prague, 1975. Is T. Ya. Paperno and V. V. Perekalin, ‘Infrared Spectra of Nitro Compounds. Textbook for Undergraduate and Graduate Students’, Leningrad Gos. Pedagog. Inst., Leningrad, 1974. l 4 N. G . Bakhshiev, ‘Vvedenie v Molekulyarnuyu Spektroskopiyu’ (Introduction to Molecular Spectroscopy), 1974. ‘Spectroscopy’, ed. D. A. Ranisay, Butterworth, 1975. G . Allen and 11. D. Pritchard, ‘Statistical Mechanics and Spectroscopy’, Butterworth, London, 1974. M. Herberhold. ‘Metal Pi-complexes. Complexes with Mono-olefinic Ligands, Vol. 11, Part 2, Specific Aspects’, Elsevier, Amsterdam, 1974. lH V. C . Farmer, ‘Infrared Spectroscopy in Mineral Chemistry’, in ‘Physico-chemical Methods of Mineral Analysis’, ed. A. W. Nicol. Plenum, London, 1975. I B A. N. Lazarev, A. P. Mirgorodskii, and I. S. Ignat’ev, ‘Vibrational Spectra of Complex Oxides. Silicates and their Analogs’, Nauka, Leningrad, 1975. 2 o ‘Infrared and Ranian Spectroscopy of Lunar a n d Terrestrial Minerals’, ed. C. Karr, juri., Academic Press, New York, 1975. 2 1 J . A. Godsden, ‘Infrared Spectra of Minerals’, Butterworth, 1975. 22 P. J. €lendra, ‘Lasar Kaman Spectroscopy’ in ‘Vibrational Spectra and Structure’, ed. J. K. Durig, Vol. 2 , Dekker, New Yorh, 1975, p. 135. B. Schrader, RLT. ~rinsc~tigcsell.si~/iu~t Phj7.Y. < ‘ h i , t i i . , 1974, 78, I 187. 2.’ D. Schrader, Atctliorl. C‘/iitii. ( A ) , 1974, 1, 2.10. 23 M. Tsuboi, Grrrdoi Kogrthri, 1975, 47, 46. ?

190

Vibratiorinl Spectra cd‘Snicill Synrmetric. Species niitl of Single Crystals

191

series;34all of which implies that our subject is i n healthy middle age - unless, perhaps, it represents that period of bright emission that precedes the final extinction of a candle or of a civilization. The matrix-isolation field is still in a state of active technical development. Both general 35 and special aspects have been reviewed : metal-gas reactions,“6 the necessary conditions for good Raman matrix-isolation studies,37 and the new technique of proton-beam radiolysis used to produce charged species from Ar-CCl,.38 The 4th International Conference on High Pressure included a little spectroscopic work, notably a review of Raiiian s p e ~ t r o s c o p y . The ~ ~ use of i.r. spectroscopy in structure determination has been competently o ~ t l i n e d4.1 ~ ~ ~ ‘Tentatively standardized symmetry co-ordinates for vibrations of polyatoniic molecules’ have been proposed,42and 893 references to vibrational mean square amplitudes sifted.43

2 Spectra of Small Symmetric Species By D . M . Adanis Diatomic Species-A variety of physical studies, and the products of niatrixisolation experiments, are again responsible for most of what falls into this Section. The fundamental rotation-vibration band of N2 has been induced by a large electric field (at 20atm) and studied i n i.r. a b ~ o r p t i o n ,whilst ~~ €itbombardment yielded N,+ with we of 2398 c111-~.~~ A Raman band at 718 cni-’ i n the matrix-isolated products from an r.f. discharge in SO,-O,- inert gas thereby supporting an earlier mixtures has been attributed to the S, report of the same species produced The RRE i n ultramarine blue shows progressions which can be attributed to both S,- ( v ~ -586.5 ~ cm-l) and S3- (vl 548.9 cm-l); the assignment was made by comparison with doped alkali halide spectra.4* 26 2i

2H

:‘I 32

:Id

511

37

SH

so

4l 41

I . R. Beattie, Clietn. Soc. Rcc., 1975, 4, 107. C. M. Penney and S. D. Silverstein, U.S.N.T.I.S., A D Kep. 1972, No. 784227/1GA. ‘Laser Raman Gas Diagnostics’, ed. M. Lapp and C . M. Penney, Plenum, London, 1974. ‘Light Scattering in Solids’, ed. M . Cardona, Springer-Verlag, Berlin, 1975. A. Mooradian, in ‘Laser Handbook, Vol. 2’, ed. F. T. Arecchi and E. 0. Schulz-Dubois, North Holland, Amsterdam, 1972, p. 1409. W. Krasser and E. Koglin, Bcr. Ki~rr~~rsc~hirtigsairlagr Jculich, 1974, 11, 1 15. Koord. Kliitii., 1975, Vol. 1. Trnnsition M r t d Chem., Verlag Chemie, Weinheim, 1975. ‘Advances in Infrared and Ranian Spectroscopy’, ed. R. J. H. Clark and K.E. IIester, Heyden, London, 1975. S. Gradock and A. J. Hinchclifle, ‘Matrix Isolation: A Technique for the Study of Reactive inorganic Species’, Cambridge University Press, Cambridge, 1975. G. A. Ozin and A. Vander Voet, t’rogr. Inorg. C ‘ h ~ t i ; . 1975, , 19, 105. A. J. Barnes, J. C. Bignall, and C. J. Burnell, J . Ramuiz Spectroscopy, 1975, 4, 159. R. 0. Allen, J. M. Gryzbowski, and L. Andrews, J . Phys. Cheni., 1975, 79, 898. E. Whalley, ‘Proceedings of the 4th International Conference on High Pressure’, ed. J . Osugi, Phys.-Cheni. SOC.Japan, Kyoto, 1975, p. 35. F. A. Miller, A p p l . Spc’ctroscopj3, 1975, 29, 461. H . Weitkarnp, Method. Cliim. (A), 1974, 1, 268. S. J. Cyvin, in ‘Molecular Structure Vibrations’, ed. S . J. Cyvin, Elsevier, Amsterdam, 1972, 366.

o4 P5 .lll 47 ,tx

S. J. Cyvin, ref. 42, p. 431. D. Courtois and P. Jouve, J . Afof. Spectroscopy, 1975, 55, 18. J. d’lncan and A. Topouzhkanian, J . Cfwm. Phys., 1975, 63, 2683. A. G . Hopkins and C. W. Brown, J . C‘krm. Pli)*.s.,197.5, 62, 1598. R. L. McBeth, J . Clii~rri.Phys., 1971, 55, 5409. R. J. Ii. Clark and M. L. Franks, Chem. Pliys. Lettcrs, 1975, 34, 69.

I92

Spectroscopic Properties of Inorganic and Organometallic Compounds Raman spectra of Cl, and Br, in Ar matrices and as vapours yielded the following molecular constant values (w,/cm-l) 35Cl,

(8)

(Ar)

559.7 554.5

35*37C12(Ar)

547.2

37Cl, (Ar) 539.3

7B,

81Br2

(g) 323.3 (Ar) 317.5

which may be compared with: 70Br2325.26 k 0.10, and *lBr, 321.24 k 0.12 extracted from RRE spectra of isotopically pure vapours in the electronic ground Similar work on I, (in argon matrices) yielded we = 213.70 f. 0.22 cm-l from an RRE progression up to 1 3 ~ . ~v(X-X) l in charge-transfer complexes of the halogens with halogenobenzenes is lowered ca. 6 cm-l for X = C1, Br (independent of solvent), but v(,I-I) is solvent-dependent and, in chlorobenzene, has a greater value than in the vapour.61 Complexes of C1, and Br,, with NH3, and substituted amines, on the other hand, show v(Br-Br) in the range 270-262 cm-l [with a similar restricted range for v(C1-CI)] but in pyridine the value is 195 cm-l, implying a different ~ t r u c t u r e .Raman ~~ spectra of gas hydrates (clathrates) of Cl,, Br,, and BrCl at - 196 "C show new bands at 103, 130, and 88 cm-l respectively: the order shows that they cannot be translational modes, unless the structures are very different.53 The following ue/cm--l values were obtained from a Ranian study of the matrix-isolated species:54 ICl(g) 384.3

BrCl(g) 440

70BPCl 436.6 81BP7Cl 424.6

1=c1

137~1

377.3 368.1

IBr(g) 269 P B ~ 268.4

Andrews (to whom this Section should be dedicated!) has also prepared many species M+X,- obtaining both v(X-X) and a counter-ion mode in some instances (Table 1); v(1-I) of I,- was seen up to 6v by RRE. In contrast, the ion Is-

Table 1 Vibrational wavenumberslcm-' for some ion pairs M+Xav(F-F) 6LiX, Li X2 NaX, KX2 RbXa

csx,

Reference

452 452 475 464 462 459 55

V(M+F,-) 708 454 342

55

V(C1-Cl) 246 246 225 264 260 259 56

v(M+CI,-)

;2

}

v(1-I) 115.6 114.6 114.2

56

57

formed in the concomitant reaction K + I, -+ K+I,- yields an intense band at 109cm-l distinguished from v(I,-) by the need to excite the latter by RRE with 647.1 nm r a d i a t i ~ n . ~ ' so b1 ba 64

sb 6(1

E.~

B. S. Ault, W. F. Howard, and L. Andrews, J. Mol. Spectroscopy, 1975, 55, 217. P. Baierl and W. Kiefer, J . Ramon Spectroscopy, 1975, 3, 353. J. M. Grzybowski and L. Andrews, J . Roman Spectroscopy, 1975,4, 99. S. Karaianev, E. D'Alessio, and H. Bonedeo, J . -4nier. Chem. SOC.,1975, 97, 6474. J. M. Kimel'fel'd, A. B. Mostovoy, and L. M . Mostovaja, Chrm. Phys. Letters, 1975, 33, 114. J . W. Anthonsen, Acta Chem. Scand. ( A ) , 1975, 29, 175. C. A. Wight, B. S. Ault, and L. Andrews, J . Mol. Spectroscopy, 1975, 56, 239. W. F. Howard and L. Andrews, Inorg. Chenz., 1975, 14,409. W. F. Howard and L. Andrews, Inorg. Chent., 1975, 14, 767.

Vibratiortal Spectra of Small Symmetric Species artd of Single Crystals

193 Reaction of alkaline-earth atoms with ozone yielded the matrix-isolated species CaO (707), SrO (620), and BaO (61 3); vibrational wavenurnber/cm-l are given in parentheses.68 A similar experiment with oxygen in place of ozone also yielded BaO, but accompanied by Ba2+O,,-, ~(0-0) 540.6cm-l, and a centrosymmetric dimer Ba,O, with stretching modes at 393.6 and 486.5 cm-1.60) However, Raman spectra of peroxides M',02 and M"02 in the solid state to a band in the region 736-944 cm-l, sometimes split by the attribute 40-0) correlation field, and show that in an earlier study a band from a CO,2- impurity was mistakenly identified with v ( 0 - 0 ) . Typical wavenumbers/cm-l are :a06 Li202 ~(0-0) 790

K202

762, 746

MgO2 934, 864

BaO, 842

Raman data have been listed for 02+, XeF+, and NO+ salts of MF6-, MF,-, and M2F11- (M = transition or non-transition metal). v ( 0 2 + )is in the range 18191861 cm-1.60c PbS (matrix-isolated) shows a Raman line at 423.2 cm-l and a weak feature at 297 k 2cm-l has been attributed to Pb2S2.61The elusive SO molecule, v ( S 0 ) 1136.7 cm-l, is apparently produced in an Ar-SO, mixture subjected to an r.f. discharge.62 The precision now attainable with laser magnetic resonance excitation is well illustrated by the latest me value for NO, 1875.8470(7) cm-1.630 Flash photolysis of POCl, yielded PO and PCI, identified from fine structure in the electronic spectrum (me = 1218, 780 cm-l r e s p e c t i ~ e l y ) . ~ ~ ~ The hydrogen halides continue to be the subject of a variety of physical and theoretical studies of which the most significant this year is a Raman spectroscopic determination of the Q-branch cross-sections of HC1, HBr, and HI, relative to that of nitrogen, as a function of frequency. The variation was successfully interpreted qualitatively in terms of the variations in &/ar [HCl 1.18(6), HBr Other 1.40(7), HI 1.56(8) x 10-l6 cm2] but quantitative agreement was studies include: the collision-induced fundamental of H D at 50 amagat;66 the spectral density (in-plane modes only) of a disordered (HF)n chain ;s6 calculations of the frequency shift in dilute solutions OF HX (X = F, C1, Br, I), DC1, CO, and NO in CCll using a Lennard-Jones potential;67changes in the i.r. bandshape of DCI in alkane solutions with length of alkane chain;68and the behaviour of the Raman Q-branches of H2 and Da in solutions of inert ~ ~ l ~ e n t ~ . ~ ~ Triatomic Species.-This Section has now settled down Iargely into two halves dealing respectively with matrix-isolated species (many of them new) and with b8 bB 60

61 02

63

64 66

07 8s 69

W. F. Howard and L. Andrews, J . Amer. Chem. SOC.,1975, 97, 2956. B. S. Ault and L. Andrews, J . Chem. Phys., 1975, 62, 2320. ( a ) B. S. Ault and L. Andrews, J . Chern. Phgs., 1975, 62, 2312; ( b )H. H. Eysel and S. Thym, Z.anorg. Chem., 1975, 411, 97; ( c ) J. E. tiriffiths, W. A. Saunders, and W. E. Falconer, Spectrochim. Acra, 1975, 31, A , 1207. R. A. Teichman and E. R. Nixon, J . Mol. Spectroscopy, 1975, 54, 78. A. G. Hopkins and C. W. Brown, J . Chem. Phys., 1975,62, 2511. (u) K. Hakuta and H. Uehara, J . Mol. Spectroscopy, 1975, 88, 316; (6) R. D. Verma and S. Nagaraj, ibid., p. 301. J . M. Cherlow, H. A. Hyatt, and S. P. S. Porto, J . Chem. Phys., 1975,63, 3996. R. D. G. Prasad and S. P. Reddy, J . Cheni. Phys., 1975, 62, 3582. B. Borgtnik and A. AZman, Chem. Phys. Letters, 1975, 31, 225. 1. Rossi, C. Brodbeck, J. P. Bouanich, and N. V. Thanh, Spectrochim. Acta, 1975, 31, A , 433. D. Richon, D. Patterson, and G. Turnell, Chem. Phys. Letters, 1975, 36, 492. K. Altmann, W. Holzer, and Y. LedutT, Chem. Phys. Lerters, 1975, 36, 259.

194

Spectroscopic Properties of Inorganic and Organometallic Compounds

the continuing saga of the water molecule in or under every conceivable situation or condition. Vibrational progressions in the vibronic spectra of matrix-isolated 03-yielded w e in the range 877-908 cm-I and anharmonicities mex of 4.3-5.7cm-' depending upon both matrix and alkali-metal counter whilst the RRE and electronic spectra of 03-produced by y-irradiation of NaCIO, or KClO, showed progressions which gave v1 ca. 857 cm-I in the first electronic excited l ~ ~matrix-isolated state, as compared with 1020 cm-l in the ground ~ t a t e . ~ The ion-pairs M+CI,- (M = alkali metal), showed vl 275 and v3 375 cni--l for the anion. Fragmentary data were obtained for K+HCl,- and Rb HCl,-.'? A variety of new data for triatoniics are collected in Table 2. Carbene complexes of the type CI-.M-.CCl, are formed by reaction of alkali metal atoms with CCI,

Table 2 New ware~irimbers/cm-~ for some trintomic species B160, ( M ) XeCI, (M) KrF, SCI, so, (MI IC1,-

vy 208 1 (l"B), 21 54 ("B) v l 253, v, n.o., v3 256.5 v3 573 v1 528P, v, 205P, v3 n.0. v1 1179.6, v2 531.9, v3 1378.1 v1 263.4

Br,Clt BrCl,+

430, 424, 421, 300 167

3 * s z 1 0 0 (M)"

v ( S - 0 ) 1 1 56, S(SS0) 382 v(S-S) 672 v I 715, v, 994 In,Se (M) vg 819 T1,Se (M) v3 741 Ga,Te ( M ) v3 360

A1,O ( M )

Ga,O (MI In20 (M) Ga,S (M)

Ref: 73 74 75 76 77 }l;: 79

v3 208 v3 180 v3 155

M = matrix-isolated. P = polarized. Data also given for many other isotopic variants.

in Ar,81and a bewildering variety of species, including CCl,+ [v(C-Cl) at 927 cm-'1, have apparently been identified in the products from proton-beam radiolysis of CCI, and CBr,.*" Matrix-isolated CBr, and CClBr show modes at 196 and 257cm-', respe~tively.~~ In contrast with previous work i.r. bands of MgF, at 70

'l

72

73 74

7s i6

77 7* 8o

L. Andrews, J . Chrm. Phys., 1975, 63, 4465. ( a ) J . B. Bates and J . C. Pigg, J . Chem. Phys., 1975,62,4227; ( b ) A . I. Karelin, V. Ya. Rosolovskii, S. A. Tokareva, and 1. I. Vol'nov, Tezisy Doklady Vses. Sueshch. Khim. Neorg. Perekisnykh Soedin., 1973, 108. B. L. Ault and L. Andrews, J . Amer. Chem. SOC.,1975, 97, 3824. L. V. Serebrennilzov, Vestnik. Moskoo. Unio. Khim., 1975, 16, 363. I. R. Beattie, A. German, H. E. Blayden, and S. B. Brumfach, J.C.S. Dalton, 1975, 1659. V. D. Klimov, V. N. Prusakov, and V. B. Sokolov, Doklady Chem., 1975,217, 549. S. G. Frankiss and D. J . Harrison, Spectrochim. Acra, 1975, 31, A , 161. D. Maillard, M. Allevena, and J. P. Perchaud, Spectrochim. Acra, 1975, 31, A , 1523. W. Wilson, R. Landa, and F. Aubke, Inorg. Nuclear Cham. Letters, 1975, 11, 529. A . G . Hopkins, F. P. Daly, and C. W. Brown, J . Phys. Chem., 1975,79, 1849. P. A. Perov, V. F. Shevel'kov, and A . A. Mal'tsev, Vestnik Moskou. Uniu.,Khim., 1975, 16, 109.

a2

83

D. A . Hatzenbuhler, L. Andrews, and F. A. Carey, J. Amer. Chem. SOC.,1975, 97, 187. L. Andrews, J. M . Grzybowski, and R. 0. Allen, J . Phys. Chem., 1975,79,904. D. E. Tervault and L. Andrews, J. Amer. Chem. SOC.,1975, 97, 1707.

Vibrational Spectra of Small Symmetric Species and of Single Crystals

195

480 and 740cm-l in various matrices are attributed to d i m e r ~ . Mononier~~ dimer equilibria are present in both molten and gaseous SeO, with the dimer probably having a trans-(C2h)structure; there is no evidence for a structure like that of the chain found in the solid.85 Reaction of active nitrogen with CH,Br yields HNC, never previously obtained terrestrially in the gas phase. A high-resolution study gave v,, 3652.9 cm-1.86 Vibrational force constants for HCP were obtained from an lib initio MO calculation but gave calculated frequencies somewhat lower than the experimental ones.*’ Among the products of the photolysis of iodomethane in the presence of oxygen is hydrogen hypoiodite, HOT, for which wavenumbers/ cni-l are:88 v(OH)

6

V ( W

HOI 341 7 1193 571.3

DO1 2524.5 874.5 566.5

Band-centre values for v(B-H) in many isotopic variants of HBS have been determined, typically 2735.7969 cm-l for H11B32S.89Monomers and dimers of matrix-isolated MCN vapours show bands at wavenumbers/cm-l NaCN KCN

monomer dimer monomer dimer

2047, 368, 2094, 31 6, 2050, 288, 2063, 237,

168 309, 270, 153 139 224, 97

In reviewing the year’s work on the vibrational properties of water it is extremely difficult, without much retrospective searching, to be sure what is new especially as this area is confused by semantic problems. Holzapfel’s excellent Raman spectra of two of the high pressure phases of ice (VII and VIII) are the first in the laser-Raman area 91 [v(OH) region only] ; whilst Whalley g 2 has returned to his old stamping ground with another instalment of the ice I/i Raman story (350-4000 cm-l) which adds to knowledge in a way hopefully recognized by those in the field. Raman spectra of amorphous solid water (3&120K) resemble those of liquid water rather than of ice Ic or Ih, but at ca. 160 K the samples are irreversibly transformed into ice Ic. In the amorphous state it is probable that there are molecules in at least two differing e n ~ i r o n r n e n t s . ~ An ~ equivalent study was performed independently using ‘a new laser-beam trapping t e ~ h n i q u e ’ . The ~ ~ Raman v(OH) band contour of the water in acid droplets of HCl, HBr, and H2S04varies with acid c ~ n c e n t r a t i o n . ~ ~ 8p *5

nu M7

an no 91

n2 ga

n4 O.5

R. H. Hauge, J. L. Margrave, and A. S. Kana’an, J.C.S. Faraday II, 1975, 1082. H. Ziemann and W. Bues, 2. anorg. Chem., 1975, 416, 341. C. A. Arrington and E. A. Ogryzlo, J. Chem. Phys., 1975, 63, 3670. P. Botschwina, K. Pecul, and H . Preuss, 2. Narurfursch., 1975,30a, 1015. J. F. Ogilvie, V. R. Salares, and M. J. Newlands, Canad. J . Chem., 1975, 53, 269. R. L. Sams and A. G. Maki, J . Mol. Structure, 1975, 26, 107. Z. K. Ismail, R. H. Hauge, and J. L. Margrave, J . Mol. Spectroscopy, 1975, 54, 402. W. B. Holzapfel, R. S. Hawke. and K. Syassen, ref. 39, p. 344. P. T. T. Wong and E. Whalley, J . Chem. Phys., 1975, 62,2418. C. G. Venkatesh, S. A. Rice, and J. B. Bates, J . G e m . Phys., 1975, 63, 1065. V. Mazzacurati and M. Nardone, Chem. Phys. Letters, 1975, 32, 99. D. D. Dylis, Opt. Eng., 1974, 13,502.

196

Spectroscopic Properties of Inorganic and Organometullic Compounds

1.r. methods have not been exhausted so far as water is concerned. The overtone region of H,O-D,O solid solutions has been given an i n t e r p r e t a t i ~ n , ~ ~ now complicated by the discovery of further unsuspected properties of ‘Russian water’. Thus, in the v(0H) overtone region the spectra of heated doubly distilled water, and of just-thawed ice frozen from doubly distilled water, are different. The former sample is thought to contain cyclic hexamers with v ( 0 H ) x 3100 cm-l. Further differences were noted when an electric field was applied.e7 Water films formed between freshly cleaved plates of mica are quasi-crystalline (i.r. study);v* i.r. properties of water on various mineral and synthetic silica surfaces have also been reviewed.99 An ‘unambiguous’ interpretation is bravely claimed for the observed thermal dependence of the intermolecular vibrations of water, and contrasted with Walrafen’s ideas.loo However, there is more agreement at lower temperature (in both senses): among the species identified in matrix-isolated water is a dinier (1) lol which is also thought to be present in H,O-D,O dirners.lo2

An i.r. band ca. 2900 cm-l found in NaOH-H,O mixtures at 2 kbar has been attributed to an ‘association’ between water and hydroxide;lo3 whereas various new bands (145, 170, cu. 700 cni- l) in the I : 1 H,O-HF vapour complex have been associated with bending modes of the complex which may have a planar Czvstructure.1o4 1.r. spectra have been simulated for several different water molecule aggregates and compared with ice and water spectra.’06 H2S in an ice matrix gives a temperature-dependent far4.r. band [60 cm-l at 290 K, 39 cm-’ at 45 K] interpreted as indicating nearly free rotation of the molecule.1o* Studies of salt hydrates have continued steadily: LizSO4,H20;lo7 M,[FeCI,(H,O)] ( M = K, Rb, NH4);lo8 BaX,,nH,O and SrX,,nH,O (n = 1 or 2),Iou the latter study resulting in assignments for the water librations. More particular mention is made of three such contributions: firstly, an assignment of the complex D. Kroh and A. Ron, Chem. Phys. Letters, 1975, 36, 527. A. V. Karyakin, G . A. Kriventsova, and N. V. Soboleva, Doklady Chem., 1975, 221, 257. M. S. Metsik, T. I. Shishelova, G. T. Timoshchenko, and T. F. Golovko, Trudy Irkutsk. Politckh. Insf., 1972, 71, 200. V. V. S. Rao, Proc. Indian Nat. Acad. Sci., India ( A ) , 1974, 40, 153. l o o 1. N. Kochnev, A. I . Sidorova, and A. I. Khaloimov, Mol. Fiz. Biofiz. Vodn. Sist., 1974, 2, 79. l o l Pham Van Huong and J . C. Cornut, J . Chim. phys., 1975, 72, 534. l o 2 L. Fredin, B. Nelander, and G. Rihbegard, Chem. Phys. Letters, 1975, 36, 375. I o 3 E. U . Franck and M. Charue!, ref. 39, p. 600. l o 4 R. K . Thomas, Proc. Roy. SOC., 1975, A344, 579. l o 6 A. A. Vetrov, 0. I. Kondratov, and G. V. Yuhnevich, Austral. J . Chcm., 1975, 28, 2099. l o 8 M. M. X. Gerbaux, C. Barthel, and A. Hadni, Spectrochim. Acta, 1975, 31, A , 1901. l o 7 l i . P. Hayward and J. SchifTer, J . C h ~ mfhvs.. . 1975, 62, 1473. 10H M . Falk, C. Huang, and 0. Knop, Cunatf.J . Chem., 1975, 53, 51. loQ H . D. Lutz, 14.-J. Kliipfel, W . Pobitschica, and B. Baasner, Z. Nati4rforsch., 1974, 29b, 723. O6

O7

Vibrational Spectra of Small Symmetric Species and of Single Crystals v(0H) region of CoC12,2H,0 :’lo

+

VT

v, -

VT’

Vi

v3 VI

2% v2

CoCI2,2H2O

CoC1,,2D20

3535 3465 3400 3275 3181 1597

2615 2600 2490 2400 2355 1183

197

where VT is an (assumed) lattice mode. Both i.r. and Raman spectra of M2CuC1,,2H20 (M = K, Rb, Cs, NH4) show minima which sharpen at low temperature: these are ‘Evans holes’ caused by Fermi resonance between the broad, intense v1 of water and the relatively narrow 2v2.ll1 Finally, the i.r. spectra of [Me,N]F,H,O and [Me,N]OH,H,O have been interpreted in terms of complex anions [H,0,I2- and [H402Fz12-,respectively, which have characteristic wavenumbers/cm-’ :112 3020, 1570, 890, 730 [H,O8F2I2- 2950, 1750, 1560, 895, 822 [ H004I2-

A new relation has been found between H-bond length and the uncoupled v(0H) frequencies in many salt hydrates.l13 Tetra-atomic Species.---New Raman measurements on SO3 (both vapour and matrix-isolated) confirm a recent suggestion that the assignment of v4 > v 2 is correct. In Ar matrices wavenumbers/cni-I are : l I 4 v,(u;)

1065; v , ( ~ i 480; ) v,(e’) 1387; v4(e’) 528

Tentative comments have been made on the i.r. spectra of matrix-isolated NH, and ND3.116 The i.r. spectrum of AlF3 in Ar shows no sign of vl, implying that the molecule is planar rather than pyramidal; a multiplet previously reported cu. 950 cm-l is not present in pure AlF3 for which wavenumbers/cm-l are :11° v3 909.4; v, 286.2; va 276.9

Similar work on LnF, (Ln = La, Ce, Nd, Y, Eu, Gd), in matrices suggests that these are pyramidal, but SmF, may be planar.”’ The assignment : A, B, B,

vl 753, v2 511, v3 324 (all polarized) va 702 (from i.r.), v5 430 v0 336

B. K. Srivastava, D. P. Khandelwal, and H. D. Bist, Appl. Spectroscopy, 1975, 29, 190. D. A. Othen, 0. Knop, and M. Falk, Cunad. J . Chem., 1975, 53, 3837. K. M. Harmon and 1. Gennick, Znorg. Chem., 1975, 14, 1840. n3 B. K. Srivastava, D. P. Khandelwal, and H. D. Bist, Proc. Nuclear Physics Solid State Physics Symposium, 1974, 17C, 267. ll‘ Sheng-Yuh Tang and C. W. Brown, J . Raman Spectroscopy, 1975, 3, 387. llli G . Ribbegard, Chem. Phys., 1975, 8, 185. Y. S . Yang and J. S. Shirk, J . Mol. Spectroscopy, 1975, 54, 39. 117 J. W. Hastie, R. H. Hauge, and J. L. Margrave, J . Less-Common Metals, 1975, 39, 309.

Spectroscopic Properties of Itiorgunic and Organometullic Compounds

198

was deduced from a Raman and i.r. study of ClF3(l). In the solid a phase transition was found at 192.6 K.ll* A complex set of equilibria has been proposed on the basis of a high temperature gas-phase Raman study of Asl,, the species present being As],, As],, As,],, and 12:11' and the qualitative features of P-SbBr, reported for the first time; differences from the a-form are chiefly in the latticemode region.120 1.r. and Ranian data for the v(OH) region of H30+Cl- and H,O+Br- confirm the authors earlier work which showed v1 :> v3;121equivalent work with the SbF,- and AsF,- salts leads to the same conclusion and helps delineate the ranges of wavenumbers/cm-l in which the H 3 0 + modes occur. The new values are :

c1-

Anion

BrSbF,AsF,[ H,S]+SbF,-

v,(A,)

2895 2900 3300 3250 2490

v3(m

2630, 2525 2700, 2570 3150 3080 2520

vdE) 1630 1615 1180

v2(A,)

970 970 900 912 1025

Ref. 121 121 122 122 123

to which the data for the first well-established sulphonium salt are added for comparison. A normal co-ordinate analysis (NCA) of H,O+ has been given.124 1.r. spectra of matrix-isolated gallium trihalides have been assigned (wavenuni bers/cm-l) : 25 v2 A" v3 E' v4 E'

GaCI, 136.2 470.3 132.1

GaBr, 107.0 354.8 88.6

Gal, 292.7

and differ substantially from a set of values calculated for GaCI, and GaBr3.12, Raman data for Pr4N+ salts of CdX3- have been interpreted in terms of CZvsymmetry monomeric ions (on the basis of comparison with spectra of CdX,in solution), in contrast with the K+, Rb+, and NH4+ salts. Thus X = C1 X = Br X = l

252 164 118

314 201 171

294 187 162

98 76 77 58 74 55

(cm-I)

where brackets indicate splitting of bands which are degenerate for CdX3- in solut 118 *19

lZo

121 122

lz4 lZ8

12'

R. Rousson and M. Drifford, J . Chem. Phys., 1975, 62, 1806. R. Hillel, J. Bouix, and R. Favre, Buff. Soc. chim. France, 1975, 2458. G. J. Cioetz and M. J. F. Leroy, J . inorg. Nuclear Chem., 1975, 37, 1302. B. Desbat and P. V. Huong, Spectrochim. Acta, 1975, 31, A , 1109. K. 0. Christe, C. J. Schack, and R . D. Wilson, Inorg. Chem., 1975,14,2224. K. 0. Christe, Inorg. Chem., 1975, 14, 2230. N. K. Sanyal, R. K. Goel, and A. N. Pandey, Current Sci., 1975, 44, 543. R. G . S. Pong, R. A. Stachnik, A. E . Shirk, and J . S. Shirk, J . Chem. Phys., 1975, 63, 1525. S. J. Cyvin and A. Phongsatha, Spectroscopy Letters, 1975, 8, 71. J. G. Contreras and D. G. Tuck, Canud. J . Chem., 1975, 53, 3487.

Vibrationnl Spectra of Small Symmetric Species and of Single Crystals

199 Raman wavenumbers/cm-' for matrix-isolated H202 and D202are close to those reported last year for the vapours:128 V1

H202

D202

3593 2653.5

v2

VS

1385 1021.5

869 871

Further data for N2H2, N2HD, and N2D2,129 and for T12F2and T12CI, I3O have been given (see previous Reports). A definitive Raman study of S,Cl,(g), in combination with earlier i.r. data, provides the following wavenumbers/cm-1:78 C2

546, 466, 202, 92 461, 244

A

B

An exceptionally thorough i.r. study (matrix and gas) of four isotopic variants of COFa allowed a determination of the general harmonic force field, and removed an ambiguity in the v3, vs assignment. For l2Cl60Fzwavenumbers/cm-l are:131 vI va

1929.9 965.6

v3 v,

582.9 1243.7

~5 v6

619.9 767.4

The 35C1/s7C1 isotope shifts for matrix-isolated Cl2CO are 3.50 (A,) and 1.96 (B,) cm-l; calculated force constants differed substantially from those obtained using data for the v a ~ o u r . ' ~ Isotopic ~ data for H2CS (in a matrix) support the assignments v(C-S) 1063, .rr(CS) 993 ~ n 1 - l . l ~The ~ Ranian spectrum of Br0,F (I and s) shows that like C102F it is monomeric pyramidal in both phases, and not like polymeric I02F. Wavenumbers/cm-l for the liquid are:13* 953, vfb8Ylll(BrO) v, 394P, S(OBr0) 908P, v,,,(BrO) v, 305P, 8,,,(OBrF) 506P, v(Br-F) v6 271, 8,,,(0BrF) P = polarized.

vb

v1 v2

Three unsymmetrical tetra-atomics have received attention this year. Gasphase i.r. data for nitrosyl cyanide, NCNO, were assigned with the aid of NCA:135 v1 v2 v,

2177.5, v(CN) 1484.3, v(N0) 820.0, v(C-N)

vp

v5 vfl

( 1 O3.2), 8(CNO) 583.3, ~ ( N C N ) (54.4), torsion

1.r. spectra for many isotopic variants of cis-HNSO in matrices have been assigned :Isa VI

v2

v3

130

132 13:'

':I4 6I.'

v,

v, vg

900.4, ~ ( H N S ) 754.7, torsion 437.4, S(NSO)

P. A. Giguere and T. K. K. Srinivasan, Chem. Phys. Letters, 1975, 33, 479. R. Minkuritz, Z . anorg. Chem., 1975, 411, 1. M. L. Lesiecki and J. W. Nibler, J . Chem. Phys., 1975, 63, 3452. P. D. Mallinson, D. C. McKean, J. H. Holloway, and I. A. Oxton, Spectrochim. Acta, 1975, 31, A , 143. €4. G . Schnockel and H. J. Becher, J . Mol. Sfructure, 1975, 25, 369. M. E. Jacox and D. E. Milligan, J . Mol. Spectroscopy, 1975, 58, 142. R. J. Gillespie and P. Spekkens, J.C.S. Chem. Contm., 1975, 314. E. A. Dorko and L. Buelow, J . Chem. Phys., 1975, 62, 1869. P. 0. Tchir and R. D. Spratley, Canad. J . Chem., 1975, 53, 231 1 .

laH 120

3308.5, v(N-H) 1248.7, v ( S 0 ) 1082.7, v(NS)

200

Spectroscopic Properties of Inorganic and Organometallic Compounds

There is Fermi resonance between v p and 2vs. Photolysis of the same matrix yielded three previously unknown species identified as SNO [v(NO) 1523, S(NS0) 789.7 cni-l], cis-HOSN, and t r a n ~ - H O S N . l ~trans-HNSO ~ in Ar absorbs at 1382, v ( S 0 ) ; 986, v(SN); 881, G(HNS); and 651, torsion, However, we must close this Section with a sad and cautionary tale. The i.r. bands previously attributed to the novel matrix-isolated molecules FONO and NO,F, are in fact due to the known compounds HONO, FON02, and N20h:130 this discovery will doubtless call forth cries of glee from those who have been bewildered by the apparently unending creations of the matrix-isolationists, although they might ponder on John 8, v. 7 before shouting too loudly. Penta-atomic Species.-To the definitive i.r. and Raman solution data reported last year for the square-planar tetrahalogeno-anions of Pd", Pt", and Au"' have been added further Raman solution data140which are in close agreement with the earlier work except for the v4, B,, values for the Pd" species for which 195.8 cm-l, [PdC1,I2- and 125.4 cm-l, [PdBr412-are now given. The differences of m.40 and 20 cm-l respectively may be due to solvent effects but this should be checked. [AuBr,]-(aq.) yields a RRE spectrum in which v, can be seen up to its eighth overtone, and also the progressions v2 + nvl and v4 + nvl.141 In acetonitrile solution 140 [IC14]- has vl, A,, 282.9 and v2,B,, 256.0cm-l: an attempt has also been made to assign the low-temperature i.r. and Raman spectra of CsIC14.142 The RRE and the activities of matrix-isolationists continue to support a resurgence of interest in tetrahedral species. Improved values for v2 (756 cm-l) and v4 (678.3 cm-l) have been extracted from high-resolution i.r. spectra of stannane, SnH4.1g3 Many isotopically substituted species of GeCl, 144 and SnCI, 145 have been studied (mostly matrix-isolated), for which the following wavenumbers/cm-l are quoted as typical : 70Ge36C14 463.2; 74Ge3SC1,458.2; 76Ge36C14 456.0 (all are v3); 11aSn36CI, 11aSn37CI,

V1

371.5 361.4

1'2

95.8

93.2

v.3 411.3

403.3

v4

127.5 125.1

Ranian intensities have been determined for MClp(g) (M = C , Si, Ge, Sn, Ti), for v 1 to v4 inclusive and shown to be compatible with those for the liquid phase,146 and similar data have been reported for MI, (M = C , Si, Ge, Sn),147as have i.r. intensities for v3 and v4 of MCI, (M = Si, Ge, Isotope shifts of matrixisoIated C3"14 and c37c1, have been corrected for Fermi interaction and used P. 0. Tchir and R. D . Spratley, Canad. J. Chenz., 1975, 53, 2318. P. 0. Tchir and R. D. Spratley, Canad. J . Chem., 1975, 53, 2331. l J D K. 0. Christe, Z . anorg. Chem., 1975, 413, 177. Y. M. Bosworth and R. J. H. Clark, Znorg. Chem., 1975, 14, 170. Y . M. Bosworth and R. J. H. Clark, J.C.S. Dalton, 1975, 381. 16* J. P. Huvenne, B. Boniface, F. Wallart, and P. Legrand, Spectrochim. Acta, 1 9 7 5 3 1 , A , 1937. l P 3 C. G . Barraclough and D. J. Kew, J . Mol. Spectroscopy, 1975, 54, 162. I P 4 F. Koniger, A. Miiller, and K. Nakamoto, Z . Naturforsch., 1975, 30b, 456. 1 4 5 F. Koniger and A. Miiller, J. Mol. Spectroscopy, 1975, 56, 200. Irn R . J. H . Clark and P. D. Mitchell, J.C.S. Faraday 11, 1975, 515. 1 4 7 M. G. Voronkov, V. S. Dernova, I. F. Kovalev, N. V. Kozlova, R. G . Mirskov, and V. F. Mironov, Doklady Phys. Chem., 1975, 217, 639. H. Stoeckli-Evans, A. J. Barnes, and W. J. Orville-Thomas, J . Mol. Structure, 1975, 24, 73.

137

lS8

Vibrational Spectra of Sniall Symmetric Species and of Single Crystals

20 1

in NCA;l@ and the validity of the relation F33(TJ/Fll(Al) = constant tested for a large number of tetrahedral The wavenumbers/cm-' 490, 498, 611, 777, 925, 1267, and 1434 have been attributed to SO4, produced by the reaction of oxygen atoms with SO3. A structure S02(02)is suggested.16' New data for tetrahedral anions include : V1

[BC14]- (SO, solution) [M e4 N 1[CS, 1

CUs [PS4I

405P 495 391

v2

v3

190 353 282

670 1000, 805 535, 512

v4

274 317, 296

Ref. 152 153 154

Fragmentary data are reported for M',SO, (MI = Li, K , Rb, Cs), M1*SO, (MI* = Be, Mg, Ca);lS5and solid solutions of CaSO, and BaS04.1b6On the basis of a NCA of the anion frequencies in M1,M2(S0,),,6H,0 (M1 = K, NH,; M2 = Mg, Zn, Ni, Co), variations of its geometry were predicted and found to be substantially correct when compared with X-ray ~ a 1 u e s . lMatrix-isolated ~~ M2SOa (M = K, Rb, Cs) have been studied by i.r. absorption but the abstract (Chern. Abs. 83, 18 058y) does not allow an A similar study of the vapours over alkali metal perchlorates, using molecular beam techniques, showed the dominant species to be M+C104- except for the lithium salt for which a large percentage is in the dimeric form. The monomer ion pairs show pronounced splitting of the v3 and v4 anion modes and the presence of three widely spaced v3 components indicates bidentate co-ordination to Mf. Typically for KClO,, v3 = 1028, 1 1 22, 1184 ~ r n - l . ' ~ ~ Force constants calculated on the basis of averaged (for solid-state splittings) values for the anion modes in AgMnO, (viz. vl 806, v 2 339, v3 879, v4 383.5 cm-') are intermediate between those obtained by a similar process for KMnO, and BaMnO,, indicating that the electronic distribution in the silver salt is complex and apparently contains both Ag' and Ag1'.160 The RRE spectra of [CoXJ2(X = CI, Br, NCO, NCS) have been interpreted to show that the main scattering process is the coupling of the two ,T1 electronic stafes.ls1 1.r. wavenumbers/cm-' have been listed for [CoXJ2- (X =: CI, Br, I) as salts of complex cations such as [CO(O-C,H~(PP~,)~)~]"+.~~~ New Raman data for C,, SeF, lE3and [SbC14]-lfi4are in Table 3 and those for several tetrahedral AMB3 species in Table 4. New i.r. and Raman data have H. J. Becher, Hg. Schnoeckel, and H. Willner, 2. phys. Chem. (Frankfurt), 1974, 92, 3 3 . A. Alix, C. Cerf, and S. N . Rai, Z . Nuturforsch., 1975, 30a, 627. 151 R. Kugel and H. Taube, J . Phys. Chem., 1975, 79, 2130. 15* M.-C. Dhamelincourt and M. Migeon, Compt. rend., 1975, 281, C , 79. l K 3 M. Robineau and D . Zins, Compt. rend., 1975, 280, C , 759. l S 4 0 . Sala and M. L. A. Temperini, Chem. Phys. Letters, 1975, 36, 652. lSs H. Takahashi, S. Meshitauka, and K. Higasi, Spectrochim. Acta, 1975, 31, A , 1617. lS8 J. Moravec, V. Sara, and 0. Vojtech, Coll. Czech. Chem. Comm., 1975, 40,815. l K 7 V. A . Narayanam, Acta Phys. Polon ( A ) , 1975, 47, 273. I K R A. A. Belyaeva, M. I. Dvorkin, and L. D. Shchevba, Optika i Spektroskopiya, 1975, 38, 516. G. Ritzhaupt and J. P. Devlin, J . Chem. Phys., 1975, 62, 1982. L. F. Mehne and B. B. Wayland, J. Inorg. Nuclear Chun., 1975, 37, 1371. G. Chottard and J. Bolard, Ch~rn.Pliys. Letters, 1975. 33, 309. la" W. Levason and C . A. McAuliffe, Inorg. Chitn. Actn, 1975, 14, 127. Io3 K. Seppelt, Z.nnorg. Chem., 1975, 416, 12. 184 J. Milne, Canad. J . Chem., 1975, 53, 888. la@

I5O

202

Spectroscopic Properties of Inorganic and Organometallic Compounds

for SeF, Table 3 Ramon ~auenumbers/crn-~ A,

A,

v(SeF,)eq. v(SeF,)ax. 6(SeF2)eq. 8(SeF2)ax.

739P

362P 200P

B,

v1 v2

v(SbCl,)eq. v(SbC1,)ax. a(SbC1,)eq.

337P 300P 170P

Bz

2’3

Table 4

163

551P

and [SbCI4]- 164

Bl

vl v2 v, v4

v5 v6

v7 ve v7

vg

v(SeF,)ax. G(SeF2) v(SeF,)eq. G(SeF2)

585 254 717 403

v(SbC1,)eq. 8(SbC12)eq.

252 146

Vibrational wauenumbers/cm-’ for CSvspecies AMB3 in the vapoirr phase A1

Species NbOF, a SPF, FCCI, BrCCI, ISCI, HS0,DS031.r. study.

I V1

1030 984.0 1080.4 730.7 482 2588 1878

E

-

v2

v3

v4

Vii

v6

695.9 537.6 419.9 292 1038 1035

260 441 .O 351.3 246.5 242 629 623

770 947.0 847.8 785.2 493 1200 1200

320 405.4 395.3 290.2 255 1123 831

190 237.7 242.8 188.0 140 509 504

700

Ref.

}

165 166 167

}

168

In a mixed crystal ‘C18SzIi.

Rarnan study.

been reported for [ MeC02H2][S03F] and tentatively assigned.lsQ An earlier study of the Raman spectrum of Mo02C12(g) has been confirmed and the following new data (wavenumbers/cm-l) obtained for MoO,Br,(g) :170 995 970 373 338 262

vl, A, v6,

B1

v3, A, v8, B, v2, A,

v(Mo0) v(MOO)

8(Mo02) v(Mo-Br) v(Mo-Br)

184 v7, Bl 161 vg, B2 147 v,, A , 87, 82, 75

p(MoO2) p(MoBr2) 6(MoBr2) others

The i.r. spectra have been obtained for four isotopic variants of matrix-isolated 15N0,: assignments support earlier ones except for &NO,) and v(N0’). Typically 1$

zH141

v(OW %,,Xn(N02)

~(NOH) %8,1n(N02) v( N 0‘)

H14N03 3490 1697 1343 1311 902

H15N03 3488 1659 1339 1294 892

?r

&NO,) 6(ON 0’) Torsion

Hl4NO3

Hi5NOs

767 660 597 479

746 658 594 479

Liquid N203shows far4.r. absorption at 76, 160, and 260 ~ m - l . ” ~ V. I. Yampol’skii, E. G . Rakov, V. A. Davydov, V. V. Mikulenok, and A. A. Mal’tsev, Russ. J . Inorg. Chem., 1974, 19, 1255. l e e R. J. H. Clark and 0. H . Ellestad, J. M o f . Spectroscopy, 1975, 56, 386. l e 7 Y . Tavares-Forneris and R. Forneris, J . M o f . Structure, 1975, 24, 205. l o 8 1. C. Hisatsune and J. Heicklen, Canad. J. Chem., 1975, 53, 2646. l B 8 M. Deporcq-Stratmains, C. Josson, and P. Vast, Compr. rend., 1975, 280, C, 513. liUV. V. Kovba and A. A. Mal’tsev, Russ. J . Inorg. Chem., 1975, 20, 11. lil W. A. Guillory and M . L. Bernstein, J . Chem. Phys., 1975, 62, 1058. li”G . M. Bradley, W. Siddall, H. L. Strauss, and E. L. Vaxetti, J . Phys. Chern., 1975, 79, 1949.

le5

Vibrational Spectra of SmaN Symmetric Species nnd of Single Crystals

203

Some details of the spectra of [NH4-nDnlf (n = 0 - 4 ) in [PtCIJ- and [TeC1J2- salts have been discussed in terms of their site symmetries and modes of hydr~gen-bonding.’~~. 174 The first known difluoroammonium salts have been characterized by i.r. and Rainan spectroscopy and the spectra assigned by reference to CH,F, 175 (see Table 5 ) ; more complete assignments have also been Table 5

Vibrational w~noenumbersJcm-lmid nssignnient f o r CZvions A H2B2 v(A-H) WH2) v(A-B) &AB,) Torsion v(A-H) p ,(A H 2) v(A-B) pa( A H2)

A,

A,

Bl €32

Reference Complex multiplet.

[PH,O,I2365 1160 1046 470 930 2308 820 1180 1093 176

“H,F,I+ 2657 1557 1064P 534P

a

-

- b

I185 1039 1474 175

[AsF,]- salt.

obtained17s for the ions [PH202]-, [PHDOJ-, and [PD,O,]- and used for NCA.17? A full assignment has been made of the i.r. spectrum of the niatrixisolated molecule LiF,BeF, and several isotopic variants, in which BeF, is co-ordinated bidentate to 1 i t h i ~ m . l ~ ~ Hexa-atomic Species.--The v7 E‘ mode of PF, is of especial interest due to its iniplication in the axial-equatorial (or pseudorotation) interchange. On the basis of new Raman data for the vapour a barrier of 1371 cm-1 has been estimated for the i n t e r ~ h a n g e . ’ ~Preliminary ~ i.r. and Raman data have been listed for (UC16)2.180 The following new assignment is reported for BrF5(l); in the solid state the observed splittings are in accord with the known Ci;, Z = 4 structure.lB1 C4,

A,

vl

~2

B,

vg v,

689 572 370 539

B2 vg E ~7 ~8

vg

316 610 419 240cm-1

I t has now been shown by electron diffraction that MoOCl,(g) is a C,, monomer and the following new i.r. data have been given: A l v, 143, E v7 396, v8 256, vg 172 cm-l.lN2 Durig and co-workers have reviewed 197 references to the vibrational spectroscopy of XzY4 molecules183and have issued further instalments in the form of I. A . Oxton, 0. Knop, and M . Falk, Canad. J . Chem., 1975, 53, 2675. 1. A. Oxton, 0. Knop, and M . Falk, Cunad. J . Chrm., 1975, 53, 3394. 175 K. 0. Christe, Inorg. Chem., 1975, 14, 2821. M. A. Benoza and V. Tabacik, J . Mol. Structure, 1975,26, 95. 17i V. Tabacik and M. Abenoza, J . Mol. Structure, 1975, 21. 369. A. Snelson, B. N. Cyvin, and S. J. Cyvin, J . Mol. Structure, 1975, 24, 165. L. S. Bernstein, J. J. Kim, K. S. Pitzer, S. Abramowitz, and 1. W. Levin, J . Chenz. Phys., 1975, 62, 3671. IHnW. Kolitsch and U. Miiller, Z . anorg. Chew., 1975, 418, 235. I r k See ref, 1 IS. In: K. lijima and S. Shibata, Bull. Ciienz. Soc. Jupan, 1975, 48, 666. In,’ J . R. Durig, B. M. Girnarc, and J . D . Odom, ref. 22, p. 1.

lid

204

Spectroscopic Properties of Inorganic arid Organometallic Compounds

the first laser-Raman spectra of gaseous N2H4 and treatment of biphosphine.lE5 For the former, IhsyrIdNH)

V,,,Il(NH) 4")

and a detailed

N2Dp,184

N2H4

N2D4

3398 3329 1076

2442 2422 1031 cm-I

and data and assignments for biphosphine are summarized in Table 6. Only the gauche-form is present in all phases thereby witnessing to the effect of the lone pairs and providing a distinction from other P2Y4 molecules. Table 6

Vibrational wmeniimberslcm-l and assignment for P2H4.lR5 (Data for the [2H,]-isomerare also given in ref. 185) Raniari

ltrfrared

2295 2268 I054 1037 882 872

2299

V8

228 1

VS

1

}

v(P-H)

I052

643 628

436 217

v4 v12

8(PPH)

v5

vt3

v(P-P)

v7

Torsion

Hepta-atomic Species.--New data for octahedral M X B species are collected in Table 7. There is a difference of opinion as to the value of v4 for UCI,. For Table 7

Vibrational wnvenumberslcm- for octahedral species

Species

d{

A,,

02MoFs

741.8

E, 652.0

CsMnF, ' K2SnCI, (MeNH,),SnCI,

592 325.6 3 1 6.0

508 246.2 24 1.1

(Me,NH,),SnCI,

3 13.9

(Me,NH),SnCI,

306.4

(Me4N),SnCI, ''

31 1 324 257

245.4 236.7 241.8 232.1 233 286

$;:-

Vlr

v2,

T,, 749.5 (741.4) 616

v35

114,

Tl,

265.7 (262.7)" 332

V5r 7-28

vt3,

T2,'

317

117

308 147.2 174.0 167.7 173.2 159.3 171.3 162.7 163 175

229

I }

Ref. 186

187

188

I89 190

J. R. Durig, M. G. Griffin, and R. W. Macnamee, J . Raman Spectroscopy, 1975, 3, 133. J. D. Odom, C. J. Wurrey, L. A. Carreira, and J. R. Durig, Inorg. Chem., 1975, 14, 2849. lee R. S. McDowell, R. J. Sherman, L. B. Asprey, and R. C. Kennedy, J . Chem. Phys., 1975,62, 3974. S. L. Chodos, A. M. Black, and C. D. Flint, Chem. Phys. Letters, 1975, 33, 344. Inn A. Urushiyania, M. Nakahara, and Y. Kondo, Bull. Cheni. SOC.Jcrpan, 1975, 48, 50. I n @ W. von der Ohe, J. Chem. Phys., 1975, 62, 3933. l o o R. J. H. Clark and W. R . Trumble,J.C.S. Chem. Comni.,1975, 318. la(

Vibrational Spectra of Small Symmetric Species and of Single Crystals

Table 7 (cont.) (M%S),WC16

NdC18-

EuC1,-

GdC1,DyC&ErC&YbC1,NdBr,EuBr,GdBr8DyBr,ErBr,YbBr,UCI, UCI,

uc1,-

a

a

f

UCl6'(Me,N),UCl, LaCle3- g f

f

252

256

258 257 260 263 154 156 157 159 161 160 369 367 348 308 300 273.9

204

(216)

(202) (198) (200) (207) (123) (126) (122) (124) (121)

(119) 325 321 267 230 236 217.9

285 226

226

227 230 229 226 167 164 163 161 166 161 355 343 310 267

121 144 135 139 (143) 139 94 97 90 94 94 96 126 101

122 116 128 110.6

113 111 120 118 111 76 81 85 90 90 78 126 133 136 126

I

205 191 (193)

(193) 192

95

}

180

2

189 196 For lo0MoF6: all other values unchanged. Lattice modes also given. At 9 0 K. Cs,SbCl,- see text. * As pyH+ salts: equivalent values given for Ph,PH+ salts v 2 from ( v z -t vs) Cs+ and Me,N+ salts. As K3, Cs,, and Cs,Na salts: temperature variation also reported.

the series [UCl,]"- (n = 0, 1, 2) the M-Cl stretching force constant varies linearly with number of bonding Dark blue Cs,SbCl, is a mixed-valence compound with a vibrational spectrum corresponding to a sum of those of SbC1,- and SbCle3-. The RRE spectrum is dominated by progressions arising from v1 of SbCl,-. For the first time progressions have been found involving a lattice mode, uiz. v 1 v4 = 384, and 2v1 + V L = 703 cm-l, from which VL z 6 0 ~ r n - ~ .IrCle2' ~ ~ (Bu,N salt in acetonitrile) shows an anomalous RRE, i.e. depolarization ratios > 0.75. Thus:

+

V1

V% v5

cm-l 341 290 161

P

0.35 1.1 2.7

It is known that anomalous p-values are associated with appearance of a contribution from the antisymmetric part of the Raman tensor but the mechanism is unknown. In the present case the cause suggested is a Jahn-Teller effect in excited electronic states.lQ7The measured isotope shifts for vs of [lo4,110PdC1,]2and [lie* 124SnC1,]2-are 3.5 k 0.5 and 3.2 & 0.8 cm-l respectively: further force lol Ioa

Io4 lo6

lV8

P. M. Boorman, T. Chivers, and K. N . Mahadev, Canad. J . Chem., 1975,53, 383. M. Choca, J. R. Ferraro, and K . Nakamoto, J. Inorg. Nuclear Chem., 1975, 37, 1425. Yu. A. Barbanel, R. B. Dushin, and V. V. Kolin, Koord. Khinr., 1975, 1, 41 1. J. Shamir and A. Silberstein, J . Inorg. Nuclear Chem., 1975, 37, 1173. J. Shamir, A. Silberstein, J. R. Ferraro, and M. Choca, J . Inorg. Nuclear Cheni., 1975, 37, 1429. G. N. Papatheodorou, Inorg. Nuclear Chem. Letters, 1975, 11, 483. H . Hamaguchi, 1. Harada, and T. Shimanouchi, Cheni. Phys. Letters, 1975, 32, 103.

206

Spectroscopic. Properties of Inorganic and Organometallic Compounds

constants have been derived t h e r e f r ~ m . ' ~NCA ~ of both ions in JF,+SbF6has been performed using UB, M U , OV, and MOV force fields but the conclusions drawn from the small differences seem to this Reporter to be invalidated due to neglect of interionic terIns.lyy A tentative identification of v3 (775) and v P (430 cm-') for the cation in BrF,+SbFe,- and BrFGSSbF,-,(SbF,), has been reported.200The pressure-sensitivity of the dPt-CI) modes of K,PtCl, and some related salts follows the order v l , A , , > Y,, E, > v3, Tlu.201 Data (not assigned) have been given for K[UOF5]:202i.r. 815, 585, 510, 480, 425; Raman 814, 598, 577, 460, 420, 315, 302, 267 cni-l. Partial or complete assignments are reported for [PtC13Br3]2-,203 [RhCI3X3I3-(X = Br, as well as v3 for [RhXJ3- (X = CI, Br), as [N(CH,C:H2NH3)J3+salts. 3 Single-crystal and other Solid-state Spectroscopy By D. M . Adants As in earlier Reports the emphasis in this Section is on acquisition of new data

on fundamental modes, and their assignment. Thus, work on mixed or doped crystals, alloys, second-order Raman scattering, detailed studies of lattice dynamics, and of mechanisms of phase transitions is excluded. An acute problem in this field is the inaccessibility of many of the sources, particularly non-translated Russian journals, and the never-ending Conference Proceedings, compounded by the writing of uninformative entries for Chemical Abstracts, which appears to have been elevated to an art form. The situation is probably saved by authors' duplicate publications, especially of work in Conference Proceedings. Some of the publications listed at the opening of this Chapter are relevant to this Section. There have been reviews of: Raman spectra of ionic, covalent, and metallic crystals ;.,Or, Raman spectra of molecular crystals ; z o a ~207 i.r. and Raman spectroscopy of liquid crystals ;zoa Raman spectra of and of solids.210 The 12th International Conference on the Physics of Semiconductors 211 contained many reviews and papers on the vibrational properties of crystals; as did that on the 'Transfer and Storage of Energy by Molecules'.212 Apart from A. Miiller, N. Mohan, F. Koniger, and M. C. Chakravorti, Spectrochitn. Acta, 1975, 31, A , 107. IUD L. J. B a d e , F. A. Hohorst, and J. R. Ferraro, Appl. Spectroscopy, 1975, 29, 260. z o o K. 0.Christe and R. D. Wilson, Inorg. Chem., 1975, 14, 694. 8u1 D. M. Adams and S. J. Payne, J.C.S. Dalton, 1975, 215. ? 0 2 P. Joubert and R. Bougon, Cotnpt. r e n d , 1975, 280, C , 193. 2 0 3 I. V. Lipnitskii, N. M. Ksenofontova, A. B. Kovrikov, V. G . Popov, and D. S. Unireiko, Vestsi Akatf. Nauk %. S.S.R., Scr. Fiz.-Mat., 1975, 83. z 0 4 S. G. Zipp and S. K. Madan, Inorg. Chini. Ada. 1975, 14, 83. "-OL G . R. Wilkinson, Ranian Eflect, 1973, 2, 811. 2 0 6 R. Savoie, Ranran Eflt>ct, 1973, 2, 759. 2n7 E. F. Sheka, Mol. Cryst. Liq. Cryst., 1975, 29, 323. "OR V. D. Neff, Liq. Cryst. Plast. Cryst., 1974, 2 , 231. L. A. Shuvalov, V. P. Dmitriev, and L. M. Rabkin, Probl. Issled. Sooisto. Segnetoelektrikov., 1974, 2, 20. 21u G . R. Wilkinson, Mol. Spectroscopy, 1975, 3, 433. 211 'Proceedings of the 12th International Conference on the Physics of Semiconductors', ed. M. H. Pilkuhn, Teubner, Stuttgart, 1974. 'Transfer rind Storage of Energy by Molecules', ed. G. M. Burnett, A. M. North, and J. N. Sherwood, Wiley, New York, 1974. lo"

Vibratiorrnl Spectra of Small Symmetric Species and of Sirigle Ct-ystals

207

general treatments of basic theory, a useful review of the vibrational spectra and crystal-chemical classification of minerals has been given.213 Factor-group analysis (F.G.A.) is now so straightforward with a choice of two r n e t h ~ d s 215 , ~ ~both ~ ~ fully documented, that one wonders at the continuing activity in this area. Brooker 218 makes a useful point in relation to book-keeping when handling orthorhombic crystals, and an aspect of the problem of selection rules in crystals under electrostatic fields has been treated.217 and Donnay and Turrell 21g have further advertised the correlation method of F.G.A., whilst Ferraro 220+ 221 has given two idiosyncratic lists of F.G.A. results. On a practical note, the important matter of a standard for i.r. reflectance has been considered ;222 and criteria for the quality of Kramers-Kronig analysis of reflectance data discussed with reference to Cd3A~2,2‘23 a method suggested for eliminating the apparatus function in the Raman spectra of crystals;22gand a reminder given of the often conveniently forgotten effects of particle size in absorption spectroscopy. 225 ‘Simple’ Lattice Types. --In an important and thought-provoking paper it has been shown theoretically and experimentally that with suitable choice of scattering geometry it is possible to demonstrate the presence of a centre of symmetry by Raman spectroscopy. With the exception of this point, all the information contained in the Raman spectrum of a cubic crystal can be obtained from measurements using crystal orientations (loo), (01 I), and ( O l i ) . To show the presence of a centre of symmetry orientations such as (1 14), ClTO), (22T), or (122) must be used. These points were demonstrated for 1nP (which has firstorder lines at 304, 346 cm-I) using i.r. excitation (the crystal is opaque to visible light).226 I t has also been shown that i t is possible to isolate the totally symmetric Raman modes from all others by measuring appropriate diagonal and offdiagonal tensor components and subtracting in a computer. The technique was illustrated by the first report of the A l spectrum of Cr3B,013C1, chromium boracite, which showed four lines in agreement with theory (176, 209, 375, 657 ~ m - 9 . ~ ~ ’ Assignment of the Raman lines 103 and 438 cn1-l of ZnO as the TO and LO components of an E2 mode has been confirmed ;22H and the thermal dependence zlJ 214

’L15

‘L1(i

z18 218 220

2c1

222

m s26 220

2a7 22n

H. H. W. Moenke, Iilfrared Spectra Miner., 1974, I 1 1. D. M. Adams and D. C. Newton, ‘Tables for Factor Group and Point Group Analysis’, Beckman, Croydon, 1970. W. G. Fately, F. R. Dollish, N. T. McDevitt, and F . F. Bentley, ‘Infrared and Raman Selection Rules for Molecular and Lattice Vibrations; The Correlation Method’, Wiley, New York, 1972. M. H. Brooker, Appl. Speclroscopy, 1975, 29, 528. S. Hayashi and H. Kanamori, Mem. Fac. Ind. Arts. Kj-oto Tech. Univ., Sci. Technol., 1974, 23, 27. V. C. Farmer, Specrrochim. Acta, 1975, 31, A , 1303. J. D. H. Donnay and G. Turrell, Chem. Phys., 1974, 6 , 1. J. R. Ferraro, Appl. Spectroscopy, 1975, 29, 354. J. R. Ferraro, Appl. Spectroscopy, 1975, 29, 418. R. J. Champetier and G. J. Friese, U.S.N.T.I.S. A D Rep., 1974, No. 786783/1GA. H. W. Ellis and J. R. Stevenson, J. Appl. Phys., 1975, 46, 3066. I. A. Gorbatov, B. M. Nosenko, and R. A. Yucupov, Nauchn. Trudy Tashk. Gos. Univ., 1973, 447, 7. T. Lukes, Nature, 1975, 255, 623. P. H. Borcherds and G. F. Alfrey, J. Phys. (C), 1975, 8, 2655. D. J. Lockwood, J. Ranian Spectroscopy, 1975, 2, 555. A. P. Gritsenko, E. G. Dubrova, and V. N. Molchanov, Fiz. Tuerd. Tela (Klturtkoc.), 1974,4,84.

208 Spectroscopic Properties of Inorganic and Organometallic Compounds of the i.r. and Raman spectra of CdS studied in the range 15-600 K.,,@ Far4.r. reflectance data have been reported for CsCl ;230 the LO mode in SmTe has been shown to decrease with increase in and the antiferromagnetic phase of MnO The optical and i.r. reflectance of SnS (distorted rock-salt structure) have been The polymorphs of AgI have been studied by Raman scattering: the 17cm-l E, mode of the wurtzite phase has a strongly negative pressure coefficient ( - 7.5 cm-l kbar-l) at > 1 kbar and shows hysteresis attributed to a sluggish transition to a zinc blende type. The NaC1-type phase shows a second-order spectrum reminiscent of that of AgBr. The disordered phase shows strong broad Rayleigh-like scatter out to 50cm-l and a broad lattice-like mode cn. 1 0 0 Factor group and normal co-ordinate analyses of NiAs and the related Fe,S, have been made.235 All the active-modes of marcasite, FeS,, have been observed in B1, 399; B,, 435, 418, 326; B3, 385, 356, 292 cm-l. All are due to translatory modes. The thermal-dependence of the i.r. reflectance spectra of a- and )5-quartz have been s t ~ d i e d , 238 ~ ~ 'as ~ has the room-temperature reflectance of or-Si,N, (2-50 pm).23u 1.r. transmission and reflection spectra in polarized light have been assigned for or-Sic crystals (the data source is inaccessible) and are said to correlate well with Raman data.240 Almost all of the Raman modes of monoclinic ZrO, and HfO, have been observed (powder samples). Data for ZrO, agree 'reasonably well' with those of earlier reports but the HfO, data appear to be the first for this material; 17 of the 18 predicted modes were found and correlated to those of ZrO,: 112, 1 1 6, 140, 153, 170, 248, 261, 322, 342, 388, 403, 504, 527, 557, 588, 647, and 680 Raman and i.r. spectral changes with temperature, which are quite dramatic, have been used to study the polymorphism of WO,. A monoclinic (I) and a triclinic (11) phase were both found to be stable at room temperature but each showed spectral discontinuities at:

wo3 (1)

WO, (11)

-52,

- 27,

+ 17, 467, 680 "C + 7-29

"C

At >200 "C (11) transforms to (I), as indicated by the behaviour of the lowB. Kh. Bairamov and 2. M. Khashkhozhev, Fiz. Tverd. Tela (Leningrad), 1975, 17, 1358. H. Shimizu and Y. Ohbayashi, J. Phys. SOC.Japan, 1975,39,448. N.A. Begum, Indian J. Pure Appl. Phys., 1975, 13, 194. 23a M. S. Gasanov, Fiz. Tverd. Telu (Leningrad), 1975, 17, 1176. 2ss P. M.Nikolic, S. S. Vujatovic, 0. H. Hughes, C. J. Doran, and J. M. Chamberlain, ref. 211, p. 331. 294 R. C. Hanson, T. A . Fjeldly, and H. D. Hochheimer, Phys. Status Solidi (B), 1975, 70, 567. 236 H. D . Lutz, H. Haeuseler, and P. Willich, 2. Nuturforsch., 1975, 30a, 308. 23a H.D. Lutz and P. Willich, 2. Naturforsch., 1975, 3Oa, 1458. 2s7 F. Gervais, J . Phys. ( C ) , 1974, 7 , L415. ass F. Gervais and B. Piriou, Phys. Rev. ( B ) , 1975, 11, 3944. 2s9 Yu. N. Volgin, G. P. Dubrovskii, and Yu. I. Ukhanov, Fiz. Tuerd. Telu (Leningrad), 1975, 17, 1677. e 4 0 M. A. Il'in and E. P. Rashevskaya, Nuuchn. Trudy., Gos. Nauchno-Zssled. Proektn. Inst. Redkome?. Proni-sti., 1974,55,94. *a E. Anastassakis, €3. Papanicolaou, and I. M. Asher, J. Phys. and Chem. Solids, 1975,36, 667.

Vibratiorial Spectra of’Snrull Symnietric Species and of Single Crystals frequency phonons. For WO, (I) the principal bands are : z 4 z ~243 Raman 1.r.

209

33, 60, 73, 93, 133, 275, 330, 719, 808 230, 285, 310, 335, 370, 665, 765, 825, 920cm-l

The thermal-dependence of the i.r. reflectivity of a-Al,O, has been analysed ;244 and an F.G.A. of ;u-Fe203 246

--

Mixed Oxides, Fluorides, and other Ternary Phases.-The perovskite-type KCaF, and KCdF3 have been studied in the i.r. by both transmission (using thin crystal sections, and polythene discs) and reflectance (with excellent agreement) and the optical constants extracted. The modes found were:247 KCaF,

LO 115 180 259 447

KCdF,

LO 88 144 255 300 451

TO 108 153 195 392

TO 83 114 211 294 403 cm-*

Two low-frequency Raman modes show soft mode behaviour in RbCdF3 (124 K) and TICdF3 (191 K) which have transitions at the temperatures The temperature dependence of the E, soft mode in tetragonal KMnF, has been studied,z4gand further Ranian data reported for KCoF, and R ~ C O F , .All ~~~ three i.r. (TJ modes expected for a cubic perovskite structure have been found fOr.251 CsSnC‘I, CsSnBr,

310 218

172 118

70 68 cni-’

A variety of details relating to the mechanisms of phase transitions and lattice dynamics in KNb0, 262-264 and BaTiO, 266 have been discussed. The polarized Raman spectrum of EuAlO, has been investigated in the range 77-1500 K. Three phonon modes softened in frequency with increase in temperature, and there is a discontinuity at 1420 K due to a first-order phase change.267 Li2Ge03 has been studied by both i.r. reflectance and Raman methods: there was good agreement between the two except that the Raman spectrum showed more modes 255p

242 243 244 246 246

247

240

261 282 2G3

‘LG4

m 26e 05’

E. Salje and K. Viswanathan, A d a Cryst., 1975, A31, 356. E. Salje, Acta Cryst., 1975, A31, 360. F. Gervais, D. Billard, and R. Piriou, Reu. Int. Hautes Temp. Refract., 1975, 12, 58. I. V. Rigina and G. S. Sakash, Zhur. priklnd. Spektrokopii, 1975, 22, 554. G. S. Sakash and I. V. Rigina, Izoest. Vyssh. Uchebn. Zaced., Fiz., 1975, 18, 159. N. S. Al’tshuler, S. A. Basoon, and A. A. Karamyan, Phys. Status Solidi ( B ) , 1975, 70, K127. M. Rousseau, J. Y. Gesland, J. Julliard, and J. Nouet, Phys. Rev. (B), 1975, 12, 1579. B. H. Torrie and D. J. Lockwood, Ferroelectrics, 1974, 8. 583. G. H. Johnson, Diss.Abs. Internat. (B), 1975, 35, 5052. J. D. Donaldson, S. D. Ross, and J. Silver, Spectrochim. A d a , 1975, 31, A, 239. M. P. Fontana and C. Razzetti, Solid State Comni., 1975, 17, 377. A. M. Quittet, M. Fontana, M. Lambert, and E. Wiesendanger, Ferroelectrics, 1955, 8, 585. D. Siapkas and R. Clarke, Phys. Statrrs Solidi ( B ) , 1974, 62, 43. A. Chaves, R. A. Katiyar, and S. P. S. Porto, Phys. Rev. (B), 1974, 10, 3522. D. Heimau and S. Ushioda, Ferroelectrics, 1974, 8, 577. P. Alain and B. Piriou, Solid State Conim., 1975, 17, 35.

21 0

Spectroscopic Properties of Inorganic and Ovgarionietullic Compounds

than theory requires: A , (7/9), A , (9/8), B, (9/7), B2 (13/9) in Ciz; the interpretation is not yet settled.258 Fragmentary i.r. data have been given for some Y and Gd garnets in the 400-800 cm-' interval. Bands at 605 and 665 cm-l are said to be v3 coniponents of (FeO,) groups on S, We list, without significant comment, the following studies which are considered borderline to this review. CdIn,S, : Resonance Raman.2GoRaman and i .r . reflectance. 26: Chromium t hiosp i nels, NCA .2(52 Vibrational spectra of ternary rare earth sulphides and their relation to crystal structure types.263 Smithite, AgAsS,, Raman and i.r.264 Raman spectra of TI,AsS, and A ~ , A s S , . * ~ ~ Ir (2--25 pm) Ag,GeS,; Ag,MSe, ( M = Si, Ge, Sn); Ag,GeTe,.'" CuGaSe, Raman.,,' ZnSiAs, Raman single crystal at 800 oC.26e ZnSiP, and ZnGeP, Raman single Sb5O71Raman."O

Sheet and Chain Structures.-The following data for AuX chains are consistent with their known struct ~ r e s . ~ ~ l X

Ratnan 289, 341 211, 192 156, 107

c1 Bl-

I

Itifrared 320, 353 236, 247 201, 169cm-l

k (N cni-I) 2.09 1.92 1.34

An assignment has been given, from single-crystal i.r. and Raman measurements, for (Me,N)NiBr, which contains (NiBr3-)n chains :272 El " A,,

J5u El u A,,

Infrared I68 159 114 83 55

Al, E2g

E2q E*, EZq

Rammi 180 166 122 84

84cm-I in C,Z,

At 10 K and a little above the quasi-one-dimensional conductor K,Pt(CN),Bro.s,3H20shows a restrahlen-like i.r. reflectance band which was fitted to an oscillator frequency ca. 5 2 cm-l 273 [cf. the value of 40 cm-l reported last year (Vol. 8, p. 230)l. 260

Bel 203

264

2b6 2Ee

2E7 188

pBB *70

p71 272

273

A. Lurio and G. Burns, Phys. Rev. ( B ) , 1974, 10, 3512. E. L. Smirnova, E. F. Efes, and Yu. N. Volgin, Poluprouodn. Elektron., 1974, 1, 45. N . Koshizaka, Y. Yokoyama, H. Hiruma, and T. Tsushima, Solid State Comm., 1975,16,1011. H. Shimizu, Y. Ohbayashi, K . Yamamotu, and K . Abe, J . Phys. SOC.Japan, 1975, 38, 750. H. D. Lutz and H. Haeuseler, Ber. Bunwngespllschaft. phys. Chem., 1975, 79, 604. S. I. Boldish and P. L. Provenzano, Proc. 11th Rare Earth Res. Conf., N.T.I.S., Springfield, Virginia, 1974, 938. D. M. Bercha, I. I. Golovach, and V. Yu. Slivka, Tezisy Doklady Vses. Konf. Khim. Suyazi Poluprouodn. Plumetallukh., 1974, 7 1. D. M. Bercha, V. A. Stefanovich, and V. Yu. Slivka, Tezisy Doklady Vses. Konf. Khim. Suyazi Poluprouodn. Poulmetallakh., 1974, 7 2 . R. Bendorius, A . Irzikevicius, A. Kindurys, and E. V. Tsvetkova, Phys. Status Solidi ( A ) , 1975, 28, K125. W. Braun and J. S. Lannin, ref. 21 1, p. 1308. Yu. F. Markov, T. M. Gromova, Yu. V. Rud, and M.Tashtanova, Fir. Tuerd. Tela(Leningrad), 1975, 17, 1226. M. Attorresi, A. Pincmk, and A. Gavini, ref. 211, p. 321. W. Prettl, K. H. Rieder, and R. Nitsche, Z . Physik, ( B ) , 1975, 22, 49. D. Breitinger and H. Leuchterstern, 2. Nuturforsch., 1974, 29b, 806. D. M. Adams and J. R. Hall, J . Phys. Chem. Solids, 1975, 36, 479. G. Winterling and T. P. Martin, Lect. Notes Phys., 1975, 34, 244.

Vibrational Spectra qj' Sirlull Synrmetric Species mid of Single Crystals

21 1

Layer structures have been more actively studied this year. The strikingly different i.r. spectra of HCrO, and DCrO, have long puzzled spectroscopists. The protiate shows a very broad v(0H) band centred cu. 1650 cn1-l whilst the deuteriate has a pair of bands at ca. 1750 cm-l: the positive shift and the doublet nature have been interpreted in terms of exceptionally different potential energy curves but it has now been shown that this is unnecessary. Fermi resonance appears to take place between a broad v ( 0 D ) fundamental and a sharp 26(ODO) An F.G.A. of CdAs, has been discussed in relation to i.r. and Ranian data,276and an unexpected feature in the far4.r. spectrum of TiCI, below the phase transition point at 217 K has been attributed to covalently bonded Ti3+ pairs.278 Previously observed restrahlen reflectance in the 5@-500 cm-l region of the i.r. spectra of G a s and GsSe has been resolved into three components using appropriate crystal orientations. The unexpected discovery of two doubly degenerate modes in both crystals, contrary to selection rules, is attributed to the large number of stacking faults in the samples.277 Red HgI, continues to draw comment: the theoretical method of Hollebone and Lever (which suggested that a pseudo-cubic cell provided a better basis for understanding the spectrum) has been severely criticized and the conclusion drawn that the only workable basis for analysis of this spectrum is the X-raydetermined factor group.278 The layer lattices BaMF, continue to excite the interests of physicists, chiefly due to phase transitions and associated magnetic changes: Raman studies have been reported for M = Mg, Zn27g and Co, Mn.280sDM LiOH is isotypic with BaFCl and has a biniolecular primitive cell. Its complete Raman spectrum has been determined and assigned (data for liquid nitrogen temperature in wavenumbers/cm-') :282 Dlh

Alu

BlU

3669 k 2 334.4 304.8

v(0H)

VT

VTWi)

Ey

624.3 531.2 287.9

VT vT(Li)

OH- libration

The chain-structures of LiOH,H20 and its deuteriate have been superficially investigated and would be worth a serious investigation. Data for MOH,H,O ( M = Rb, Cs) in the v(OH), 8(OH), and rocking regions have been listed but inadequately Relations between crystalline and amorphous As,Se, vibrational spectra have been discussed.z84 Silicates.-The difficult field of silicate spectroscopy continues to be represented by many fragmentary and qualitative studies such as those on vermiculite and M. F. Claydon, N. Sheppard, B. C. Stace, and J. A. Upfield, J.C.S. Chem. Comm., 1975, 31. A. S. Poplavnoi, Yu. I. Polygalov, and S. I. Skachkov, IzUcst. Vyssh. Uchebn. Zaued., Fiz., 1975, 18, 18. C. A. Emeis, F. J. Reinders, and E. Drent, Solid Stare Contm., 1975, 16, 239. E. Finkman and A. Rizzo, Solid State Comm., 1974, 15, 1841. E. L. Burrows and S. F. A. Kettle, Znorg. Chem., 1975, 14, 2867. M. Quilichini, Phys. Status SoliJi B, 1975, 68, K155. V. V. Eremeako, A. P. Mokhir, Yu. A. Popkov, and Q. L. Reznitskaya, Ukrain. Fiz, Zhur. (Russ. Edn.), 1975, 20, 144. Yu. A. Popkov, S. V. Petrov, and A. P. Mokhir, Fiz. Nizk. Temp. (Kieo), 1975, 1 , 189. F. Harbach and F. Fischer, J . Phys. Chem. Solids, 1975, 36, 601. 1. Gennick and K. M. Harmon, Inorg. Chem., 1975, 14, 2214. E. Finkman, A. P. DeFonzo, and J. Tanc, ref. 21 1, p. 1022.

274 z76

276

277 27H

*8O

284

8

21 2

Spectroscopic Properties of Illorganic and Orgnnonietnllic Comnpoiinc1.y

talc,286synthetic 287 chlorosodalite,*8B and various silicate g l a s s e ~xw, ~ ~ ~ ~ SiO, and y-Ca,(the i.r. and Raman spectra are very like those of olivine),2f” and on the use of i.r. spectroscopy in studying isomorphism in minerals.*B2 However, a sprinkling of more definitive studies by single-crystal methods continues to appear. Polarized i.r. spectra (400-1 150 cn-I) have been used to determine the out-ofplane vibrations in antigorite and in platy liazardite, as well as the vibrations parallel to the fibre axis in chrysotile and fibrous l i a z a r d i t e ~ a, ~good ~ ~ example of the way towards rational understanding of these complex materials. 1.r. reflectance curves (400-1200 cm-I) have been published for all three orientations of (orthorhombic) topaz but oscillator frequencies were not extracted.2u4 The wavenumbers/cm-’ of vibrations with their electric vector parallel to the (unique) b-axis of monoclinic LizSi205,determined by i.r. reflectance, are: 445, 465, 630, 1040, 1105, and 1215 cm-l. The use of 7Li isotopic substitution revealed that the most sensitive region was 3 0 & 5 5 0 ~ m - ~ . ~ A~most ~ valuable NCA has Basically, it is a fairly good approximation been made of forsterite, Mg2SiOp.2B8 to regard the spectrum as composed of the modes of tetrahedral (Si04),-, factor group split. The lowest modes (v,) run into an extensive series of lattice modes which can be broadly classified as rotatory or translatory. Further data on silicates are mentioned in Chapter 5.

Oxoanionic Crystals.-The general features of crystals containing tetrahedral oxanions is that, as in forsterite (above), they consist of regions of complex behaviour (due to site and correlation field effects) centred around the vl and v3 v(M=O) modes, with the v 2 , v4 deformations drifting down into a complex set of lattice modes. This year has seen further qualitative studies of several systems of this type which confirm these features: Mg3(V04)2 (i.r. and Ranian of powders);297and the LiMg, LiCd, and NaCd salts of VO,”, all of which are said to have the Na2Cr04structure, although they obviously cannot.20nEntirely analogous treatments have been given for Pb2V207,2BB and for Cd2V20,, Mn2V20,300 (qualitatively interpreted lists of frequencies are given), H g MOO,, HgWO,, and CdW04.301The i.r. spectrum of CsDy(MoO,), indicates a phase transition at ca. 38 K;302and a further NCA of scheelite has been D. K. Arkhipenko and G . B. Bokii, Zhur. srrukr. Khim., 1975,16, 450. A. A. Kubasov and K . V. Topchieva, Sovrem. Probl. Fiz. Khim., 1975, 8, 309. 287 J. B. Scherzer, J. L. Bass, and F. D. Hunter, J . Phys. Chem., 1975, 79, 1194. 1n8 G. A. Golubova and I. A. Belitskii, Eksp. Issled. Mineral, 1974, 99. 28B S. Brawer, Phys. Rev. ( B ) , 1975, 11, 3173. S. Brawer and W. B. White, J . Chem. Phys., 1975, 63, 2421. *@lE. Goerlich and M. Handke, Cement- Wapno-Gips, 1975,29, 201. 29a E. S. Rudnitskaya, E. V. Vlasova, and T. A. Ziborova, Ocherki Fiz.-Khim. Petrol., 1975, 5 , 286

28a

aB7

290

Oo0

235. S. Yariv and L. Heller-Kallai, Clays Clay Minerals, 1975, 23, 145. L. T. Kovaleva, Zhur. priklad. Spektroskopii, 1975, 22, 311. A. N. Lazarev, V. F. Pavinich, and A. P. Mirgorodskii, Probl. Khim. Sili, ., 1974, 115. V. Devarajan and E. Funck, J . Chem. Phys., 1975, 62, 3406. E. J. Baran, Monatsh., 1975, 106, 1. M. T. Paques-Ledent, Chem. Phys. Letters, 1975, 35, 375. E. J. Baran, J. C. Pidregosa, and P. J. Aymonimo, Monatsh., 1975, 106, 085. P. Schwendt and V. Graus, Chem. Zvesti, 1974, 28, 743. G. Blasse. J . Inorg. Nuclear Chem., 1975, 37, 97. A. I. Zyvagin, S. D . Yel’chaninova, and T. S. Stetsenko, Fir. Nizk. Temp (Kiev), 1975, 1, 79. I. Kazuaki, 2. Krist., 1975, 141, 31.

Vibrational Spectra of Small Symmetric Species a d of’Single Crystals

21 3

Single-crystal i.r. reflectance ( E I] a and to c ) for P2/c(C,4,,) NiWO, yielded the following TO oscillator frequencies (Kramers-Kronig) 305 :3049

E E

11 a (B,) 11 c (B,)

232, 298, 378, 470, 775 268, 328, 584 cni--l

Much further effort has been invested but little light shone on series of quaternary oxides in which at least one metal atom is in octahedral coordination: the authors seem determined to interpret these spectra in terms of an unacceptable model based upon disturbed MO, octahedra. Systems studied include: SrLaLiW0,;306 Ba,BTe06;307Ba2-zSr,MgW0,;308 MTiTaO, (M = Y, L~-LU);~O~ MTiNbO, ( M = La, Ce, Pr, Nd, Sm, E U ) ; ~ ~Li,MO, O (M = Te, W) and Li,M06 (M = Nb, Bi);311SrLaMgSbO,, and Ba4LiSb30,,. Occasional mention of further 0x0-species is made under the appropriate transition metal in Chapter 6. Complex Cationic Salts.-The major part of this Section again comes from increasingly complex investigations into the lattice dynamics of ammonium salts nearly all of which show phase transitions. NH,F is unique among ammonium halides in having the wurtzite structure, which has a polar space group and hence gives rise to LO-TO splitting of A l and E modes. These symmetry species have been studied in the region of the lattice modes by the single-crystal Raman technique (at 80 and 300 K ) . The LO-TO splitting was 125 cm-l and, clearly, the effect of the long-range electrostatic forces dominates the anisotropy of the short-range interatomic forces.312 Changes in the NH4Br Raman spectra consequent upon the 111 IV phase transition have been shown to agree with and the effects of pressures up to 42 kbar demonstrated.314 A result of particular interest in a theoretical study of NH4Br, based upon the shell model, is that it is not necessary to assume short-range order among NH4+ ions to account for the appearance of sharp Raman bands in the disordered phase.316 The mechanics of the phase transition in (NH4),S04have been examined by i.r. and Raman method^,^^^-^^* and a further single-crystal Raman study --f

Ioe

t.O0

B1o 811

al)

s14 s18 81* 817

V. I. Kut’ko, Fiz. Kondens. Sostoyaniya, 1974, 30, 108, Yu. V. Pereverzev, V. I . Kut’ko, V. M . Naumenko, and A. I. Zvyagin, Fiz. Kondens. Sostoyaniya, 1973, 26, 96. D. Krol and G . Blasse, J . Inorg. Nuclear Chem., 1975, 37, 1328. M. Liegeois-Duyckaerts, Spectrochim. Acra, 1975, 31, A , 1585. G. Blasse, J . Inorg. Nuclear Chem., 1975, 37, 1347. V. I. Rogovich, E. I. Krylov, V. K . Slepukhin, and B. V. Shul’gin, 2hur.fiz. Khim., 1975,49, 266. A. M. Sych, E. M. Verlau, and V. G. Klenus, CJkrain.3~.Zhur., 1974, 19, 2034. A. Muller, E. J. Baran, and J . Hauk, Spectrochim. A m , 1975, 31, A , 801. M. Couzi, J . Phys. and Chem. Solids, 1975, 36, 913. G . G. Mitin, V. S. Gorelik, M. M. Sushchinskii, and A. A. Khalezov, Zzvest. Akad. Nauk S.S.S.R., Ser. fiz., 1975, 39, 728. V. Ebisuzaki, J . Chem. Phys., 1975, 63, 4947. T. Geisel and J. Keller, J. Chem. Phys., 1975, 62, 3777. G. N. Zhizhin, T. P. Myasnikova, and V. N. Rogovoi, Fiz. Tverd. Tela (Leningrad), 1975,17, 1270. M. V. Belousov, V. A. Kamyshev, and A. A. Shultin, Izvest. Akad. Nauk S.S.S.R., Ser. Jz., 1975.39, 744. M. V. Belousov, V. A. Kamyshev, and A. A. Shultin, Prohl. Issled. Svoistv. Segnetoelektrikov., 1974, 2, 23.

214

Spectroscopic Pt.opei*tiesof Imrgariic arid Orgatinmetallic corn pound.^

reported for this material at room ten~perature."~Fragmentary i.r. data have been reported for NH,CI0,."20 A most valuable i.r. and Karnan study has been made of oriented single crystals of N,H,CI (orthorhombic) and N,H,Br (monoclinic) both of which have tetramolecular primitive cells. The i.r. mrork was done on crystallized films whose orientation was determined by X-ray diffraction. The assignment deduced for N2H5+is shown in Table 8 and differs from a much earlier one due to Decius

Table 8

Wnueririr?ibers/cni-' atid assigrinieiil -for N2H5f and N2D5+ 321 iri N,HBCI H5 3252 3141 1632 1421 1255 3037 2952 2901

D, 2436 2309 1193 1104 1005 2268 2216 2100

and Pearson, as well as being more complete. The authors did not consider the region below 350 cni-l where the lattice modes lie.321 The related compound (N2H6+)(H+)(C,0,2-) and its deuteriate have been similarly investigated in polycrystalline form and the spectra shown to be consistent with the known crystal structure. A phase change to a larger but centrosymmetric cell was indicated at ca. 240 K.322 Fairly full assignments have been offered for Raman spectra of Mg(HzPOz),,6H20, Mg(H,P02),6D20, and Co(H2P0,),6H20 in conformity with earlier and some fragmentary data given for single-crystal CoC1,,6H,O in the course of an electronic spectral Much effort has been expended in work325 on single-crystal studies of [ C O ( N H ~ ) ~salts ] ~ + and those of [ C O ( N H ~ ) ~ N Oand ~ ] ~[Co(NH,),(NO,),]+ but the paper lacks essential practical detail and it is not clear in some cases which assignments did in fact originate on the basis of the new measurements. Further, the hexa-animine salts of CI- and CIO,- have such large primitive cells as to make interpretation almost impossible and this aspect of the work therefore adds little to our understanding. Data for the external mode region are not reported. The clearest work is on [Co(NH,),NO,]CI, for which i.r. dichroic measurements were made: unfortunately the crystal decomposed in the laser beam and singlecrystal Raman spectra could not be obtained although powder-sample spectra were obtained. Nevertheless, the interpretation offered is inconsistent with the data.326 [Co(imidazole),](N03), has a monomolecular primitive unit cell in which the molecular, site, and factor group symmetries are all S6. This is an ideal situation, 310

3ao y21

s2a

324

326

P. Venkateswarlu, H . D. Bist, and Y . S. Jain, J . Rainan Spectroscopy, 1975, 3, 143. M. E. Hills and W. R. McBride, U.S.N.T.I.S., A D Rep., 1974, No. 787504/OGA. J. DeVillepin and A. Novak, Mol. Cryst. Liq. Cryst., 1974, 27, 391. R. Savoie and M. Guay, Canad. J . Chein., 1975, 53. 1387. M. Abenoza and L. Martin, J. Rainan Spectroscopy, 1975, 4, 185. J. Ferguson and T. E. Wood, Inorg. Chem., 1975, 14, 184. M. Le Postollec, J. Chini. phys., 1975, 72,675.

Vibrational Spectra of Sniall Symmetric Species and of Single Crystals

21 5

especially as both A and E species are involved. v(M-N) was located at ca. 250cm-l. The most notable result, however, was the discovery that the lowfrequency spectra are dominated by a series of intense bands (i.r. and Raman) due to ligand torsional and M-N-C deformational modes: these are formally analogous to the well-known S(MC0) modes in c a r b o n y l ~ . ~ ~ ~ The symmetry species of all of the i.r. and far4.r. bands in Pd(en)CI, have been assigned using single-crystal methods. The experimental account is exemplary and gives the kind of detail that would enable another person to repeat the work. Ranian single-crystal work was disappointing as there was polarization scrambling in the very small crystals used. Although the crystal symmetry species have been determined their relation to molecular internal modes was not readily

Complex Anionic Salts.-Considerable activity continues to elucidate the mechanisms of phase transitions in azides. New i.r. reflectance data for p-NaN, (stable above 18 "C) established values of 642.8 and 2179.9 cm-l for the v,(E,) and ~ 3 ( A 2 , ) fundamentals (in 0gd).328 In the Raman spectrum the splitting of the E, mode into A, + B, components at the phase transition was used as an indicator in studying the T-P variation of the t r a n ~ i t i o n . ~ 330 ~ ~Ing NaN, the v, 6(N,) mode remains degenerate on a DJd site but in tetragonal KN3 with its bimolecular E,. These cell v2 appears as factor group components A2,, + Bl,(inactive) modes have been located at 642.2 (Azu) and 649.3 (15,)cm-' by single-crystal i.r. t r a n s m i ~ s i o n . ~The ~ ' Raman spectrum of polycrystalline CsN, has been obtained for phases I (at 436 K), I1 (at 295 and 20K), and III (ambient and 8 kbar). The remarkablc broadening of the E, rotatory mode with increase of temperature and the observation of quasi-elastic low-frequency scatter in I support the orderdisorder character of the transition. Phase 111 shows much sharper Raman lines and seems to have a more complex and compact Similar softening of a librational mode has been seen in TlN3 near its phase transition ca. 240 K (Raman study).,,, 1.r. and Ranian frequencies have been listed for M2Zn(N,), (M = K, Rb, Cs), but not assigned.334 A most important and comprehensive i.r. and Raman single-crystal study of KHF, and KDF2 has been reported. All of the predicted modes were found (Table 9). In particular, the half-width of the antisymmetric hydrogen motion in HF2- was shown to be 40 cm-I, much smaller than previous estimates. There is a small contraction of the H-F bond length on deuteriation as shown by the ~ ~ phase ~ transitions in change in the A l , v 1 mode from 600 to 601.5 ~ n 1 - l .The NaNO, and K N 0 2 at cu. 10 kbar have been observed by i.r.

+

yJG

D. M. Adams and W. R. Trumble, J.C.S. Dalton, 1975, 30. R. W. Berg, Spectrochim. Acta, 1975, 31, A , 1409. L. R. Fredrickson and J. C. Decius, J. Chenr. Phys., 1975, 63, 2727. G . J. Simonis and C. E. Hathaway. Phys. Reu. (B), 1974, 10. 4419. Z. Iqbal and C. W. Christoe, Solid Srate Coninr., 1975, 17, 71. R. T. Lamoureux and D. A. Dows, Spectrochinr. Acta, 1975, 31, A , 1945. Z . Iqbal and C. W. Christoe, J. Chcm. Phys., 1975, 62, 3246. Z. Iqbal and C. W. Christoe, Chctn. Phys. Letters, 1974, 29, 623. W. Dobramysl, H. P. Fritzer, and S. F. A. Kettle, Spectrochim. Acta, 1975, 31, A, 905. P. Dawson, M. M. Hargreave, and G. R . Wilkinson, Spectrochim. A d a , 1975, 31, A ,

336

D. M. Adams and S. K. Sharma, Chern. Phys. Letters, 1975, 36, 407.

32R 327

338 32R :I:"'

331

336

3:L3

304

1055.

-

Spectroscopic Properties of Inorganic and Organornetallic Compounds

216

Table 9

Wavenumbers/cm-' and assignment for KHF, and KDF, at 100 K KHF,

I.r.

A Di:, Z = 2 A,,

v1

E" Et'

v2 v2 v3

B2,

y1

TO

LO

Raman 605 615

}1225 1425

7

TO

I.r.

LO

} 884

907

1665

995

1170

153

182 138

Raman 601 61 1

1258

155 1 04

s25

KDF,

235 165

155 104 153

A rigid-ion model analysis of published vibrational data for calcite and magnesite showed that the observed TO and LO modes could be accounted for with effective charges:337 Ca C 0

1.21 0.20 -0.47

Mg C 0

1.28 0.21 -0.50

A similar calculation was performed for dolomite, CaMg(C0,),.838 Asymmetry on the high-frequency side of vl of NO3- in its Na+, Cs+, and Ag+ salts arises from a combination of correlation field splitting and hot bands.33g Raman spectra of polycrystalline MBr03(M = Li to Cs) have been qualitatively discussed in terms of factor group analyses.34oThe v1 mode of [7aBr160,180]differs by 1.6 cm-l from that of [81Br1602180]-and a similar separation was observed for [79Br160,170]and [s1Br1602170]-, although there was no difference for [7gBr1603]and [81Br1603]-.341 Further i.r. and Raman single-crystal data have been reported for O L - L ~ I O Both ~ . ~internal ~~ 343 and external 344 modes of alkali metal trihydrated selenites have been studied (title only translated in Chem. A h . ) . A full single-crystal i.r. and Raman study has been made of sulphanic acid, NH3SOs, and its deuteriate. 23/24 Raman and 6/15 i.r. modes in the Dfi, Z = 8 cell were located at 30 K.345

s40

a'1 spa

a44

A. Yamamoto, Y. Shiro, and H. Murata, Bull. Chem. Soc. Japan, 1975, 48, 1102. A. Yamamoto, T. Utida, and H. Murata, and Y. Shiro, Spectrochim. Acta, 1975,31, A , 1265. D. W. James, M. T. Carrick, and H. F. Shurvell, Austral. J. Chem., 1975, 28, 1129. 1. I. Kondilenko, P. A. Korotkov, and N . G. Glubeva, Optika i Spektroskopiya, 1975, 38, 689. J. B. Bates and H. D. Stikham, Solid State Comm.,1975, 16, 1223. S. A. Kutolin, L. F. Belova, R. N. Samiolova, 0. M. Kotenko, I. M. Dokuchaeva, and N . M. Ivanova, Zzvest. Akad. Nauk S.S.S.R.,Neorg. Materialy, 1975, 11, 862. L. M . Rabkin, V. P. Dmitriev, and L. A. Shuvalov, Probl. Issled. Svoisrv. Segnetoelektrikou., 1974, 2, 20. V. P. Dmitriev, L. A. Shuvalov, and L. M. Rabkin, Probl. Issled. Svoistv. Segnetoelektrikov., 1974, 2, 21. G. Lucazeau, A. Lautie, and A. Novak, J . Raman Spectroscopy, 1975, 3, 161.

Vibrational Spectra of Small Symmetric Species and of Single Crystals

21 7

A detailed i.r. dichroism study (plus polycrystalline Raman data) has been made of H2S04and D,SO,. For the S-0 modes a rough correlation to those of tetrahedral sulphate was found : H,SO4 Ba 1393 A,

B, Al

1169} 998 914

v3

T,

1128

vl

A,

989

The 0 - H modes were located at: v(0H) 2980-3092 cm-l, 6(OH) 1238, y(0H) 620-647 cm-l with a group of lattice modes at ca. 140 cm-l due essentially to H-bond Vibrational data have been listed for polymorphs of Na2S04,347 and Raman data for RbHS0,.34R The splittings observed in anion niodes in many different crystalline sulphates have been attributed primarily to static field effects, with the dynamic or correlation field modulating crystal frequencies about the average values set by the static field.340A further singlecrystal Raman study of LiaS04,H20 has appeared 3s0 (see earlier Reports). Single-crystal Raman data for NaNH4S04,2H20,351s 352 K2Se04,363 and NaNH4Se0,,2H,0 3 5 4 in both para- and ferro-electric phases have been discussed in terms of the structural rearrangements involved. A most thorough single-crystal i.r. and Raman study has been made of KzS206which has an enantiomorphic trimolecular cell and hence presents some technical These were overcome and a full assignment produced which was essentially in agreement with earlier work on the sodium salt. A further complete i.r. and Raman study has been made of single-crystal apatite, Ca,(PO,),F 356 (Vol. 8, p. 239); Raman powder data have been listed for b r ~ m o a p a t i t e 1.r. . ~ ~and ~ Raman data (250-1 500 cm-l) for cubic pyrophosphates MP,O, fall into two groups for M = Ge, Sn, Pb, or M = Ti, Zr, Hf; no assignments were made.358 Many phosphates and arsenates exist in para- and ferro-electric forms and are the object of many detailed spectroscopic studies aimed at uncovering modes of phase transition and lattice dynamics. Accordingly, we simply note that the following have been reported: KH,P04 R a m a ~ ~361*, ~365~ ~Raman . at high 3dB

347

n4u 361

353 363 3b4 36h

Bbo

35u

A. Goypiron, J. de Villepin, and A. Novak, Spectrochim. Acta, 1975, 31, A , 805. J . E. D. Davies and W. F. Sandford, J.C.S. Dalton, 1975, 1312. J . W. Arthur and W. Taylor, Ferroelectrics, 1974, 8, 533. 13. J . Berenblut and P. Dawson, Spectrochim. Acta, 1975, 31, A , 1541. R. P. Canterford and F. Ninio, J . Phys. (C), 1975, 8, 1750. V. Fawcett, D. A. Long, and V. N. Sankaranarayanan, J. Raman Spectroscopy, 1975, 3, 197.

V. Fawcett, D. A. Long, and V. N. Sankaranarayanan, J . Raman Spectroscopy, 1975,3, 217. V. Fawcett, R . J. B. Hall, D. A. Long, and V. N. Sankaranarayanan, J . Raman Spectroscopy, 1975, 3, 229.

V. Fawcett, D . A. Long, and V. N. Sankaranarayanan, J . Raman Spectroscopy, 1975,3, 177. 1’. Dawson, M. M. Hargreave, and G. R. Wilkinson, Specfrochim. Acta, 1975, 31, A , 1533. D. K. Arkhipenko, V. N. Stolpovskaya, and B. A. Orekhov, Trudy. Znst. Geol. Ceofiz., Akad. Naitk S.S.S.R. Sib. Otd., 1975, 50, 89. R. A. Condrate, B. C. Cornilson, and E. Dykes, Appl. Spectroscopy, 1975, 29, 526. C. Huang, 0. Knop, D . A. Othen, F. W. D. Woodhams, and R. A. Howie, Canad. J. Chem., 1975, 53, 79.

A. M. Pope1 and 1. V. Stasyuk, Ukrain.fiz. Zhur ( R u m Edn.), 1974, 19, 1955.

21 8

Spectroscopic Properties of Inorganic and Organometallic Cornporrnds

i.r. 362 and K D 2 P 0 4 Raman and i.r.363-366Of more general interest, however, is a group of experiments on the Al and B1 modes of KH,P04.S66~ 367 These employed a cylindrical single crystal (optic axis normal to cylinder axis) which was studied by Raman scattering as a function of angle of rotation about the b-axis. Theory for k z 0 modes requires the spectral intensities to be constant but a periodic variation was observed. Such behaviour is well known for polar modes but has not previously been reported for non-polar ones and requires an explanation. Raman and i.r. spectra have been reported for polycrystalline MBF4 Cs,MgCl, (M = K, Rb, Cs) at low temperatures and assigned in contains discrete MgC142-ions; a single-crystal Raman study of it (Dift, 2 = 4) revealed a spectrum close to that reported for (Et4N)2MgC14but with some splitting about those frequencies due to the correlation field; only a few of the expected lattice modes were found. K2MgC14 has an entirely different structure (Dii, 2 = 1) with Mg in six-co-ordination; it yielded poor Raman spectra from which only the two E, modes (77, 212 cm-l) could be discerned, apart from some weak second-order features.36e The values of Table 10 resulted from an i.r. and Raman study of M2GeS4corn pound^.^^^ ;350e

Table 10

Wavenumbers/cm-l for M,GeS4 compounds 370 Td M = Sr Ba Pb

a

vs(T2)a

416 415 385

V I M 1) a

382 393 36 1

v4(T2)a

258 254 237

v2(JV

206 202 199

These are average values; crystal effects cause splitting.

New single-crystal X-ray and other tests indicate that [Et4N],[MCI5] (M = T1, In) are isomorphous and that the reported P4/n space group is incorrect and should be Pq. This prompted a reinvestigation of the single-crystal Raman spectra which yielded improved data and a slightly modified New single-crystal Raman data for (Me4N),UC16were given in Table 7; the same work included a full assignment for the cation.18* On lowering the temperature a phase transition occurs to a space group which is possibly Raman spectra for K2SnBr, at 140°C are in accord with the known cubic 3R0 3R1

362 3f13 8f14

3R5

3efl 3f17

sR8 3BD 370 871

372

P. S. Peercy, Solid State Comm., 1975, 16,439. C.Y. She and C. L. Pan, Solid State Comm., 1975, 17,529. B. N. Crib, I. I. Kondilenko, P. A. Korotkov, A. I. Pisanskii, and Yu. P. Tsyashohenko,

Optika i Spektroskopiya, 1975, 38, 73 1 . T. Kawamura, A. Mitsuishi, and N. Furuya, Technol. Rep. Osaka Univ., 1974, 24, 1191. T. Kawamura, A. Mitsuishi, N. Furuya, and 0. Shimomura, Technol. Rep. Osaka Univ., 1974, 24, 429. D . S. Bystrov, A. P. Vorob’ev, and E. A. Popova, Izaest. Akad. Nauk. S.S.S.R.,Ser. fiz., 1975, 39, 738. M. K. Srivastava, C. H. Wang, and R. W. Grow, Chem. Phys. Letters, 1975, 35, 264. M. K. Srivastava and C. H. Wang, J . Chem. Phys., 1975, 62,3439. J. B. Bates and A. S. Quist, Spectrochim. Acra, 1975, 31,A , 1317. M. H. Brooker, J . Chem. Phys., 1975, 63,3054. M. Neyrand, M. Ribes, E. Philippot. and M. Maurin, Rev. Chim. mindrule, 1975, 12, 406. G. Joy, A. P. Gaughan,jun., I. Wharf, D . F. Shriver, and J. P. Dougherty, Inorg. Chem., 1975, 14, 1795. W. von der Ohe, J. Chem. Phys., 1975, 63,2949.

Vibrational Spectra of Small Symmetric Species and of Single Crystals

219

symmetry and show only the three internal modes (ul, v2, us) with n o lattice mode. At room temperature and below the structure is tetragonal ( D t , Z = 2) but, although no significant change was seen in the internal modes, three lattice modes appeared and, by - 178 "C, were joined by three more: 33,47, 57, 75, 80, 88 cm-', about half the number allowed.373 A most thorough study of M,Cr3CI, (M = K, Rb, Cs) by single-crystal i.r. reflectance and Raman methods resulted in identification and unambiguous assignment of almost all of the allowed modes. A n N C A of the anion assisted in the assignment 374 (Table 11). Further data (see Vol. 8, p. 241) from single-

Table 11 Vibrational wavenurnbers/cm-' and assignment O3h

vl

terminal stretch bridge stretch terminal bend CrC1,Cr breathing

E'

u4

368 274 206 131

Ag" vs v6 v7

339 243 182

terminal stretch bridge stretch terminal bend

E"

Al'

u2

vg

~9

~ 1 0

ull vI2 ~ 1 3 ~ 1 4 ~ 1 5

v16 a

374

for [Cr,C1J3-

358 238 206 159 80 330 198 170 138

terminal stretch -

-

CrCl, wag terminal stretch -

CrCI, wag

No assignment indicates heavily mixed mode.

crystal Raman studies of K3[U02F3]and the rubidium salt, in combination with other results, yielded the ranges for anion modes:376 A,' A,:

VI

V,

EZ

VS

784-819 423-440 318-329

UQ

ul0

E2: El

209-219 250-271

cm-'

Following the i.r. and single-crystal Raman work o n K,Zn(CN), reported in the last two years comes another study dealing specifically with isotopically substituted Selected data are in Table 12. Force-field calculations

Table 12

Vibrational waveriumber.slcn~-l and assignments of Ramart data for isotopically enriched species K2iZn(kCLN)4 Aqueoirs solution :

Al,

Ev

T2v

k, 1 V1

v2 V3

v:,

12, 14 2151.4 341 3 16.6 2149.5

13, 14 2105.1 333 306 2103.1

12,15 21 19.7 33 1 3 15.6 21 17.9

were performed: the results showed that in comparison with Ni(C0)4 there is negligible back-bonding from zinc to anions. 3i3

siJ 3:6

J. W. Anthonsen, Acta Chem. Scand. ( A ) , 1974, 28, 974. J . D. Black, J . T. R . Dunsmuir, 1. W. Forrest, and A. P. Lane, Inorg. Chem., 1975, 14, 1257. H. Brusset, Nguyen Quy Dao, and M. Knidiri, Spertrochinz. Acfa, 1975, 31, A , 1819. L. H. Jones and B. I. Swanson, J . Chem. Phys., 1975,63, 5401.

220

Spectroscopic Properties of Iiiorganic and Organometallic Compounds

A solution Raman study of K,Mn(CN), led to the assignment:377 Al,

v1 v2

2123P 373P

E,

vB v4

2123 353

T2,

v10

vll

413

96 cm-l

However, single-crystal Raman spectra failed to reveal any bands in the region 175-2110 cm-l apart from 372 cm-l: this may be due to failure to use low temperatures. Polarized i.r. work 3 7 8 on K,Cr(CN), has improved an earlier assignment. the O Detailed Raman observations have been made of C U ( H C O ~ ) ~ , ~inH ~ vicinity of its ferro-electric phase transition (235.5 K). A broad Raman band associated with external water modes splits into five lines below Tb,and the doubling of the cell is indicated by splitting of the forniate modes v,, v3, and v,8a3” Absence of angular dispersion of the polar modes favours the space group P2,/n rather than P2, for the low temperature phase.380 Molecular Crystals.--The commonly used oriented gas model gives good qualitative agreement with experiment for molecular internal modes but for lattice modes, especially librations, agreement is sometimes very poor indeed. Available Raman single-crystal data have been analysed for 1 1 organic crystals; it was found that only three were compatible with the model, but it was not possible to say Green’s function method, developed for the study of molecular vibrations, has been extended to the optically allowed vibrations of crystals, using BzFl as an example.382 In a technically impressive investigation the symmetry species of single libron modes in solid hydrogen have been determined using oriented single crystals. The results provide the first experimental basis for the Pa3 structure. Spectra of various rotational transitions in disordered phases of H2 and D2 were also The vibrational properties and certain crystal energetics of a- and y-N2 crystals have been tolerably well reproduced using a 12-6 atom-atom intermolecular potential,384and a similar calculation has been performed for CI, and Bry.385 Raman lattice-mode frequencies of CI, and Br2 were redetermined and found to be in close agreement with those of Raman data have been listed (18 and 79 K) for polycrystalline XCN (X = CI, Br, New i.r. data have been obtained for crystalline films of 14N21G0,with particular attention being paid to two phonon processes. The crystal is cubic (T4, Z = 4) with the molecules on C , sites: the expected factor group splitting of the v2 band was observed for the first time. LO mode positions were determined directly using samples at non-normal incidence.388 377

378 378

a80

3*1

382

383 384 586

B87 388

P. Waage Jensen, J. Raman Spectroscopy, 1975, 4, 75. J. Hanuza and B. Jezowska-Trzebiatovska, A c f a Phys. Polon. ( A ) , 1975, 47, 155. J . Berger, J . Phys. Chetn., 1975, 8, 2903. R. P. Canterford and F. Ninio, J . Phys. ( C ) , 1975, 8, 385. E. Burgos, H. Bonadeo, and E. D’Alessio, J . Chetn. Phys., 1975, 63, 38. K. M. Padmaja and G. Aruldhas, J . Phys. Chem. Solids, 1975, 36, 563. W.N. Hardy, I . F. Silvera, and J. P. McTague, I’hys. Rev. ( B ) , 1975, 12, 753. A. Zunger and E. Huler, J . Cheni. Phys., 1975, 62, 3010. G. G . Dumas, F. Vovelle, and J. P. Viennot, Mol. Phys., 1974, 28, 1345. A. Anderson and T. S. Sun, Chetn. Phys. Letters, 1970, 6, 6 1 1. T. S. Sun and A . Anderson, J . Raman Spectroscopy, 1975, 2, 573. V. Schettino and P. R. Salvi, Spectrochini. A d a , 1975, 31, A , 399.

Vibrational Spectra of Small Symmetric Species and of Single Crystals LO v3 V1

v2

22 1

TO

2258 1298.5 591.5

2237 1292.5 588.5, 586.0 cm-I

The v3 band of OCS has long been a puzzle as it is exceptionally broad and odd in shape. In the Raman v3 appears as a sharp band at 2004cm-l, and this coincides with the observed i.r. maximum of what is a highly asymmetric band on the high frequency side. It has now been shown that this shape is due to reflection effects between the TO and LO frequencies.389 The complexity of the vibrational spectra of solid BF3 indicates that it is not isomorphous with the other boron trihalides; X-ray measurements showed that it is PI, 2 = 8. For this group four Raman and four (non-co-incident) i.r. bands are expected for vl, for example, compared with the four and three respectively, revealed by experiment; Raman 873, 875.5, 880, 882; i.r. 877, 880, 881.5 cm-l. Fewer than the theoretical number of lattice modes was found but this is not surprising with such a large cell.390 Three simple tetrahedral-molecule crystals have been re-investigated. CF, freezes at 89.5 K to a plastic phase I in which there appears to be free rotation. At 76.2 K there is a transition to phase I1 for which the far4.r. spectrum now reported is in conflict with predictions based upon the reported space group. The i.r. spectrum shows bands at 51, 57, and 66 cm-l which are accounted for on the basis of C2/c, 2 = 4 which was found to be consistent with an alternative interpretation of the X-ray powder data.391 1.r. spectra of SiH3D in SiD, revealed a second-order phase transition at 38 K.392 New Raman data for SnI, are consistent with extant values: Solution Solid, 1 0 0 K

V1

150 150

v2

41 55

v3 208 212, 218

v4

65 67 cm-l

Only v3 shows factor group splitting.393Seven lattice modes are allowed but the only bands observed were at 23, 28, and 37 cm-l. A soft mode (frequency not in Chern. Abs.) was found in the Raman spectra of HgZC12 and Hg,Br2 at temperatures below the phase Although VO(acac), crystallizes in the triclinic system ( P I , 2 = 2) it has been shown that meaningful i.r. dichroic experiments can be performed on it. The results were used to establish the assignment for the molecular B2 (in C2w) Further data have been reported (polycrystalline samples) for cO(~6-c&)a (i.r.) and Ni(qa-C6H6)a(i.r. and Raman). At liquid nitrogen temperature the spectra were consistent with predictions on the basis of the room temperature 3H0 s9n

381 3DZ

as4

V. Schettino and P. R. Salvi, Spectrochim. Acta, 1975, 31, A , 411. 0. S. Binbrek, J . K. Brandon, and A. Anderson, Canad. J. Spectroscopy, 1975, 20, 52. Y. A. Sataty, A. Ron, and F. H. Herbstein, J . Chcnt. Pliys., 1975, 62, 1094. R. E. Wilde and T K. K. Srinivasan, J. Phys. a n d Chem. Solids, 1975, 36, 119. P Dawson, Spectrochim. Acta, 1975, 31, A , I I0 I . C. Rarta, A. A. Kaplyanskii, V. V. Kulakov. and Yu. F. Markov, Pis’maZhur. eksp. teor. Fiz., 1975, 21, 121. D. M. Adams and W.R. Trumble, Inorg. Chim. Acm, 1975, 13, 17.

222

Spectroscopic Properties of Inorganic and Organometaiiic Compounds

crystal structure. An inverse order of the v, and v16 v(M-ring) modes, as compared with other metallocenes, was claimed.396 J.r. and Raman spectra of M(CO), ( M = Cr, Mo, W) in the 4000cm-l region are much simpler than in the 2000c1n-~region in that factor group splitting is negligible.3Y7aA further instalinent has appeared of the v ( C 0 ) study of 7r-arene complexes, viz. Cr(CO),(.rr-R) [R = Me&, or Me,HC,J.3B7b It is concluded, essentially, that factor group analysis works: and that is an encouraging note on which to end. 4 Vibrational Spectra of Solutions By P. Gaits

This new section draws together information on solution spectroscopy, where both solute and solvent are often well-characterized species individually, but where new species may arise by solvent-solvent or solvent-solute interaction. A rotating cell for solution Raman spectra has been described.398 Water and Aqueous Solutions.-Among many theoretical studies of pure water structure that of Lemberg and Stillinger is impressive for its simplicity and notable for its predictions. These authors return to the Bernal-Fowler model in which the atoms are represented by point Other studies using a more realistic, and more complicated, 0-H bond potential function have concentrated on small cluster models to predict the frequencies 400 and i.r. intensities 401 for the low-frequency vibrations. On the experimental side stimulated Raman studies of pure H,O and DzO, H 2 0 - D 2 0 mixtures, and NaCIO, solutions have been made.402 The authors show that the majority of the results can be explained by a simple macroscopic theory which yields no information about the microscopic structure of water that could not be obtained from simple Raman spectroscopy alone. They do not believe that stimulated Raman scattering provides any unequivocal evidence for the two-state model proposed by Wal~afen.~O~ Other evidence against 'ice nuclei' was obtained from the Raman spectra of supercooled water.403 Another approach to the examination of small water clusters is via matrix but it is very tempting to over-interpret the results in terms of almost every conceivable monomer, dimer, or oligonier species.4o6 The effects of dissolved ions on water structure continue to be investigated v2 v g was resolved through the solvent spectra. The combination band v1 into three Gaussian components for water in aprotic solvents at less than 1%

+

+

V. Bohm, B. F. Gaechter, and M . Shushani, Izvest. Akad. Nimk S.S.S.R., Ser. khim., 1975, 3, 572. ( a ) E. L. Burrows, L. Harland, and S. F. A. Kettle, J.C.S. Dalton, 1975, 2353; ( h ) H . J. Buttery, S. F. A. Kettle, and I. Paul, J.C.S. Dalton, 1975, 969. w R A. K. Covington and J M. Thain, Appl. Specrroscopy, 1975, 29, 386. H. L. Lemberg and F. H. Stillinger. J . Chent. Phys., 1975, 62, 1677. '0° J. Bandekar and B. Curnutte, J . Mol. Spectroscopy, 1975, 58, 169. (01 J. C. Owicki, L. L. Shipman, and H. A. Scheraga, J . Phys. Chem., 1975, 79, 1794. '02 M. Sceats, S. A. Rice, and J. E. Butler, J . Chem. Phys., 1975, 63, 5390. Gy. Beke, Gy. Inzelt, and L. Jancso, Actu Chirn. Acacf. Sci. Hung., 1974, 88, 237. B. Mann, T. Neikes, E. Schmidt, and W. A. P. Luck, Ber. Bunsengesellschuft phys. Chem., 1974,78, 1236. (06 Pham Van Huong and J. C. Cornut, J . Chirii. phj*s., 1975, 72, 534.

Vibrational Spectra of'S t w l l Sytmietric Species arid of Sirigle CZystcrls

223

concentration. This was followed by a reinterpretation of data on bulk aqueous ~ o l u t i o ~ Variation ~ s . ~ ~ ~ of the i.r. l i brational modes of water (500-700 cm-1) with concentration of addcd salts AX (A = NH4, Li, Na, K ; X = F, C1, Br, 1 except LiF, Lil, NaF, KF) was studied at 30 "C and it was claimed that water in different cation hydration spheres could be d i s t i n g u i ~ h e d .The ~ ~ ~procedure depends upon removal of the Rayleigh scattering by d e ~ 0 n ~ 0 1 ~ t i oIncreasing n.~~~ hydrogen ion concentration (in the form of hydrochloric acid) leads to a general broadening of both the Raman v(0H) and Rayleigh bands, associated with hydrogen-bonded ~ t r ~ ~ t The ~ r einfluence ~ . ~ ~ of ~dissolved CsBr, NH,Br, Me,NBr, and Bu",NBr on v(0D) and v(0H) at 40 and 80 "C was investigated, but the soundness of the curve-fitting procedure used must be questioned,410 Symons and Waddington find further support for a controversial assignment of v(0H) in weakly bonded H,O-C10,- interactions by a correlation with n.m.r. data.411 The same authors have examined the spectra of perchlorate and fluoroborate solutions in HOD in the v(0D) region and, by making some simplifying approximations, obtain the 'solvation number' of 4 for the C104- and BF,anions.412 Raman spectra of binary and ternary solutions involving H,O, DMF and NaClO,, NaNO,, Zn(C104),, or Zn(NO,), have been analysed consistently in the v(0H) region by a four-band model: typically for NaNO, systems shifts of 3623, 3542, 3430, and 3265 cm-l were found. The bands were interpreted in terms of H-bonded and non-H-bonded OH oscillations rather than a continuum or any other This paper has a useful bibliography of 84 references. In studies on dissolved cations Irish and co-workers414 found that thc 390 cm-l band observed in aqueous zinc(r1) solutions increases in half-width, wi, with increasing temperature. With the Mg2+ a similar trend is accompanied by a small frequency shift. The bands are interpreted as v(M-OHz),ytnvibrations with contributions from hot bands.414Changes in the i.r. spectra of the Zn(CIO,),HCl0,-H20 system with increasing perchloric acid concentration were taken to indicate that the zinc ion changes from octahedral to tetrahedral c o - ~ r d i n a t i o n . ~ ~ ~ Spectra of nickel chloride in heavy water gave evidence for a quasi-lattice ordering involving Ni(D20)4CI, species and hydrogen bonding.41GRaman and i.r. studies of Fes+ hydrolysis have yielded the following [Fe(OH,),I3+, v(Fe-OH,) 501 cm-'; [Fe(0D,),l3+, v(Fe-OD,) 488 cm-l; [(H,O),FeOFe(H20)5]4+,v(Fe-OH,) 388 and 336 cm-l; [(D,0)5FeOFe(OD2)5]4+,v(Fe-OD,) 378, 325 cm-l and v(FeOFe),,,, 870 cni-l. 4no 4n7 (Ox

llU

dl:(

415

41'1

(I7

0. D. Bonner, R. K. Arisman, and C. F. Jumper, Infrmed Phys., 1974, 14, 271. D. W. James and R . F. Armishaw, Austral. J . Cheni., 1975, 28, 1179. D. W. James and R. Irmer, J . Raman Spectroscopy, 1975, 3, 91. I. Pernoll, U. Maier, R. Janoschek, and G . Zundel, J.C.S. Faruday 11, 1975, 71, 201. M. Lucas, A. D e Trobriand, and M. Ceccaldi, J . Phys. Chem., 1975, 79, 913. M. C. R . Symons and D. Waddington, Chmi. Phys. Letters, 1975, 32, 133. M. C. R. Symons and D. Waddington, J.C.S. Furuday I I , 1975, 71, 22. G . E. Rodgers and R. A. Plane, J . Chem. Phys., 1975. 63, 818. J. T. Bulmcr, D . E. Irish, and L. Odberg, Canad. J . Cheni., 1975, 53, 3806. P. P. Andreev, L. A. Myund, and L. S. Lilich, Vesrttik Leningrad Univ. (Fiz. Khint.), 1975, 142. N. H. March and M . P. Tosi, Phys. Letters ( A ) , 1974, 50, 224. J. M. Knudsen, E. Larsen, J. E. Moreira, and 0. F. Nielsen, Acta Chem. Scand. ( A ) , 1975, 29, 833.

224

Spectroscopic Properties of Itiorgnnic and Orgunometallic Compounds

The study of ion-pairing continues to provide the basis for healthy controversy, with effort being concentrated on the nitrate ion. Balshaw and Smedley examined the Ranian spectra of ‘C.‘a(N0,),,6H20’ and ‘Ca(NO,),,3.24H20’at pressures up to 60 bar. The more concentrated ‘solution’ showed a slight increase of ion-pairing at high pressures.418 Lockwood calculated the spectrum of the hypothetical NO3- gaseous ion and concluded that, even allowing for the collisional damping present in the liquid phase, rotational motion is not the primary cause of the solution doublet structure of v3 (antisymmetric N-0 stretching vibration).41s Much more informative results were obtained by matrix isolation studies of alkali metal nitrates in mixed matrices varying from pure Ar to pure H,O or NH,. The huge splitting of v, in LiN0,-Ar of 260 cm-l is reduced to 65 cin-’ in the pure H,O matrix because the cation charge, which is responsible for the large splitting in inert media, is very effectively cancelled through interactions with the H,O or NH, lone pair.420 Contact ion-pairs are observed at all compositions, and some typical v3 wavenumbers are given in Table 13. A similar study of alkali metal perchlorates reveals that the C104-

Table 13

Wauenrimberslcm-I for the v 3 region of LiN03 and KNOs in non-inert matrices Matrix H2O NH,

Salt LiNO, 1347, 1412 1345, 1392

Salt KNO, 1348, 1498 1350, 1370

vQ vibration, v(Cl-O),,,,,, is split into three components, indicative of a bidentate mode of ion-pairing. Again the splittings are much smaller in the donor matrix than in the inert matrix.421 Raman studies of crystalline and aqueous cadmium nitrite show no bands in the 1000-1520cm-1 region that are not present in sodium nitrite solution, though some changes in intensity and I V ~were found. The bending region shows a ‘free’ nitrite band at 817 cm-’ and new bands at 846 and 861 cm-l associated with nitrito-cadmium complexes. Four cumulative stability constants were computed, though the spectra contain no direct evidence for the existence of four species.422 In contrast, the predominant species in aqueous Hg(ClO,),NaNO, solutions were thought 423 to be Hg(N02)2 and [Hg(N0,),I2-. Raman spectra of sodium and zinc chlorates were obtained (using Hg 435.8 nm excitation) and indicated that no ion-pairing was present for NaClO,. However, solvation destroys the anion’s three-fold symmetry and a complicated spectrum results because of the proximity of the v 1 and v, vibration frequencies - in symmetry lower than C,, extensive ‘remixing’ takes place.424Zinc was said to form a solventshared ion pair with shifts at 308, 950, and 1025 cm-l. The state of iodate in

“* B. Balshaw and S. I. Smedley, J . Phys.

Chenz., 1975, 79, 1323. D . J. Lockwood, J.C.S. Faraday ZI, 1975, 71, 1440. u 0 G. Ritzhaupt and J. P. Devlin, J. Phys. Chmz., 1975, 79, 2265. w1 G. Ritzhaupt and J. P. Devlin, J. Chem. Phys., 1975, 62, 1982. ‘la D. E. Irish and R. V. Thorpe, Canad. J . Chem., 1975,53, 1414. u3 A. G . Cram and M. B. Davies, J . Inorg. Nuclear Chem., 1975, 37, 1693. u4 J. C. Sprowles and R. A, Plane, J. Phys. Chem., 1975, 79, 1711.

Vibrational Spectra of' Srnoll Symnretric Species atid of Single Crystals

225

aqueous solution has also been investigated.425Raman and i.r. spectra of gaseous SO, and of SO2 solutions in H,O and D,O have been reported, but unambiguous evidence on the structure of the pyrosulphite ion was not Non-aqueous Solutions.-Popov has reviewed the results from vibrational and n.m.r. studies on alkali metal The N-H stretching region of ammonia is still the subject of hot debate. Buback, investigating both Raman and i.r. spectra of ammonia, mostly in the supercritical region, found sufficient evidence to assign unambiguously four bands as vI, 1'3, 2vp2(sym)and 2~,~(antisym).~*~ He later extended the range of his experiments to temperatures 30-300 "C and pressures to 1250 bar.429Lundeen and Koehler, examining the Ranian spectra only, rejected the four-band model in favour of the Schwarz-Wang coupledoscillator theory ( J . Client. Pliys., 1973, 59, 5258), but it is a pity that Buback's i.r. data were not available to them.430A study of the u(NH) vibrations in binary NH3-C6D6 mixtures led to the suggestion that molecular association in ammonia is greater at lower t e ~ n p e r a t u r e s .The ~ ~ ~ i.r. spectra of NH3 and ND, in N, matrices have also been Solutions of NH4N03, AgN03, NaNO,, KN03, and Ca(N03), in liquid ammonia have been studied by Raman spectros c ~ p y The . ~ ~nitrate ~ v3 region showed splittings that might be associated with ion-pairing, though v4 showed a splitting only with the Ca2+ solutions. The band at 260 cm-l was assigned to a quasi-lattice mode in Ca(NO,), solutions, not v(Ca-N) 'since it was not observed in the C104- salt solution', but this is contrary to its previous observation (K. R. Plowman and J. J. Lagowski, J . Pliys. Chern., 1974, 78, 143). A six-co-ordinate structure was suggested for Ag+ on the basis of shifts observed at 296 and 329cm-'. Solutions of Li and Ca metals in ammonia were so dilute (3 x moll-l) that the Raman spectra were those of the pure A phase-sensitive detection technique has been used to extract solvate spectra from overlying solvent bands. The solutions studied were of LiNO,, LiCI, and NaNO, in f ~ r m a m i d e . ~Raman ,~ spectra of concentrated solutions of lithium chloride in formic acid show that ion-pairing and ion-solvation substantially alter the solvent s p e ~ t r u n i .v(C=O) ~~~ is lowered by ca. 45 cm-l and v(C-0) rises by ca. 90 cm-l. A new study of silver nitrate in methyl cyanide merits particular attention because the v1 nitrate band was examined at the very low solution concentration of moll-l. The ion-pair formation constant obtained by Raman spectroscopy was 84 k 14 compared to the value of 70.3 k 1.2 calculated from the Fuoss-Onsager theory of conductance.437 Solutions of Ag[TeOF,] were 416 426 427 42H 428 430

431 43a

434 436 436

m

T. G. Balicheva and G. A. Petrova, Probl. Sourem. Khitn. Koord. Soedin., 1974, 4, 266. A. R. Davis and R . M. Chatterjee, J . Solution Chem., 1975, 4, 399. A. I. Popov, Pure Appl. Cheni., 1975, 41, 275. M. Buback, Ber. Bunsengesellschuft phys. Chem., 1974, 78, 1230. M. Buback and E. U. Franck, J . Chim. phys., 1975, 72, 601. J. W. Lundeen and W. H. Koehler, J . Phys. Chem., 1975, 79, 2957. J. H. Roberts and B. de Bettignies, J . Phys. Chem., 1975, 79, 1852. G. Ribbegard, Chent. Phys., 1975, 8, 185. J. W. Lundeen and R. S. Tobias, J . Chem. Phys., 1975, 63,924. T. R. White and W. S. Glaunsinger, J. Phys. Chem., 1975, 79, 2942. D. J. Gardiner, R. B. Girling, and R. E. Hester, J.C.S. Fumduy ZI, 1975, 71, 709. B. M. Rode, Chem. Phys. Letters, 1975, 32, 38. G . J. Janz and M . A. Muller, J . Solution Chem., 1975, 4, 285.

226

Spectroscopic Properties o f Inorgntiic‘

atid

Organoriietallic Cotnpuicnc1.v

thought to contain 0-bonded ion pairs because of the appearance of new bands at 852 and 588 cm-l (see Chapter 5, p. 272).438 I t has been confirmed that ReF, retains octahedral symmetry in hydrogen fluoride The i.r. spectrum of (NC),)(PF,) dissolved in arsenic trifluoride containing fluorosulphuric acid provided evidence that the nitroniuni ion was hydrogen bonded to HS03F.440Raman and i.r. spectra of BrF, and ClF, in condensed phases suggest that both species are polymerized.441 Solvent shifts of the hydrogen halides, CO and NO dissolved in carbon tetrachloride have been calculated using a simplified model with mixed success.442 The i.r. band profiles of ICI and IBr in benzene and cyclohexane are predominantly determined by collisional broadening, but with IC1 rotational diffusion is also a contributory factor.443Rotational correlation was also studied in CH,CN, CH,I, CHCl,, and CHBr3..144The Raman spectra of liquid CO, at 0.1, 1.5, and 3 kbar pressure show little pressure dependence.445 The Bu”,NCl-C,H, system has been reinvestigated under improved instrumental conditions, and the far-i.r. spectra interpreted in terms of i~n-aggregation.~~, Solutions in Molten Salts.-The structure of molten AlF,-alkali fluoride mixtures has been studied by Raman emission using a captive liquid windowless and the presence of octahedral AIF,,- ions confirmed 4 4 8 by observation of v1 at 555 cm-I, v 2 at 390 cm-l and v5 at 345 cm-l. The v1 frequency was very dependent upon cation, and AIF4- was also found to be present. Tetrahedral anions were also observed in fused chlorides of alkali metals containing Mn2+, Co2+,Ni2+, or Zn2+ ions, though the CuCla2- species which was formed had only MnC1,-KCl melts showed a band at 208 cm-l (wi 110 cm-l) in pure MnCl,, shifting to 245-251 cm-l and narrowing to wh = 30cm-’ as the KCl proportion increase^.^" Raman spectra of molten mixtures of Cu’, Ag‘, and Au’ halides with alkali halide have been For copper and silver no firm structural conclusions emerged. For AuC1,-KCl mixtures the spectra are like those of the AuC1,- ion. In the Raman spectra of molten NaN0,-AgNO, mixtures splitting of the nitrate v, and v4 bands was observed at high silver concentration, attributed to the effects of the cation field, which were estimated by the UBFF method.452 E. Mayer and F. Sladky, Inorg. Clieni., 1975, 14, 589. J. H. Holloway and J. B. Raynor, J.C.S. Dalton, 1975, 737. 4 4 0 G. A. Olah, A. Germain, H. C. Lin, and D. A. Forsythe, J. Anrer. Chem. SOC.,1975,97,2928. 441 R. Rousson and M. D. Drifford, J . Chew. Phys., 1975, 62, 1806. u2 I. Rossi, C. Brodbeck, J. P. Bouanich, and N. V. Tanh, Spectrochim. Actu, 1975, 31, A , 433. 4 4 3 J. Yarwood, J.C.S. Faraday 11, 1975, 71, 714. 44Q G. D. Patterson and J. E. Griffiths, J. Chem. Phys., 1975, 63, 2406. M. Perrot, J. Devaure, and J. Lascombe, M o l . Phys., 1975, 30, 97. l r 6 C. Baker and J. Yarwood, J.C.S. Furuduy I I , 1975, 71, 1322. p47 B. Gilbert, G. Mamantov, and G. M. Begun, A p p l . Spectroscopy, 1975, 29, 276. ‘On H. Gilbert, G. Mamantov, and G. M . Begun, J . 1 : 3 ; at higher Li concentrations the characteristic bands of B04- and BO,- appear.lo8 Lanthanum borate has also been examined.log Trimethylchloroalumoxane-diethyl ether (14) has v(A1-0--1) modes at 770 and 800cm-l which are intense in the i.r.llo Most other bands have been Mc,

,O,

HAL0 CI

,.Me

PA'\.

hlc

assigned by comparison with Me,AICI,OEt,. By tortuous arguments it has been deduced that the tetranieric product from the reaction of AIBus, with HOCH2C H 2 0 H contains some bidentate and some unidentate ligands."l In another alkoxide,Il2 In(OMe),,2MeOH, v(In-0) is at 510 cm-I. The i.r. spectrum of LiGaO, gives the following wavenumbers for the vibrations of the GaO, octahedron: v3(Tlu) 610, vp(Tlu) 390cm-', but coupling with La-0 modes is recognized to be present.'13 The new semiconductor CdInGaS, shows five strong i.r. bands in the 400-180 cm-l region.l14 Compounds containing M-Halogen Bonds (M = B, A4 Ga, or In).-The apparently anomalous intensities of the isotopic components of vl in BCI, are said to derive from intermolecular interactions rather than from Fermi resonance or hot bands.115 The new compound BQBrQ,which is structurally similar to L. V. Serebrennikov and A. A. hfal'tsev, Vestnik Moskov. Unio., Khim., 1975, 16, 250. J.-F. Herzog, B. Bonnet, and G . Mascherpa, Compt. rend., 1975, 280, C , 197. l o 6 M. Fouassier and M. T. Forel, J . M o l . Structure. 1975, 26, 315. P. Sochor, H. Kadlecovri, and 0. Strouf, CON. Czech. Chem. Comm., 1975, 40,3177. T. E. Paxson and M. F. Hawthorne, fnorg. Chem., 1975, 14, 1604. I o 8 A. Bertoluzza, C. Fagnano, and P. Monti, Atti Accad. naz. Lincei, Rend. Classe Sci. fis., mat., nat., 1974, 55, 506. '""J . H . Denning and S. D. Ross, C o d . Digcst Inst. Phys. (London), 1971, 3, 234. M . Boleskawshi, S. Pasqnkiewicz, K . Jaworski, and A. Sadownik, J . Organometallic Chcni., 1975, 97, 15. P. Maleki and M . J. Schwing-Weill. J . 1nor.q. Nuclear Chem., 1975, 37, 4 3 5 . P. Bianco and J . Haladjian, Bull. Soc. chirn. Frmce, 1975, 2009. 113 E. J. Baran, 2.N o t i i r f i m i h . , 1975, 30h, 136. G . B. Addullaev, N. V. Bozhovskaya, N. D. Dzhuraev, D. B. Kusher, R. Kh. Nani, and V. K . Subaghiev, Fiz. T d h . Poluprocot-ln., 1975, 9, 819. 115 A. Loeumschuss, Spec trochim. Acta, 1975, 31 A. 679. lo3

lo(

Characteristic Vibrutioriul Frequeiicies of' Cotripoirnds

239

B,CI,, shows i.r. bands at 957, 865, 660, 457, and 387 cm-l. The i.r. spectrum of C13SiBC12shows 117 u(~OB-CI) at 935 and u(l'B-CI) at 975 cm-l. It reacts with propane to give the 'linear' compound Cl,SiC3H6BCI,, with u(B-CI),, at 1040 and u(B-Cl), at 940 cni-'. The compound 118 Cs[BF(OMe),] has v(B-F) at 7 1 0 cm-l, and the conipounds (1 5 ) and (16) have v(9-F) in the region 1000- 1 050 cm -- l . 119

(IS) K

=

(Rur~O)Pli,Por MePli,P

Adducts of the boron halides with various bases have been studied superficially. I n adducts of BF3 with Me,X (X = 0, s, or Se) the decrease inf(B-F) is comparable to the decrease in going from BF, to BF4-.lP0 With Me,X (X = P, As, or Sb) the B-X force-constant shows some correlation with the heals of reaction.121 The compounds BX,_,(SeH),, (X = CI, Br, or I ) have been shown to be planar.',, J.r. spectra of the conipounds (Me,N)(MF,) ( M = Al, Ga, or I n ) and their monohydrates provide evidence 123 that the aluminium atom is four-co-ordinate in the anhydrous salt, with u(AI-F) at 290cni-'. In all other cases the central metal is six-co-ordinate, with u(M-F) in the ranges 330-390 (Al), 295 322 (Ga), and 430-475 cm-l (In). These trends are not the usual ones where variation of co-ordination number or atomic number are concerned. Amongst great tabulations of i.r. data for the compounds K[Al(BH,),], K[Al(BH,),X] (X = C1 or Br), and Me,N[AI(BH,),X] (X = CI, Br, or l), the only assignments offered are in Table 8 . A Rarnan spectroscopic study of the Li,AIF,-A1F3

Table 8

W u i ~ e t i i ~ ~ ~ b ~ ~for s i csorile i i i - ' A1 -hulogen atid In-halogen vibtwtiotis

Compound K [Al(BH&iX] Me4"AKBH4)&1 Ph,InX PhlnX,

x

=

c1

432 477 184 243

X = Br 336 376

159 185

X = l

Rej:

124

137

eutectic at 7 3 0 "C led to the conclusion that the equilibrium AlFR3-6 AlF4- + 2F- ( K = 3 x lo-, at 730 "C) was the only one present, as in the corresponding sodium system.125 116 IL7

llH

12'

M. S. Reason and A. G . Massey, J . Inorg. Nuclear Chent., 1975, 37, 1593. M. Zeldin, D . Solan, and B. Dickman, J . Inorg. Nuclear Chern., 1975, 37, 25. V. N. Plakhotnik, N. G. Parkhomenko, and V. V. Evsikov, Russ. J . Inorg. Cheni., 1974, 19, 686. W. B. Beaulieu, T. B. Rauchfuss, and D. M . Roundhill, Inorg. Chem., 1975, 14, 1732. P. Labarbe and M. T. Forel, Specfrochini. Acra, 1975, 31A, 525. D. C. Mente and J. L. Mills, Inorg. Cheni., 1975, 14, 1862. J. Bouix, M. Fouassier, and M. T. Forel, Ann. Chirn. (France), 1975, 10, 45. P. Bukovec and J. $iftar, Monarsh., 1975, 106, 483. K. N. Sernenenko, V. B. Polyakova, 0.V. Kravchenko, S. P. Shilkin, and Yu. Ya. Kharitonov, Russ. J . Inorg. Chem., 1975, 20, 173. E. Rytter and S. K . Ratkje, Arta Chent. Scand. ( A ) , 1975, 29, 565.

Specrroscopic Properties of Inorganic and Organometallic Compounds

240

Raman spectra of molten and solid mixtures of GaCl, and CsCl have been interpreted 126 in terms of successive formation of GaC1,-, Ga,Cl,-, and, for the first time, [Ga,C13,+l]- (n 2 3). Other Raman work provides evidencelZ7for tetrahedral [GaCl,]- and [GaBr,]- as [Me,PhN] or [Ph4P] salts, and for the monomeric anions [GaCI,Br]- and [GaBr,CI]-. The i.r. spectra of Prn,GaC1,-, (m = 1 , 2, or 3) have been illustrated.128 An extensive N.C.A. (but hardly a harmonic force field, as is claimed) on Ga&& has confirmed the most recent assignments and been used to calculate that the unobserved v,(AzU) is at 106 cm-l. For cia2&, and Ga,I,, a similar procedure predicts 130 v5 at 68 cm-1 (Br) and 52 cm-l (I). Vibrational spectra 63 of the alkylgallium di-iodides (Table 5 ) give v(Ga-I) in the ranges 197-321 and 154-169 cm-l. The V, vibration of [InCIJ- has been identified at 317 cm-l in the i.r. spectrum Other indium-halogen of a compound formulated 131 as In,CI,(H,O)(S,N,),. stretching frequencies are included in Table 8.132 4 Group I V Elements

Compounds containing M-H Bonds (M = Si, Ge, or Sn).-In what may well be the largest ab initio calculation to date, the spectrum of H2Si=CH2, given in Table 9, was calculated in order to confirm the existence of this transient species; Table 9 Ab initio calculated wauenumberslcm-' in silaethylene H,Si=CH, 3160 3096 2483 2479 1490 1140 993 777 317

H,Si=CD2 2341 2260 2484 2480 1238 954 1002 700 266

a band at 1407 cm-1 had been assigned to it in a low-temperature trapping An exceptionally complete study (vibrational, electronic, photoelectron, and n.m.r. spectra electron-diffraction structure) of the unstable the data listed in Table 10. Very extensive silylsulphinylamine H,SiNSO gave vibrational data on ClCHaSinH2Cl(n = 1 or 2) have been assigned with the aid of N.C.A.*35In the solid state only the trans-isomer persists, but in the liquid

+

H. A. Oye and W. Bues, Acta Chem. Scand. ( A ) , 1975, 29, 489. R. Rafaeloff and A. Siberstein-Hirsh, Spectrochim. Acta, 1975, 31A, 183. lS8 R. A. Kovar, H. Derr, D . Brandan, and J. 0. Callaway, Znorg. Chem., 1975, 14, 2809. lZ9 A. Phongsatha and S. J . Cyvin, Spectroscopy Letters, 1975, 8, 91. l S 0 S. J. Cyvin and A. Phongsatha, Spectroscopy Letters, 1975, 8 , 405. lS1 M. L. Ziegler, H . U. Schlimper, B. Nuber, J. Weiss, and G . Ertl, Z . anorg. Chern., 1975, 415, l2o

lP7

Is1 1s)

la'

193.

S . B. Miller, B. L. Jelus, and T. B. Brill, J . Organometallic Chem., 1975, 96, 1. H. B. Schlegel, S. Wolfe, and K. Mislow, J.C.S. Chem. Comm.,1975, 246. S. Cradock, E. A. V. Ebsworth, G. D. Meikle, and D. W. H. Rankin, J.C.S. Dalton, 1975, 805.

K. Sera, Bull. Chenr. SOC.Japan, 1975, 48,649.

lSb

Characteristic Vibrational Frequencies of' Compounds

24 1

Table 10 Injiiared data for silylsuphiiiylamiiie H,SiNSO Mode

u(SiH) V"SO),, v(NSO), 8(SiH,) p(Si H,) v(Si- N) 6(NSO) Y ( Si N S)

Wcruenunrberlcm-l 2195 1310 1147 940 740 605 505 275

and gas phases this is accompanied by the gaiiclie-form. 1.r. data 136 for some new chlorinated trisilylamines are given in Table 1 1. Interestingly, there is no 14N--16N

Table 11 Infrared wavenuntbers/cm-' for sotm chlorinated trisilylaniines Assignment v( Si H) v(SiN) 8(SiH,) 8(SiH2) v(SiC1) v( Si- N),

CISiH214N(SiH3)2 2195, 2170 922 94 1 887 550

48 8

(ClSi H2)24N(SiH,) 2200, 2178 1002 946, 880 742, 715 572, 542 483

(C1Si H2),N

2210 990 949, 876 74 1 584, 548 49 8

shift in the bis- and tris-compounds. Other reports on silyl compounds are more sketchy. Adsorption on SiOa during the action of a low-temperature highfrequency discharge though Ha gives rise137 to bands from -SiH groups at 2280, -SiH2 groups at 2277, and -OH groups at 3749cm-l. Unassigned i.r. data have been listed for a variety of silyl and germyl corn pound^,^^^-^^^ including the first cyclic silane SigH10.143 A variety of M-H stretching frequencies are given in Table 12.144-160Those who enjoyed last year's farrago of empirical relationships will eagerly read how the effect of 7r-bonding on v(Ge-H) depends upon the OR constant.151 The compounds studied are of the types R2XGeH,RX,GeH, RXYGeH, and X,YGeH, where R is a substituent 'incapable of 7r-bonding' and X, Y are substituents 'capable of d,,-p,, interaction with Ge'. S. Cradock, E. A. V. Ebsworth, and N. Hosmane, J.C.S. Dalton, 1975, 1624. S. E. Ermatov, Doklady Phys. Chem., 1975, 218, 999. l y 8 J. L. Bellama and L. L. Gerchrnan, Inorg. Chem., 1975, 14, 1619. K. G . Sharp and J. F. Bald, jun., Inorg. Chem., 1975, 14, 2553. 140 J. A. Morrison and J. M. Bellama, Inorg. Chem., 1975, 14, 1614. 141 U. Klingebiel, D. Fischer, and A. Meller, Monarsh., 1975, 106, 459. l t a A. R. Dahl, C. A. Heil, and A. D. Norman, Inorg. Chem., 1975, 14, 2562. 143 E. Hengge and G. Bauer, Monatsh., 1975, 106, 503. M. Hofler, J. Scheuren, and D. Spilker, J. Organomerallic Chem., 1975, 102, 205. E. M. Dexheirner, L. Spialter, and L. D. Smithson, J. Organometallic Chem., 1975, 102, 21. 140 J. E. Bulkowski, N. D. Miro, D. Sepelak, and C. H. Van Dyke, J. Organometallic Chem., 1975, 101, 267. 147 H. Okinoshima, K. Yamarnoto, and M. Kurnada, J. Organornetallic Chem., 1975, 86, C27. W. P. Neumann and A. Schwarz, Angew. Chem. Internat. Edn., 1975, 14, 812. IPp H. Weichrnann and A. Tzschach, J. Organometallic Chem., 1975, 99, 61. lb0 T. Birchall and A. R. Pereira, J.C.S. Dalton, 1975, 1087. 161 A. N. Egorochkin, S. Ya. Khorshev, J. Sat& P. Rivihre, and J. Barran, J. Organometallic lye

ly7

Chem., 1975, 99, 239.

Spectroscopic Properties of Itlorgattic and Orgatiometallic Compoutids

242

Table 12 Some Si-H and Sn-H Conipound (v5-C,H5)Fe(CO),SiH, But,% H (y5-C5H,)Fe(CO),CH2Si(H)Me, MeO,C,

wauetrumbers/cm-l Wuvenumberlcm-1

Ref.

2100 2094 2100

144 145 146

v(Si-Hj

21 50

147

v(Sn-H) v(Sn-H) v(Sn- H) v(Sn-H) v(Sn- H) v(Sn- H) v( Sn -H)

1785 1816

148

Mode v(Si- H) v(Si-H) v(Si-- H )

,CO,hlc

C=C\

€1 Mc,Si’ Sih1c:Il Me,SnSnBu”,H Bun,Sn( H)( CH,),PH Et,Sn(H)(CH,),P( H)Ph EtzSn(H)(CH,),PH, Et,Sn(H)(CH,),P(H)Ph (PhCH,),SnH (PhCH,),SnH,

1820 1841

150

Compounds containing M-C Bonds (M = Si, Ge, Sn, or Pb).--Many of the reports in this category are only marginally of interest to inorganic chemists, being mainly concerned with the organic part of organo-silicon or -germanium c o r n p ~ u n d s . ~Group-frequency ~~-~~~ assignments have been given for the i.r. spectra of RMMe, (M = C, Si, Ge, Sn, or Pb; R = furyl) and related compounds, but again the interest focuses on the organic moiety and the v(CC) of the furan ring, which decreases in the sequence Ge 2 Si > Sn 2 Pb.158 From the very complex spectra (which are illustrated) it is claimed that bands at ca. 10oO cm-l allow the authors to distinguish between monomers, dimers, and

-

I

polymers of compounds of the type R1,MCH2CHR2CHR30 and R12MCH=

1

CHCR2RS0(R1,M = Me,Si, Et,Ge, or Bun,Sn; R2=R3=H or Me). Typically for the Me,Si series, v ( C 0 ) is at 1030 for the monomer (17), 1005 for the co-

’52

153 164 160 166

157

168

R. Tacke and U. Wannagat, Monatsh., 1975, 106, 1005. J. D. Lewis, T. H. Chao, and J. Laane, J . Chem. Phys., 1975.62, 1932. M. Rivikre-Baudet and J. Satgk, Rec. Truu. chim., 1975, 94, 19,-22. M. Capka and J. HetflejS, Coll. Czwh. Chem. Comm., 1975, 40, 3020. H. C. Haas and M. A. Ring, Znorg. Chenr., 1975, 14, 2253. R. A. Bekka, G. G. Melikyan, B. L. Dyatkin, and I. L. Knunyants, Doklady Chem., 1975, 221, 261. D. Seyferth, R. L. Lambert, and M. Massol, J . Organometallic Chem., 1975, 88, 255. E. Lukevits, N. P. Erchak, I. Dipans, and L. A. Ritevskaya, Latv. P.S.R. Zinat. Akad. Vestis, Kim. Ser., 1975, 209.

Characteristic Vibrational Frequencies of’Conipoutids 243 ordination dimer (18), 1050 for the true dimer (19), and 1090cm-’ for the polymer. 159 The i.r. of n-type a-SiC(6H) samples, alloyed with nitrogen, have been studied le0 at 90, 295, and 500 K. Solution intensities for Me,-,Si(C=CD), (n = 1, 2, or 3) have been measured.la1 The only small molecule to have been studied this year is dimethylcyanosilane, Me,Si(H)CN. The selected data given in Table 13 are for the Raman spectrum of the liquid, assigned on the basis of C, symmetry.16a

Table 13 Selected wavenumberslcm-l for dimethylcyanosilane Me,Si(H)CN Assignment

v(SiH) 8(SiH) (in plane) v(Si-C),, Y( Si- C), p(Si-H) v(Si-C) 6(C- Si- C)

8(Si--C-N) 6(Si-C-N) 6(C- Si- C)

Symmetry a‘ a’ U”

a‘ a” a’

n‘

U”

a‘

U”

Wavenumberlcm-l 2175 847 782 743 637 5 50 345 222 176 138

M-C stretching vibrations have been assigned, mostly on slender evidence. For the compounds (20) the relevant wavenumbers are:le3M = Si, 760; M = Ge, 604, 570; M = Sn, 535, 515cm-’. With the trifluoromethyl group the data in Table 14 were le5 The data for the corresponding methyl compounds, Table 14 v(Ge-C)

wavenumberslcm-’ for some organo-germanium halides

Compound

X = F

F,GeX, (F,C),GeX, H,CGeX,

340 337 634

x

=

c1

300 318 627

X = Br 333 347 617

X = I 310

326 598

included in Table 14 for comparison purposes, are vastly different, and some doubt must attach to the assignments. Triphenyltin compounds have been studied by three groups. The hydroxide has a five-co-ordinate structure, as for Me,Sn(OH), but observation of v(Sn-C),, at 492 and v(Sn-C), at 420cm-l means that the Sn-C, fragment cannot be entirely p1anar.le6 A variety of v(Sn-C) values have been given for the N-(triphenylstanny1)cyanamides lo7 A. Marchand and P. Gerval, J. Organometallic Chem., 1975, 88, 337. V. D. Kulakovskii, A. G. Belov, V. D. Egorov, M. A. ll’in, and E. P. Rashevskaya, Fiz. Tekh. Poluprovodn., 1975, 9, 744. lel M. G. Voronkov, T. M. Shidakov, U. F. Kovalev, and 0. G. Yarosh, Izvest. sibirsk. Otdel. Akad. Nauk S.S.S. R., Ser. khim. Nauk, 1975, 86. la* J. R. Durig, P. J. Cooper, and Y. S. Li, Inorg. Chem., 1975, 14, 2845. laS M. Schmidt and E. Wiessflog, Z . anorg. Chem., 1975, 418, 208. l R 4 H.Burger and R. Eujen, Spectrochim. Acta, 1975, 31A, 1645. IoG H. Burger and R. Eujen, Spectrochim. Acta, 1975, 31A, 1655. R. Y . K. H o and J. J. Zuckerman, J . Organometallic Chem., 1975, 96, 41. E. J. Kupchik and J. A. Feiccabrino, J . Organometallic Chem., 1975, 93, 325.

lb9

leu

9

Spectsoscopic Properties of Inorganic and Organometdlic Compounds

244

R(CN)NSnPh,. Triphenylvinyltin shows v(Sn-C) at 526 and 239 cm-l for the vibrations involving vinyl and phenyl groups, respectively.lss The compound Me,SnCl(en) shows v(Sn-C), at 556 cm-l, but no asymmetric vibration, so a trigonal bipyramid structure has been proposed, with equatorial methyl 1.r. and Mossbauer studies indicate that Me,SnOH, Me,SnNCS, Ph,SnOH, and Ph,SnN, are also five-co-ordinate, with polymeric structures containing bridging OH, NCS, or N, groups.17oThe trigonal-bipyramidal structure appears yet again in an i.r., n.m.r., and Mossbauer study of the pentane-2,5-dionato-complexes R,SnL (R = Me or Ph; L = acac, acbz, or bzbz). u(Sn-C) was found in the regions 574-589 and 548-556 cm-l for the methyl Organic group frequencies have been given for the compound 172 CH,=CH-S-SnEt,. The organolead compound (21) exhibits i.r. wavenumbers 173 as follows : ~(Pb-c,)~.,495, v(Pb-C& 488; v(Pb-N) 455; G(PbC,) 270 cm-l. A linear

C-Pb-C skeleton has been inferred from the presence of v(Pb-C), only in the Raman spectrum of Me,PbX, (X = acac or acbz); the frequencies observed are 474 and 480 cm-l, Compounds containing M-M Bonds (M = Si or Ge).-The cyclic pentasilane (22) has v(Si-Si) at 515 and 527 cm-l for the symmetric and antisymmetric ring vibrations and 391 cm-l for the exocyclic Si-Si ~ i b r a t i 0 n . l Data ~ ~ for some methoxylated oligosilanes are given in Table 15. The original paper gives values for individual v(Si-0) Table 15

Wavenumberslcm-l for some methoxylated oligosilanes

Compound [(MeO),Si],Si [(MeO),Si],SiH [(Me0)3Si],SiH2 [(MeO),Si],SiCI [(MeO),Si ],Si(OMe)

G(SiH,)

-

917 919 I

v(SiH,) 2094 2125 -

v(SiC1) -

-

508

-

U. Kunze and J. D. Koola, Z . Naturforsch., 1975, 30b, 91. us G. Eng and J. H. Terry, Inorg. Chim. Acta, 1975, 14, L19.

170

171

17% 178

17' 176

v(Si-Si,) 510, 489 507, 500 527, 504 524, 455 517, 491

v(Si0) 808-695 835-649 810-650 825-692 835-640

G. Alonzo, N. Bertazzi, F. Di Bianca, and G . C. Stocco, Atri Accad. Sci.,Lett. Arti Palermo, Parte 1 , 1973, 33, 77. G. M. Bancroft, B. W. Davies, N. C. Payne, and T. K. Sham, J.C.S. Dalton, 1975, 973. M. G. Voronkov, R . G . Mirskov, 0. S. Ishchenko, S. P. Sitnikova, and E. 0. Tsetlina, Dokladv Chem.. 1975, 219, 880. H. Leimester and K. Dehnicke, Z . anorg. Chem., 1975, 415, 115. M. Aritorni and Y . Kawasaki, J . Organometullic Chem., 1975, 90, 185. E. Hengge and G . Kollmann, J . Organoriretallic Chem., 1975, 92, C43. F. Hofler and R. Jannach, Z . anorg. Chem., 1975,413, 285.

Characteristic Vibrational Frequencies of Coinpounds

245 Ge-Ge vibrations have been assigned at 339 cm-l for Ge,Br,, 347 cm-l for Ge,Ph,, 343 cm-l for Ge,CI,Ph,, and 345 cm-l for Ge,Br,Ph,. However, N.C.A. suggests that there is extensive mixing of v(Ge-Ge) with v(Ge-C) or v(Ge-Br), SO that the group-frequency assignment is rather uncertain.177

Compounds containing M-N Bonds (M = C,Si, Ge, or Sn).-The new sulphenyl (sic) shows v(CN) at 1940 cm-l, compared isothiocyanate CH,FC-S-N=C=S isomer.178 Spectra of the methylurea variants to 2251 cm-l for the -S-C=N "H3CNmHCONPH2(n, m, p = 1 or 2) have been assigned with the aid of a MUBFF Unassigned i.r. data are listed in ref. 180. Amongst silicon compounds, Si2(NCO), has been prepared for the first time, and its i.r. and Raman spectra have been assigned,la1 as shown in Table 16.

Table 16

Wauenumbers/cm-' for disilicon hexacyanate Si,(NCO), Vibration V(NCO),, v(NCO), v(SiN) v(SiN) v(SiSi) v(SiN) 8(NCO) v(Si-N) v(SiSi) v(SiN) 8(SiN,) 8(SiN,) 8(SiN,)

+

+

I.r. 2270 1460 716

Raman

602

-

-

-

380 270

-

-

1474 740 71 5 61 5

-

408

-

218

Tentative i.r. assignments for the compound (FSiH2)2NSiH3in the gas phase are as follows:182v(SiH) 2264; v(SiN),, 1050; 8(SiH, and/or SiH2) 992; v(Si-F) 878; p(SiH, and/or SiH,) 738; and v(SiN), 482 cm-l. Alkoxy- and aryloxyamino-fluorosilanes of the composition (Me,Si),NSiF(R1)OR2 (R1= Me or F ; R 2 = Me, Et, Pr, or Ph) have been prepared.ls3 They consistently show i.r. bands assigned as follows: G(SiCH,) ca. 1270; v(SiOC),, 1100; v(SiOSi),, 1000; v(SiNSi),, 980; v(Si-F) ca. 900 cm-l. Compounds of the formula Si(oxine),Cl, should probably be written as [Si(oxine),]CI,, and they show i.r. bands at 343 and 383cm-l, thought to be due to Si-N vibrations.la4 1.r. bands have been listed for some disilazacycloal kanes la5 and fluorosilylamines.la6~ The compound Me2Si(NEt,)CH2Fe(CO),(q5-C6H5) is said lQ8to have v(SiN) at 1050 cm-l. The i.r. transmission spectra of a- and P-Si,N, have been identified in terms of Td symmetry .la* F. Hofler and E. Brandstiitter, Monatsh., 1975, 106, 893. E. Kuhle, H. Hagemann, and L. Oehlmann, Angew. Chem. Internat. Edn., 1975, 14, 698. Y. Saito, K. Machida, and T. Uno, Spectrochim. Acta, 1975, 31A, 1237. l B 0 K. E. Peterman and J. M. Shreeve, Znorg. Chem., 1975, 14, 1106. lal F. Hofler and W. Peter, Z . Naturforsch., 1975, 30b, 282. Isa L. H. Marcus and C. H . Van Dyke, Znorg. Chem., 1975, 14, 3124. lS3 U. Klingebiel, D. Fischer, and A . Meller, J . Organometallic Chem., 1975, 85, 141. M. M. Millard and G. Urry, Znorg. Chem., 1975, 14, 1982. l a b K. A. Andrianov, K. V. Kotrelev, A. M. Kononov, and 1. M. Prudnik, DokIady Chem., 1974, 216, 401. ln8 U. Klingebiel and A. Meller, J. Organomefallic Chem., 1975, 88, 149. U. Klingebiel and A. Meller, Chem. Ber., 1975, 108, 155. Yu. N. Volgin and Yu. I. Ukhanov, Optika i Spekrroskopijpa, 1975,38, 727.

17'

178

246

Spectroscopic Properties of Inorganic arid Organometallic Comporrircls The new germylamine Pri,GeNH, has v(Ge-N) at 643 (i.r.) and 649 (Raman), shifting to 606 and 610cm-' in the N-deuterio-derivati~e.~~~ A study of the stannylamine (Me,C),SnnMnzH2 (n = 14 or 15; rn = 1 or 2) indicates a tetrahedral arrangement at the Sn atom, and a low Sn-N bond The tin(I1) compound Sn(NMe,), shows v(Sn- N) at 440 cm-l, understandably much lower than the 534cm-l of the tin(rv) analogue.1B1 v(Sn0) and v(Sn-N) bands were foundlB2at 330 and 340cm-l in SnY,H,O (H4Y= edta). In the series of compounds R,SnX4-,,2(isoquinoline) (x = 1, 2, or 3; R = Ph or Bu; X = C1 or Br) v(Sn-N) is placed lB3in the range 358-430 cm-l, but in the compounds RSn(04C2H,),N (R = Me, Et, Bu, or Ph) a tentative assignment of v(Sn-N) to a band in the region 484-495 cm-l has been made.lBa 1.r. bands in the compounds Me,SnOH,L (L = Me,SnNCS, Me,SnNCO, or Me,PbN,) have been assigned using existing correlation^.^^^

Compounds containing Si-P, Ge-P, Sn-P, or Ge-As Bonds.--Last year's work on F3SiPH2 (G. Fritz, H. Schafer, R. Demuth, and J. Grobe, Z.anorg. Chem., 1974, 407, 287) appears to have been published again,lg0 now with computed force-constants. The value for f(Si-P) of 215 N m-l is slightly higher than in the comparable compounds H,SiPH2 (204 N m-l) and (H,Si),P (200 N m-l). However, co-condensation of SiF, and PH, yielded a mixture of F,HSiPH2 and F3SiPH,, which could not be separated by fractional d i ~ t i l l a t i o n . ~ " ~ This mixture gave i.r. bands at 2310, 2302, 2220, 1030, 960, 880, and 526cm none of which is in agreement with the bands quoted by Demuth. I t must be concluded that these compounds are imperfectly characterized. In the compounds [Me,C],[PSiMe,Cl,_,] (n = 0 or l), v(P-Si) was placed 1 ~ 3 H in the range 42-30 cm-l. Some characteristic i.r. vibrations of the compound (CFs),PSiH3 have been listed.lBB Thermal condensation of R2Ge(PH2), yields compounds of the formula (R2Ge),P, (R = Me or Et). The structure of the methyl derivative shows that it has a P,Ge, skeleton like P,O,,, but unfortunately only the Ge-C vibrations were assigned, in the 545-586 cm-l range.200 [(ButP),GeC1,-,Me,] (n = 1 or 2), by contrast, show v(Ge-P) in the 380cm-l region.2o1 Some stable Geli compounds have been synthesized,202but proximity of v(Ge-P) and v(Ge--1) does not permit their unambiguous assignment, as in Table 17. The i.r. absorptions of high-purity Ge,,Sb,,Se,, and Ge,,As,,Se,, have been studied at CN. 943 cm(10.6 yrn).,O3 H.-J. Gotze, Chem. Ber., 1975, 108, 988. H.-J. Gotze and G . Bergmann, 2. analyt. Clicvn., 1975, 273, 417. P. Foley and M. Zeldin, lnnorg. Chem., 1975, 14. 2264. lo1) S. K. Dhar and W. E. Kurcz, J . Inorg. Nuclear Chem., 1975, 37, 2003. lo3 T. N. Srivastava, P. C. Srivastava, and K . Srivastava, J . Inorg. Nuclear Chern., 1975,37, 1803. lo4 M. Zeldin and J. Ochs, J . Organometallic Chem., 1975, 86, 369. IB6 N. Bertazzi, G . Alonzo, F. di Bianca, and G . C. Stocco, Inorg. Chint. Acta, 1975, 12, 123. led R. Dcmuth, Spectrochim. Acta, 1975, 31A,2 3 3 . lo' G . R. Langford, D. C. Moody, and J. D . Odom, Inorg. Chem., 1975, 14, 134. lD8 H. Schumann and W. W. DuMont, 2. anorg. Chem., 1975, 418, 259. l o g L. Maya and A. B. Burg, Inorg. Chern., 1975, 14,698. A. R. Dahl, A. D. Norman, H. Shenov, and R. Schaeffer, J . Amer. Chem. SOC., 1975, 97,

lag

lD0

6364.

*01

*03

H. Schumann and W.-W. du Mont, Chern. Ber., 1975,108,2261. W.-W. du Mont and H . Schumann, Angew. Chem. Internat. Edn., 1975, 14,368. A . R. Hilton, D. J. Hayes, and M . D . Rechtin, J . Nun-Crysr. Solids, 1975, 17, 319.

-

Character is t ic Vibrational Frequencies of Compounds

247

Table 17 Skeletal vibrations of the Sn" arid Ge" compounds R,PECl (wavenumberslcm -l) Conipound R,PGeCI R,PSnCI

v( P- E) and v( E- CI)

Raman 326 288

l.r.

318 297

r

\

Raman 575, 603 572, 596

l.r.

598 600

Compounds containing M - 0 Bonds (M = C, Si, Ge, or Sn).-In contrast to last year's meagre offering, this section contains so much material that data on silicates etc. are given separately. Complexes of methyl formate, nHC02CmH3 (12, m = 1 or 2), with 1°BF3 and 11BF3 have been studied, but a regrettable precedent is set in that the spectral and N.C.A. data are given in separate papers.2o4 In the same Journal, vibrations of methylene oxalate (23) are only numbered, making it impossible to know what assignment is proposed.206 An empirical assignment of bands in calcium oxalate monohydrate and monodeuterate has been presented, but not all the oxalate bands were assigned with

(24) M

(23)

=-

A!, G ~ I0,1

111

certainty. The five u ( 0 H ) bands arise from a combination of hydrogen bonding and Fermi resonance.2os The compounds (R,M),[O,C,(NCH,),] (M = Al, Ga, or In; R = Me or Et), having the structure (24), have the u ( 0 C N ) vibrations 207 listed in Table 18. Assignments for germyl formate and acetates are given in Table 19, where the values of the corresponding a' modes of the Si analogues are given for comparison purposes.2o8 Table 18

Wavenumberslcm-l for the Y(OCN)modes of compounds with structure (24) Metal A1 Ga In

Wavenunrbers/cm-' 1668, 1652, 1449, 1330 1651, 1637, 1442, 1333 1632, 1603, 1413, 1277

-

Table 19 Selected wauenumbers/cm-l for some formates and acetates HCO, M H,

Vibration u(M-0)

S(OC0) S(CC0) S(C0M) ':OG

?07

Ge Si 605 702 590(?) 530 245 245

* Si MeCO,MH, 690 590 381 323

Ge 612 539 331 270

F,CCO,MH, Si 732 570 335 235

Ge 630 545 285 195

E. Taillandier and T. B. Lakhdar, Spectrochirn. Acm, 1975, 31A, 541, 549. B. Fortunato and G. Fini, Spectrochirn. Acta, 1975, 31A, 1233. I . Petrov and B. Soptrajanov, Spectrochirn. Acta, 1975, 31A, 309. H . U. Schwering, J . Weidlein, and P. Fischer, J . Organonierallic Chem., 1975, 84, 17. P. C , Angus and S. K. Stobart, J.C.S. Dalton, 1975, 2342.

Table 20

Approximate description Si-0-Si symmetric stretch Six, antisymmetric stretch (in-phase) Six, symmetric stretch (in-phase) Six, symmetric deformation (in-phase) Six, antisymmetric deformation (in-phase) Six, in-plane rock (in-phase) Si-0-Si bend Six, antisymmetric stretch (out-of-phase) Six, antisymmetric deformation (out-of-phase) Six, out-of-plane rock (out-of-phasej Six, torsion SiOSi antisymmetric stretch Six, antisymmetric stretch (out-of-phase) Six, symmetric stretch (out-of-phase) Six, symmetric deformation (out-of-phase) Six, antisymmetric deformation (out-of-phase) Six, in-plane rock (out-of-phase) Six, antisymmetric stretch (in-phase) Six, antisymmetric deformation (in-phase) Six, out-of-plane rock (in-phase) Six, torsion B2

B1

A2

A1

Symmetry

-

218 106 640 312 146

-

=

Raman 730 640 419 355 332 188 63 619 230 131 619 ca. 476

x

Wacenumbers/cm-l for hexachlorodisiloxane and hexafluorodisiloxane (X3?&O

-

636 144 -

-

1131 619 476 248 22 1

-

-

I.r. 636 419 337 179 63 -

c1

-

341 182 949 440 225 -

-

989 358 157

Raman 598 949 63 1 557 46 1 242

-

I.r. 60 1 632 555 85 -

434 -

I

1206 989 838 402 179

X = F

Characteristic vibrational Frequencies of' Compoiinds

249 Extensive spectral data on the siloxane (CI3Si),O are summarized in Table 20. The assignment, in terms of C2, symmetry, was satisfactory, though in the solid phase there was some evidence that the SiOSi angle was tending towards 180°, probably because of crystal-packing An equally thorough study of the fluoro-analogue (F3Si),0 (gas-phase data are also in Table 20) showed that there is extensive mixing in the Al modes because of the similarity in mass of the F and 0 atoms and the near equality off(%-F) andf(Si-0) (507 +_ 8 and 548 k 13 N m-l, respectively). The compound has C2, symmetry in all phases.20QR No other studies approach this degree of thoroughness. An N.C.A. based on published data for Me,SiOMe yielded f(Si-0) of 435 N m-l, said to be 'high enough to require a p,-& contribution to the bonding'.210 Other data for siloxanes include 211 1180 cm-I for v(Si0Si) in the compound (F,CSiF2)z0, 1045 cm-l for the same vibration in R,P=N-Si(Me,)OSiMe, (R3 = Me,, Et,, or PhMe2),212109&1105 cm-1 again for v(Si0Si) in the difunctional derivatives O[SiPh,(C,H,X)], (X = a variety of meta- and para-sub~tituents),~'~ and 1060-1070 cm-' for v(Si0Si) in compounds with the structure (25).214 Assignments for the phenoxysilanes (PhO).SiMe,-, (n = 1, 2, or 3) and (PhO),SiEt, are given in Table 21. The vibration v(SiO,C,-,), had previously

Table 21 SeIected wauenumberslcni-' for some phenoxy-methyl- and -ethylsilanes Assignment v(SiOnC4- n)aa v( SiO C,- n ) s v(C- 0- Si), v(C- 0- SQa8

Rangejcm-' 700- -7 60 6 12--680 9 I6--93 1

925--970

been assigned at cn. 925 cm-'; that band is now assigned to 6(CH) and 6(CC) vibrations of the phenyl group.21s Vibrational data for many other organooxy-silanes have been reported.21a-2zo1.r. spectra of the silanols Me,-,Ph,SiCH,Si(Me,)OH show decreasing hydrogen bonding in the order n = 0 >

*Onn

ylo

*I1 212

*I3 2*4

"Is ?Ie

J. R. Durig, M. J. Flanagan, and V. F. Kalasinsky, J . Mol. Structure, 1975, 27, 241. J. R. Durig, V. F. Kalasinsky, and M. J. Flanagan, Inorg. Chem., 1975, 14, 2839. A. Marchand and M. T. Forel. Bull. Sor. chini. France, 1975, 72. K. G. Sharp, Inorg. Chem., 1975, 14, 1241. W. Wolfsberger, 2. Naturforsch., 1975, 30b, 907. L. W. Breed and J. C. Wiley, jun., J . Organometallic Chem., 1975, 102, 29. K. A. Andrianov, M. N. Ermakova, N. A. Dmitricheva, V. E. Sklover, N. G. Bokii, and Yu. T. Struchkov, Doklady Chcm., 1975, 220, 149. N. V. Kozlova, I. F. Kovalev, Yu. I. Khudobin, N. P. Kharitonov, and M. G . Voronkov, Doklady Phys. Chem., 1975, 220, 85. J. SouEek, K. Strdnskg, R. Reficha, and J. HetflejS, CON. Czech. Chem. Comni.,1975, 40, 261 1.

"I7

N. V. Kozlova, I . F. Kovalev, Yu. 1. Khudobin, and M . G. Voronkov, D o k l d y Phys. Chem.,

"*

N.S. Nametkin, V. M. Vdovin, V. A. Poletaev, and M . B. Sergeeva, Doklady Chent., 1974,

LIU

22''

1975, 221, 328.

217, 505. K . A. Andrianov, I. A. Shikhiev, G . A. Abbasova, R . Yu. Gasanova, and A . A . Mamedov, Doklady Chcni., 1975, 218, 593. A. G . Brook, J. B. Pierce, and J . M . Duff, Crmad. J . Chct?~.,1975, 53,2874.

250

Spectroscopic Properties of lnorganic and Organometallic Compounds

n = 1 > n = 2. Miscellaneous i.r. data on these and other organosilicon compounds have been salted away in supplementary p u b l i ~ a t i o n s . ~ ~ l - ~ ~ ~ The ‘germylenes’ PhGeOGePh show bands at 840 and 870cm-l which have been assigned to v(Ge0Ge) Features at 915 and 612 cm-l have been assigned226to Ge-0 modes in the oxalato-compound formulated as H2[Ge(C2O4),],6H,O. Some partial assignments 226 are also given in Table 22.

Table 22 Selected wavenumberslcm-l for germyl phosphato-derivatives Compound

(Me,GeO),P(O)H [ Me,GeOP(O)(H)O],

i

Assignment

WaoenurnberJcm-l 2331 1227 1010 67 1 2338 1018

V(PH) v(P=O) v[ 0- P(=0)- 01 v(0-Ge-0) V(PW v[ 0- P(=0)- 01 v( 0-Ge- 0)

668

The species Sn,O, and Sn30,, formed by diffusion-controlled reactions of SnO-N2 at 4.2 K, have i.r. absorptions at 517 and 760 cm-l, Compound (26) has v(Sn-0) at 520 cm-1,228and fragmentary i.r. data have ,OSi Ph@, X Si--0Si Ph., 1 1 2 8 0 > 11,20 is more consistent with a unidentate n i t r a t o - g r ~ u p .Two ~ ~ ~ other papers 487 discuss charge-transfer complexes of the TI SO

f

J. D. Donaldson. S . D. Ross, J. Silver, and P. J. Watkiss, J.C.S. Dalton, 1975, 1980. G. W. Frazer and G. D. Meikle, J.C.S. Dalron, 1975, 1033. Q7G K. 0. Christe, 2.anorg. Chem., 1975, 413, 177. 478 B. Bonnet, C. Belin, J. Potier, and G. Mascherpa, Compt. rend., 1975, 281, C, 101 1. 4 7 7 K. Wada, T. Takenaka, S. Hayashi, and S. Takeno, ‘Proceedings of the Second International Conference on Solid Surfaces’, ed. H. Kumagai and T. Toya, Tokyo, Japan, 1974, p. 109. 47n R. R. Smardzewski and W. B. Fox, J. Phys. Chem., 1975, 79, 219. Ya. M. Kimel’fel’d, E. M. Smirnova, and E. P. Eremina, Izoest. Akad. Nauk S.S.S.R.,Ser. khim., 1974, 2714. u0 Ya. M. Kimel’fel’d, A. B. Mostovoi, and L. M. Mostovaya, Zhur.fiz. Khim., 1975, 49, 284. 481 E. V. Belousova, Ya. M. Kimel’fel’d, and A. P. Shvedchikov, 2hur.fiz. Khim., 1975,49, 1075. IH2 A. I. Karelin, Z. I. Grigorovich, and V. Ya. Rosolovskii, Spectrochim. Acta, 1975, 31A, 765. 4n3 C. J. Schack, D. Pilipovich, and K. 0. Christe, Inorg. Chem., 1975, 14, 145. u4 H. D. Lutz and H. J. Klueppel, Ber. Eunsengeselfschaft phys. Chem., 1975, 79, 98. IH6 D. W. Amos and G. W. Flewett, Spectrochim. Acra, 1975,31A, 213. 486 V. E. Sahini and M. Ciureanu, Fiz. Mat. Metody Koord. Khim., Tezisy Doklady, Vses. Sooeshch., 5rh, 1974, 41. w 7 G . Maes and T. Zeegers-Huyskens, Spectroscopy Lettcrs, 1975, 8,415. 473 474

274

Spectrmcopic Properties oj' Itiorguiiic and Orgaiionietullic Compounds

Two new interhalogen cations have been characterized as fluoroantimonate Br,CI+ has Raman shifts of 424 and 300cm-l, assigned to u(BrC1) and v(BrBr), respectively. BrCI, I yielded the assignments v(BrCl,),, 421, u(BrC1,),v 430, and S(BrC1,) 167 cin l . The I : 1 adduct of IF, and SbF5 has been shown to be constituted of the known ions IF,;+and SbF,- by i.r. and Raman The reaction of graphite with SbF,-CIF, mixtures leads to a compound formulated as C, '(SbFs ),CIF, because t h e i.r. spectrum contains the characteristic bands of CIF, and the SbF,In solution the compound F,ClF, is monomeric, but chain structures with fluorine bridges are formed in the solid The stability of adducts of ICN has been studied by i.r. spectrophotometry.4Q2 The Raman spectrum of the broniine oxide Br,O, has been assigned, without supporting evidence, to the structure OBrOBrO, rather than 0,BrBr0,.493 lsopropyl perbromate, Pr'OBrO,, has been synthesized and displays a strong i.r. absorption at 790 cm-l in cyclohexane The reaction of potassium bromate with liquid bromine pentafluoride has led to the isolation of the compound K[BrO,F,], whose Raman spectrum has been assigned as follows: v(Br-0) 885, 893 cni-'; v(BrF) 389, 375 cm-l; u(BFO),, 910 cm-'. However, the Raman polarizations were not The Raman and i.r. frequencies of the barium salt of the new ion [103F]have been given, but the authors had difficulty in assigning the spectra, and the structure is far from certain.4gs The compound I02F3,SbF6,it was concluded, is not [1O2F,]+SbF6, but is likely to be a simple adduct with 1 = 0 -+ Sb co-ordir~ation.~~' v(I=O) is at the low value of 855 cm-l and v(0-Sb) has been assigned at 447 cm-'. The spectra of CsI0,F4, T02F3,and liquid SbF, have also been discussed. The spectra of Cs[H(IO2F,),],2H,O have been interpreted on the basis of a hydrogen-bridged and bands associated with co-ordinated iodate assigned in the complexes M[Mn(lO:,),] (M = Na,, Mg, or Sr).498

8 Group VIII Elements Emission spectra have yielded the following vibrational wavenumbers: for XeBr, 180; for XeCI, 210; and for KrF, 400 cm-'. These frequencies 6oo are close to those of the diatomic caesiuni halides, and differ slightly from related results where the molecules are not vibrationally relaxed. Ferraro and co-workers have W. W. Wilson, B. Landa, and F. Aubke, Jtrorg. Nuclear Chem. Letters, 1975, 11, 529. E. Gebert, Inorg. Chem., 1975, 14, 2233. A. A. Opalovskii, A. S. Nazarov, and A. A. Uminskii, Russ. J . Inorg. Chcwr., 1974, 19, 827. 4L)1 E. Lehmann, D. Naumann, and W. Stopschinski, Spectrochim. Acta, 1975, 31A, 1905. 492 J. De Leeuw, M . Van Canteren, and Th. Zeegers-Huyskens, Spectroscopy Letters, 1974, 7 , 607. 4u3 J.-L. Pascal, A.-C. Pavia, J. Potier, and A . Potier, Conzpr. rend., 1975, 280, C, 661. 494 K . Baum, C. D. Beard, and V. Grakauskas, J . Amer. Chem. Sur., 1975,97,267. m6 G . Tantot and R. Bougon, Compt. rend., 1975, 281, C , 271. 496 S . Okrasinski, R. Jost, R. Rakshapal, and G . Mitra, Inorg. Chin]. Acta, 1975, 12, 247. u7 H . A. Carter, J. N. Ruddick, J. R. Sams, and F. Aubke, Inorg. Nuclear Chem. Letters, 1975, 11, 29. 4 Q y J. B. Milne and D. Moffett, fnorg. Chmr., 1975, 14, 1077. 4y9 A . V. Melezhik and V. L. Pavlov, Rws. J . Jnorg. Chem., 1975, 20, 532. C. A. Brau and J. J. Ewing, J . CIit~tir.P l i j ~ ~1975, ., 63, 4640. J. E. Velazco and D. W. Setser, J . Chenz. Ph)ts , 1975, 62, 1990.

inn

uQF. A. Hohorst, L. Stein, and

Clmruclet-istic Vibrutiorid Frequericies of Compounds 275 given a good overall account of the Urey-Bradley force-constants of XeOF,, XeO,F,, and XeO,F,, though no new assignments have been It has been suggested that the adduct XeF,,WOF, is best regarded as a covalent molecule with the structure (64). Raman bands at 573 and 577 cm-’ are due to v(Xe-F) and a weak band at 458 cm-’ to v(Xe-F). The value of v(Xe-.F) is

intermediate between those of XeF+ and XeF,. Similarly placed bands in XeF2,2WOF, support the structure (65).”03 By contrast, the adducts 2XeF,,MF, ( M = Sb or Ta) and XeF2,nMF, (n = 1 or 2 ; M = Sb, Ta, or Nb) give spectra which are best interpreted in terms of ionic formulations involving XeF+ and Xe,F,+ ions and varying degrees of semi-covalent interaction.604 The i.r. and Mossbauer spectra of the adduct 2XeF2,SnF, are likewise consistent with an ionic formulation, uiz. (XeF),SnF,.605 The semi-covalent interaction features again in the krypton complex [KrF]+[AuFJ+, with v(Kr-F) at 597 cm-l and v(Kr*-F) at 346 cm-l. A band at 163 cm-l has been assigned to a (F-Kr-F) bending mode.506 The adduct KrF,,XeF, has been shown to be a weakly associated molecular coniplex and not to have an ionic

606 6oe

R. D. Willett, P. LaBonville, and J. R. Ferraro, J . Chem. Phys., 1975, 63, 1474. J. H. Holloway, G. J. Schrobilgen, and P. Taylor, J.C.S. Chem. Comm., 1975, 40. B. Frlec and J. H. Holloway, J.C.S. Dalton, 1975, 535. V. N . Sarubin and A. S. Marinin, Russ. J . Inorg. Chem., 1974, 19, 1599. J. H . Holloway and G . J. Schrobilgen, J.C.S. Chem. Comm., 1975, 623. V. D. Klimov, V. N. Prusakov, and V. B. Sokolov, Dohludy Chem., 1975,217, 549.

10

6

Vibrational Spectra of Transition-element Compounds ~~

BY M. GOLDSTEIN

1 Introduction One of the dangers inherent in compiling a review of this type is that, i n an attempt to fulfil the aim of being comprehensive in coverage, the more important aspects of the subject become lost in an ocean of information, much of which is without conclusion and consequence, or (in all too many cases) is without credulity and foundation. Consequently, there has been increased emphasis in recent editions of this chapter on new correlations and on the higher-quality spectroscopic papers, while data reported for characterization, and those of doubtful validity, are given only the briefest of mentions. This trend has been extended this year, particularly by expanding and sub-dividing the ‘General’ section. Selection of material for this special mention has naturally been subjective, and should not be taken necessarily to mean that other papers are to be disregarded in any way, or that they are not, in their own right, valid and worthwhile contributions. It is hoped that the Report has been made more digestible by this modification. The material for other sections has been arranged in the same way as in previous Reports, to which the reader should refer for details. 2 General and More Significant Aspects

Detailed Studies.-While Chapter 4 deals with definitive reports on small, highly symmetric species, larger systems involving transition-metal atoms are considered here. Table 1 1-20 collects together some of the references describing the more complete and thorough studies. In many of these, NCA of some sort ‘L

lo l1

K. H. Schmidt and A. Miiller, Inorg. Chem., 1975, 14, 2183. L. H. Jones and 13. I. Swanson, J. Chem. Phys., 1975, 63, 5401. H. Siebert and M. Weise, Z. Nuturforsch., 1975, 30b, 669. C. Jeanne, R. Prince, and R. Poilblanc, Spectrochirn. Actu, 1975, 31A, 819. J. R. Johnson, D. M. Duggan, and W. R. Risen, jun., Inorg. Chcm., 1975, 14, 1053. C. W. Schliipfer and K. Nakamoto, Inorg. Chem., 1975, 14, 1338. E. Koniger-Ahlborn, A. Muller, A. D. Cormier, J. I>. Brown, and K. Nakamoto, Inorg. Chetn., 1975, 14, 2009. A. Miiller, M. G. Chakravorti, and H. Dornfeld, %. Nafurforsch., 1975, 30b, 162. T. A. Keiderling, W. T. Wozniak, R. S. Gay, D. Jurkowitz, E. R. Bernstein, S. J. Lippard, and T. G. Spiro, Inorg. Chem., 1975, 14, 576. J. G. Contreras and D. G. Tuck, Cunud. J. Chenr., 1975, 53, 3487. C. S. Creasear and J. A. Creighton, J.C.S. Dalton, 1975, 1402. A. Muller, N. Mohan, F. Kijniger, and M. C. Chakravorti, Spectrochirn. Acfa, 1975,31A, 107. Yu. A. Barbanel, K. B. Dushin, V. V. Kolin, N. K. Mikhailov, and G. P. Chudnovskaya, Koord. Khirn., 1975. 1, 411. I. V. Lipnitskii, N. M. Ksenofontova, A. M. Prima, and D. S. Umreiko, Dokludy Akud Nuirk Bolgarsk. S.S.R., 1974, 18, 1074. I. V. Lipnitskii, D. S. Umreiko, and A . R. Kovriliov, 1;iz. Mat. Mefody Koord Khinr. T ~ z i s y Doklady, Vses. Sooeshch., 5th, 1974, 30.

276

Vibrational Spectra of Trnrisition-element Cotnpouttds

Table 1

277

Coitipoiimls f i w whidi fairly complete. urid detailed studie; hnce beet1 made COF?lpOWld

[ M (NHS), l2

'

+

[M(NH3),l2 [M(N Hs),l3+ IPt(NHs),l4+ K2 [zn( cN 14 1 M[Pt(CN),I tM(CO),(PH,)I tReM(CO),rJI"i(S2C,R,),I"[Ni(MoS4),I2[WWS,),12Hf(BH414 [Prn,N]CdX3 [Bun4N]TiX, [PdC1J2Cs2NaLnC1, K,[PtBr,CI,-,,I CS,[OSCI,Fs - ,] Cs2[OsBrC1F4] [Re,0Cl,,14 [Ru,OX,,I~[Ru2NX8(H20),l3KIOsOsN] [ReOF,] -

M = Co, Zn, Cd, Cu, Pd, or Pt M = Mn, Fe, Co, Ni, Zn, o r Cd M = Cr, Co, Ru, Rh, Os, o r Ir M = Mg, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, or Cd M = Cr, Mo, o r W M = Cr, Mo, o r W R = H, Ph, CF,, o r CN; JZ = 0, 1 , o r 2

X = C1, Br, o r I X = CI o r 13r Ln = Nd or Er n = 0-6 n = 1-4

2

b, c

3 c

4b 5 b 6 b,C 7 b, c 8 9b 10 11 12 b * c 13 14-16

j:lb

X = CI or Br X = CI o r B r

a Excluding matrix-isolated species; see also Chapter 4. studied: see Table 2.

} ,x"

19 b * c 20

NCA carried out.

' Isotopic shifts

was carried out; in several instances the assignments were also assisted by isotopic substitution (cf. Table 2). Particularly pertinent conclusions from these studies are included in the appropriate later sections of this Report.

Use of Isotopic Substitution.-The use of deuteriation as an aid to assignment of v(MH), v(M-NH3), etc. is a long-established technique, and more recently the application of metal isotopes has emerged. The list assembled in Table 2 2 # l 2 v 19* 21--31 serves to illustrate the wide range of compounds being 39

l6 l' la

l9 2o 21

2a 29

24

pL 27

29

6g

' 9

I. V. Lipnitskii, N. M. Ksenofontova, A. B. Kovrikov, A. M. Prima, and D. S. Umreiko, Koord. Khim., 1975, 1, 220. W. Preetz and Y. Petros, 2. anorg. Chem., 1975,415, 15. R . Mattes, M. Moumen, and 1. Pernoll, Z. Naturforsch.. 1975, 30b,210. K. H. Schmidt, V. Flemming, and A. Muller, Spectrochini. Acta, 1975, 31A, 1913. J. H. Holloway and J . B. Raynor, J.C.S. Dalton, 1975, 737. J. Kincaid and K. Nakamoto, J. Inorg. Nuclear Chent., 1975, 37, 85. H. Ogoshi, E. Watanabe, Z. Yoshida, J. Kincaid, and K. Nakamoto, Inorg. Cheni., 1975, 14. 1344. Y. Nakamura and K. Nakamoto, Inorg. Chem., 1975, 14, 63. K. Schmidt, W. Nauswirth, and A. Muller, J.C.S. Dalton, 1975, 2199. E. Miki, K. Mizumachi, and T. Ishimori, Bull. Chetii. Soc. Japan, 1975, 48, 2975. Y. Mori, H. lnoue, and M. Mori, Inorg. Chem., 1975. 14, 1002. C. A. Fleming and D. A. Thornton, J. Mol. Structure, 1975, 27, 335. G. C. Percy, J. Inorg. Nirclear Chrm., 1975, 37, 2071. D. Pawson and W. P. Griffith, J.C.S. Dalton, 1975, 417. J. F. Myers, G. W. R. Canham, and A. B. P. Lever, Inorg. Chem., 1975, 14, 461. B. Hutchinson, R. L. Hance, B. B. Bernard, and M. Hoffbauer, J. Chem. Phys., 1975,63,3694.

278

Spectroscopic Properties of Inorganic and Organometallic Compounds

Table 2 Cornporiticis studied b y isotopic substitiction a Con i p und K2 [Zn(CN),I Ni [Pt(CN),] Z~(CN),I [M(tetrapheny1porphin)l [M(octaethylchlorin - 2H)] [Mg(octaethylchlorin - 2 H)(py),] “i(S2C2R2)2ITt[Ni( M o S ~ ) ~ ] ~ [PdC16]2M[PtCl(acac),], Fe[PtCl(acac),], “i(NH3)6lCI2 [Co(NH3)61C13 [Zn(NH,),l12 [Rh(NO)(Ph,P)3I [Rh(NO)XY(PhaP)2I [Cu(NO2)2(N H3)21 trans- [Co(N 02)(acac),( R C, H,N)] tr~ns-[Co(NO~)(acac)~(RC~H,NH~)]} [Ni(N-salicylidenegl ycinato)] [N=RuX3L1,] [NEOSX~L~~] K[Os03N]

Ref.

>: >::: >:1

15N

}

[CoCl,(phthalocyanine-)] [F~(co),I

7

24 25 26 27 28

}

[FeCl,(phthalocyanine-)]

6 d

29 19

}

30 1 31

Excluding matrix-isolated species and the use of deuteriation. Spectra assigned for MI’ = Ag, Co, or Pd by analogy. (octaethylchlorin - 2H) = dianion formed by loss of 2H+ from the quadridentate macrocycle related to chlorophyll-a and haem, trans-octaethylchlorin; assignments also made for Ni” analogue and [Fe(octaethylchlorin -- 2H)Xl (X = F, X = C1 or Br; Y = X or NO,. R = H, Ph, CFS, or CN; n = 0, 1, or 2. C1, Br, or I). f T w o forms thereby characterized. R = substituent in 3- or 4-position (31 compounds in all). X = C1 or Br; L1 = bipy or tertiary arsine or stibine; Lz = L1 or tertiary phosphine. Cr”’ and bromide analogues assigned by comparison.

Table 3 Assignments for coniplexes derived f r o m octaethylchloriri (oec) a [24Mg(oec 2H)(py),] VI Avl cm-1 cm-l 343.7 0.8 326.0 0.0 277.0 256.0 227.5 176.5 142.0

Av

2.5 0.0 5.5 4.0

3.0

[64Zn(oec - 2H)I vl Avl cm-1 cm-l 334.0 0.0 312.5 0.0 281.5 0.0 0.0 267.0 254.0 0.0

[63CU(oec - 2H)] VI Avl cm-l cm-I 340.5 0.0 317.0 0.0 290.0 1.0 276.0 0.5

212.0 168.0

233.0 168.0

-

1.0 0.5

1.6 0.0

= Y ( ~ ~ M v(26Mg), ~ ) v(&’Zn) - v(RaZn),or

[Ni(oec

-

2H)]

Vl

cm-l 358

Assignment

298 284 256

14~~Cu) - ~(‘WU), as appropriate.

Vibrational Spectra of Transition-element Compounds Table 4 Assignments for [Ni(MoS,),J2- (cm-l)

279

(I

v(58, 92) 455.5 323.8 181.0 50.0 494.0 442.5 331.5 222.5 179.5

v(58,92)

- ~ ( 6 292) ,

'

0.5 4.7 0.7 0.5 0.0 0.4 4.7 0.3 1.2

v(58,92) ~ ( 5 8 100) , 6.0 0.3 2.3 0 6.0 1.4 0 2.5 2.0

v(58, 92) corresponds to values,km-' for [58Ni(BaM~S,),]Zerc. tions given.

Table 5 Assignments of Ni-S [Ni(S2C2R2)2]n(cm-l) Complex

[Ni(S,C2Ph,),I-

(I

Species v(NA) 428 B2u 398 B*lU 41 1.5 B2u 385 B3u 475 B2u 408 B2U 454 B3u (40.9) B3U 465 Bzu 406 B2u 428 B3u 450 Bzu 401 B2U 41 8 B,, 465 B2U 425 B3u 449 B2u 41 5 B3U 422 B,U 394 B3u 468 B2l4 396 B2u (444.8) B3u 365 B3U 457 B2u 365 B2u (433.7) B3u 357 B311

6.0 5.0 2.9 0.5 6.0 1.7 4.7 2.5 3.3 Potential energy distribu-

stretching and bending modes in complexes v(NiS) v(58Ni)- v(62Ni) &NA) 6.5 (7.3) 237 76 4.8 (6.9) 233 8.0 (7.0) (6.7) 76 6.5 (5.7) 202 1.0 (1.8) 130 5.0 (6.0) - (0.4) 5.3 (2.6) (204.1) 1.4 (4.3) 130 4.2 (5.0) (40.5) f 207 f 128 f (40.8) f 21 1 f (38.4) I 210 f (38.4) I 208 I (38.3) 3.8 (1.9) 224 5.8 (4.0) - (2.9) (42.3) 3.9 (3.5) 2196 3.0 ( 1 .O) (5.7) - (1.8)

4.0 (4.5)

8(SNiS) 8(68Ni) - 8(62Ni) 2.5 (1.7) 0.0 (0.5) 2.0 (1.7) 0.0 (0.5) 2.2 (2.6)

(42.3)

Calculated values in parentheses. NA = natural abundance. Coupled mode. f N o isotopic data obtained.

be observed.

v(58, 92)

- ~ ( 6 2 100) ,

G(SNiS').

-

- (2.6) - (0.3) f

f f

Y

f

1 f

1 Y

2.2 (2.2)

- (0.3) 2.2 (2.3)

- (0.3) Could not

280

Spectroscopic Properties of Inorganic and Organometallic Compounds

studied by isotopic substitution. Some very elegant studies are being carriep out, and useful correlations and structural conclusions are emerging. For example, l4*laNshifts are useful in identifying v(MN) in complex sy~terns,2~-2~ and particularly where confusion with v(M0) might occur.26-28The additional information afforded by isotopic substitution has also been used in refinement of force fields.2.7, 12, 19, 24, 31 For the octaethylchlorin complexes listed in Table 3, the presence of only one i.r.-active v(MN) mode [other than v(Mg-py), identified by comparison in the series] implies an essentially planar MN4 skeleton.22The data for [Ni(MoS4)J2in Table 4 follow those given for [84~68Zn(Q2J00M~S4)2J2-in last year's Report. Of particular interest are the assignments given in Table 5 , since these are in disagreement with several empirical results described in the literature; for example, the strong band at 351 cm-l in the i.r. spectrum of [Ni(S2C2Ph2)2] was previously assigned as v(NiS) but is now found to be insensitive to cs~62Ni isotopic substitution.6 Inevitably, upsets such as these will occur, but metal isotope effects should not be considered necessarily to be the panacea for problems i n assigning v(ML) modes. For example, results on tetraphenylporphine complexes showed that in most cases several bands shift, indicating substantial mixing of internal co-ordinates ; however, some trends were found consistent with expected ligand-field effects, so that substantial contribution from v(MN) can be assumed:21

M

Pd 302 218

Ni 322 255

Co 313 252

Cu 268 219 207

Ag

245 200 188

Zn ca. 245 cu. 203 188

A similar trend has been found for v(MO), located by metal isotopic substitution, in complexes believed to have structure (1):23

M

vlcm-'

Fe 262

Ni 267

Cu 283

Zn 233

Resonance Raman Spectra.-Techniques and understanding appropriate for studies of resonance Raman phenomena have now developed sufficiently for application to a whole range of inorganic systems, as illustrated by Table 6.32-40 32

33

s4

s6

W. F. Howard, jun. and L. Andrews, Inorg. Chem., 1975, 14, 1726. H. Hamaguchi, I. Harada, and T. Shimanouchi. Chem. Phys. Lefters, 1975, 32, 103. R. J. H. Clark and M. L. Franks, J. Amer. Chem. Soc., 1975, 97, 2691. A. Miiller and E. Ahlborn, Spectrochim. Acra, 1975, 31A, 75. S. Sunder, L. Hanlan, and H. J. Bernstein, Inorg. Chem., 1975, 14, 2012.

Vibrational Spectra of Transition-element Compounds 28 1 The method is having a clear impact in the field of bio-inorganic hemi is try,^^-^^ but one hopes that investigators will not seize too readily on any odd band below 500 cn1-l in an attempt to assign a v(ML) mode. For the simpler species listed in Table 6, observation of band progressions has led to improved understanding Table 6 Resonance Raman spectral studies Species

Principal assignments

Re3CI, (matrix-isolated) Re3Cl, (solid) [IrClJ2M,[Mo,CI,] (M = K , NH,, etc.) Cs,WOSe, [M(S,PPh,),] (M = Cr or Ni) [(NC)6C0(02)C0(CN)6 i5~

~

~

S

~

~

S

~

0

~

0

} 2

~

~

0

~

[Mn(Ph,PorPh)Xl ~ ~ ~ $ ~ b l n }O2 a or n d CO complexes 'Blue' copper proteins

f

~

~

,

v( ReRe)

32

vl( Ir CI)

33 34 35 36

v,(MoMo), v,(MoCl) v,(WSe) Vd,,,(MS) v(OO), v ( C o 0 )

~

,

1

6

v(1igand)

{

Ref.

+

cp

37 38

v(1igand) c s *

39

u(1igand) v(CuN), v(CuS)}

40

Isolated and associated Re,CI, units. Use of 488 nm excitation results in selective Internal ligand modes. enhancement of v2 via a W-Se charge-transfer absorption. Ph,porph = tetraphenylporphin; X = C1, Br, or 1; bands attributable to v(MX) coupled to v(MN) also noted. Bands below 500 cm-' thought to be v(FeN). f Azurin, plastocyanin, and caeruloplasmin.

of the vibrational In matrix-isolated Re3Clo, different band progressions due to monomeric (Re&],) or somewhat associated species have been observed, depending on the matrix deposition concentration^.^^ Anomalous polarization (including of vl) in the resonance Raman spectrum of [IrC1J2- has been discussed in terms of the Jahn-Teller effect in the excited electronic ~ t a t e . 3 ~ Harmonic frequencies and anharmonicity constants have been presented for various [Mo,Cl#Matrix-isolation Studies.--Chapter 4 includes references to several investigations

of this type, but in addition reports have been published of carbonyls and simple 0x0-species. Thus studies have been made of the i.r. spectra of (a) [Fe(CO),], largely substantiating previous as~ignments,~~ (6) [Mo(CO),], where n = 6, 5 , 4, or 3 (NCA gave CZubond angles of 174" and 107" for n = 4, C3vbond angle of 105" for n = 3),42 (c) [W(CO),], from photolysis of [W(CO),(py)] in Ar at 12 K,43 (d) CrO, and MOO,, from reaction between O2 and the corresponding 37

sn 30 40

41

4a 43

T. C. Strekas and T. G. Spiro, Inorg. Chem., 1975, 14, 1421. R. R. Gaughan, D. F. Shriver, and L. J. Boucher, Proc. Nar. Acad. Sci. U.S.A., 1975, 72, 433. L. Rimai, I. Salrneen, and D. H. Petering, Biochemistry, 1975, 14, 378. V. Miskowski, S. P. W. Tang, T. G. Spiro, E. Shapiro, and T. H. MOSS,Biochemistry, 1975, 14. 1244. J . D. Brown, D. E. Tevault, A. D. Cormier, and K. Nakamoto, Spectrochim. Acra, 1975,31A, 1773. R. N. Perutz and J. J. Turner, J. Amer. Chem. SOC.,1975, 97,4800. A. J. Rest and J. R. Sodeau, J.C.S. Chcnz. Comm., 1975, 696.

282

Spectroscopic Properties of Inorganic and Organometallic Compounds

Table 7 Assignment of metal-metal stretching modes

Ref. 46 34 47

a

48

49 50

101 < 204, 216 9 178,213, 195 180,201,205;g 260,265 170, 175, 179;g 221, 225 176,207;g 231 212, ca. 177 0

'

[

I I I

CQ.

51

'

52

I I

5

[ 1

I

277 277 277 277 316 245 305 177

I I

(

I

[

1 I I

I I I

32 4

>

53

< k

54

< >

145

55

56

1 1 1

57

1

I I I I

58 59

60

P

n = 3, 2, 1, or 0. X = CI, O,CCF,, SnCl,, or Y ; M = K, Rb, Cs, NH4, or JenH,. Ar = Ph (crystal structure determined) orp-tolyl. * Assigned as vBy,(WHW), Y = Br or I. in which the H atom is symmetry-constrained; the band is unshifted on deuteriation. f L = py, v(M1M2M1) mode of ring; see (2). v(MIMZ)t. v(ReRe). f v(1nRe). Me,CO, or Ph,CO. Matrix-isolated. Rpy = C,,H5N or 3-MeCpH,N. R = Bun, HOCH,, Ph, etc. From thia = 1,3reaction between PF, and (Hg2)*+in SO,. O Structure shown by X-ray diffraction. or 1,4-dithian or 1,3,5-trithian.

'

'

Vibrational Spectra of Transition-element Compounds

283

metal and ( e ) U 0 2 + or U02+-N02- charge-transfer complexes, from interaction between U 0 2 or UO with NO2 in Ar Metal-Metal Vibrations.-As is evident from Table 7,'~ 32, 46-60 assignment of so-called metal-metal stretching modes has come back into fashion, although the reasons for this are as unclear as some of the evidence (where given) for many of the assignments. Indeed, the difficulties of assigning such modes in Raman 341

spectroscopy, particularly when based on intensity criteria, have been emphasized and some literature errors corrected.61 For example, the band reported as v(FeFe) in [Fe,(CO),] at 225 cm-l is attributable to a decomposition product rather than the dinuclear carbonyl itself.61 Equally striking is the assertion 61 that the intense 125 cm-l Raman band of [Re,(CO),,] cannot be v(ReRe) as presupposed because it is present also in the spectra of [Re2(CO)BX2](X = C1 or Br), which complexes are not metal-metal bonded. However, some reliable and valuable results are emerging. Thus a detailed NCA treatment of the spectra of [ReM(CO),,]- species has shown that the force constants vary in the order9 k(Re-W) > k(Re-Mo) > k(Re-Cr). The values for these constants have also been compared with similar data for [MnMl(CO),,]- and [M'M2(CO),,] (M1 = M2 = Mn, Tc, or Re; M1 = Re, M2 = Mn).6 It has similarly been found that Au-TM bonds (TM = transition metal) are more ionic than Hg-TM bonds, and that there is a strengthening of metal-metal bonds in the order: Pd"-TM < Pt"-TM < Aul-TM < I-Ig'1-TM.67 '4

"

47 4fl 49

6n

53

G3 64

6R KR

67

6R

an O0

G1

L. V. Serebrennikov and A. A. Mal'tsev, Vestnik Moskou. Uniu. Khim., 1975, 16, 251. S. D. Gabelnick and G. T. Reedy, U . S . N . T.I.S., ADIA Rep. 1974, No. 00543318GA [Gou. Rep. Announce. Index ( U S . ) , 1975, 75, 751. D . H. Harris, M. F. Lappert, J. S. Poland, and W. McFarlane, J.C.S. Dalton, 1975, 311. G . Holste, 2. unorg. Chem., 1975, 414, 81. C. D. Garner and R. G . Senior, J.C.S. Dalton, 1975, 1 171. F. A. Cotton, T. Inglis, M. Kilner, and T. R. Webb, Znorg. Chem., 1975, 14, 2023. D. C. Harris and H. B. Gray, J . Amer. Chem. Soc., 1975, 97, 3073. F. Neumann and H.-J. Haupt, J . Organometallic Chem., 1975, 84, 329. H.-J. Haupt, F. Neumann, and H. Preut, J . Organometallic Chem., 1975, 99, 439. J. R. Ebner and R. A. Walton, Znorg. Client., 1975, 14, 1987. G. C. van den Berg and A. Oskam, J . Orgunometallic Chem., 1975, 91, 1. P. Braunstein and J. Dehand, Buff.Soc. chim. France, 1975, 1997. L. V. Konovalov and V. S. Myl'nikov, J . Struct. Chem., 1974, 15, 612. P. Braunstein and J. Dehand, J . Organometallic Chern., 1975, 88, C24. P. A. W. Dean and D . G. ibbott, Inorg. Nuclrar Cham. Lcrters, 1975, 11, 119. K. Brodersen, N. Hacke, and G. Liehr, Z . nnurg. Chem., 1975, 414, 1 . K. Brodersen, G . Liehr, and W. Rolz, Chem. Ber., 1975, 108, 3243. B. I. Swanson, J. J. Rafalko, D . F. Shriver, J. San Filippo, jun., and T. G. Spiro, Inorg. Chem., 1975, 14, 1738.

Spectroscopic Properties of Inorganic and Organometallic Compounds

284

General Series of Complexes.-Assignment of metal-ligand stretching modes in series of complexes of a given ligand, sometimes spanning several periodic groups or periods, was a common event in 1975, and Table 8 38s 62-B1 gives references to literally hundreds of alleged v(ML) bands (nearly all ix.). Frequently, such assignments are given essentially for characterization purposes, but one wonders what the value is of bands being quoted as such with obviously suspect (or even untenable) labels. Among the more questionable assignments quoted last year are v(MS) values for 1,3,4-thiadiazole-2,5-dithioIderivatives, 39

21p

231

303

Table 8 Metal-ligand assignments in various series of complexes Series

a

IHgM(NCS)4L4I, [M(NCS),I2-, etc. [ M Hg(SCN),LI

M

l-

-

M [Pt(CN),I

[M{(2-pyCH2),C0NH},(NCS),I

{

[MZ,{SC(NH)NHC(O)CH,}2] etc. [MZ2(GH,NCONHAI 7 [MZ,(ON=CMeCH=CMe),] I

v(M-NCS)

62

v(M-NCS)

63

Co, Ni, Cu

[MZ,(ON=CMeCH=CPh),] [M(PhNHNCSN=NPh),]

Co, Ni, Zn, Cd Fe, Cu Mg, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd Co, Ni Ag, Zn, Cd, Hg

1

Ref.

Assignments

V(MN) v( M -NCS) v(MN), V(MS), {v(MX) v(MO), v(MN)

3"

}

64 656 66

Co, Ni

v(MN), v(MZ)

67

Co, Ni

v(MN), v(MZ)

68

Mg, Mn, Co, Ni, Cu, Zn, Cd

v(MO), v(MX)

70'

co, c u Ti, Cr Cr, Co

v(MN), v(MX) v( M Cl)

71 72 73

etc.

Co, Ni, Cu, Zn

Co, Ni, Cu Mn, Fe, Cu, Zn Co, Ni, Zn, Cd Fe, Co. Ni Cr; Fe,'Co, Mn, Co, Ni, Cu, Pd,

[ M(Ph,porphin)]

{

Rh, Ir, Pd, Pt Mn, Fe, Cu Cu, Zn, Cd h$, Co, Ni, Zn, Co, Ni, Cu, Zn Fe, Ni, Cu, Zn Co, Ni, Cu, Zn

21 Y( MCI)

79

V(MX) v(MO), u(MC1) v(MO), v(MZ)

80

v(MO), v(M2)

83

dMO) v(MO) v(MN), v(M0)

84 23 d , 85

81

82

' ri

Vibrational Spectra of Transition-element Compounds

28 5

Table 8 (cont.)

-

Series O [M(thio-one),J2+ etc. [M(S,PPh,),l [ M n{(S,CN W2(CHz)a1mI [ MX,(t hiopyrone),] [M{SC=NN=C(SH)S),] [(MXz)tn(sulPhide)l [M(MeCOCHCOMe),]

M Co, Ni, Cu Cr, Ni Cr, Mn, V O Co, Zn

etc.

g;;be"' {;;;

Assignments v(MO), v(MS) v(MS)

} Zr, Hf, Ce,Th, } ",

A u , Rh,

Pt

v(MS) v(MS), v(MX)

Ref. 86 36 87 a 88

4MS)

89

V W X )

90 *

v(MO)

91

a X = halogen, Y = other anions (NCS, NOs, C104, etc.), Z = X or Y. L = pyrazine L = nicotinamide o r 2-aminopyrimidine (M = Cu); 2-carboxamide, 2-aminopyrimidine, etc. L = Ph,P o r Ph,As (M Cu or Fe). v(MS) for M = Hg See Table 1 and/or Table 2. only. 'The only v(MX) assignments made are for M = Zn (X = C1 or Br) or Cu (X = C1). a ti = 1 o r 2 (M = Cu), n = 1 (M = Co); thiaz == 5-(2-hydroxyethyl)-4-methylthiazole. Pc- = phthalocyanine radical. f n = 3 ( M = Rh or Ir) o r 2 (M = Pd Fc = CsHsFeCsH,. o r Pt). n = 2 (M = Mn or Cu) or 3 (M =: Fe). n == 2 ( M = C o o r Zn) or 1 (M = Mn, Co, Ni, or Hg); acridineO = acridine N-oxide. L = phen, bipy, o r py2. n = 2 (M = Ni, Cu, or Zn) or 3 (M = Fe). ttfaH = 2-thenoyltrifluoroacetone, amine = py or 4-MeC,H,N. p thio-one = thiomorpholin-3-one, thiomorpholine-3-thione, or thiazolidine-2-thione; n = 4 or n = m = 1 (M = VO o r Mn); n = 2, m = 3 (M = Cr); a = 2 o r 6. 6. thiopyrone = 2,6-dimethyl-4-thiopyrone. ' sulphide = ligand (3); m =I 1, n = 2 (M = Ni); m = 2, n = 1 o r 2 ( M = Cu, Pd, o r Pt) or 3 (M = Pd o r Pt). =;

a2

O3 R6

6H " ?"

7a

74

7G 7(i 7i

7H

i' "I1

"' nz

84

R6 HR H7 XR

no y1

P. P. Singh and J. N. Seth, Inorg. Chim. Acra, 1975, 15, 227. P. P. Singh, S. A. Khan, and R. B. Pal, Inorg. Nuclear Chem. Letters, 1975, 11, 807. M. Nonoyama, J. Inorg. Nuclear Chem., 1975, 37, 1897. M. R. Udupa and M. Padmanabhan, Inorg. Chim. A m , 1975, 13, 239. M. Noji, Y. Kidani, and J. Koike, Bull. Chem. Soc. Japan, 1975, 48, 2274. G. Devoto, G. Ponticelli, and C. Preti, J . Inorg. Nuclear Chem., 1975, 37, 1635. M. Massacesi, G. Ponticelli, and C. Preti, J . Inorg. Nuclear Chem., 1975, 37, 1641. A. C. Fabretti and G. Peyronel, J. Inorg. Nuclear Chem., 1975, 37, 603. J. Reedijk, T. M. Mulder, and J. A. Smit, Inorg. Chim. Acra, 1975,13, 219. G. V. Fazakerley and J. C. Russell, J. Inorg. Nuclear Chem., 1975, 37, 2377. J. Hughes and G. R. Willey, Inorg. Chim. Acra, 1975, 13,L1. C. D. Flint and A. P. Matthews, Inorg. Chem., 1975,14, 1219. Y. Kidani, M. Noji, and H. Koike, Bull. Chcm. Soc. Japan, 1975, 48, 239. M. Noji, Y. Kidani, and H. Koike, Bull. Chem. Soc. Japan, 1975, 48, 245. R. J. Collin and L. F. Larkworthy, J. Znorg. Nuclear Chem., 1975, 37, 334. S. Smit and W. L. Groeneveld, Inorg. Nitclrnr Chcm. Letters, 1975, 11, 277. P. P. Singh, R. Chand, and R. Rivest, J. Inarg. Nuclear Chem., 1975, 37,45. R. B. King, J. A. Zinich, and J. C. Cloyd, jun., Inorg. Chem., 1975, 14, 1554. L. Sindellari, L. Volponi, and B. Zarli, Inorg. Nuclear Chem. Letters, 1975, 11, 319. A. Yu. Tsivadze, Yu. Ya. Kharitonov, G. V. Tsintsadze, A. N. Smirnov, and M. N. Tevzadze, Russ. J. Inorg. Chem.. 1974, 19, 1818. A. Yu. Tsivadze, Yu. Ya. Kharitonov, G. V. Tsintsadze, A. N. Smirnov, and M. N. Tevzadze, Russ. J . Inorg. Chem., 1975, 20, 406. G. B. Aitken and G. P. McQuillan, Inorg. Chim. Acta, 1975, 15, 221. F. Izumi, R. Kurosawa, H. Kawamoto, and H. Akaiwa, Bull. Chem. Sac. Japan, 1975, 48, 3188. H. Akaiwa, H. Kawamoto, and F. Izumi, J . Inorg. Nuclear Chem., 1975, 37,65. C. Preti and G. Tosi, Canad. J. Chem., 1975, 53, 177. W. Kwoka, R. 0. Moyer, and R. Lindsay, J . Inorg. Nuclear Chem., 1975, 37, 1889. K. Kato, Y. Sugitani, and K. Nagashima, J. Inorg. Nuclear Chem., 1975, 37,2057. M. R. Gajendragad and U. Agarwala, Z. anorg. Chem., 1975,415, 84. W. Levason. C. A. McAuliffe, and S. G. Murray, J.C.S. Dalton, 1975, 1566. D. Brown, B. Whittaker, and J. Tacon, J.C.S. Dalton, 1975, 34.

286

Spectroscopic Properties of Inorganic and Organometallic Compounds

(3)

which seem to be the same for any metal complex (independent of metal, coordination number, and protonation of the ligand itself),89and G(X2nX) values which are purported to be only 4-23 cm-l below corresponding v(ZnX) in some EtCONH, adducts (X = CI or NCS).82 However, many acceptable assignments have been made, and the spectrastructure correlations are now so well established that credence can be given to the conclusions drawn. For example, the tetrahedral/octahedral and terminal/ bridged games have again been played, this time with metal halide complexes of 2-imino-4-oxo-1,3-thia~olidine,~~ 8-quinolinecarboxamide,ss 2-acet~lpyridine,~~ 2-amin0methyIpyridine,~~ and acridine N - o ~ i d e .The ~ ~ erroneous assignments for [MX,(pyrazine),] (M = Co or Ni; X = C1 or Br), noted in last year's Report, have now (finally ?) been laid to Trends in the positions of v(ML) bands, as the metal is changed in a series, have been noted and generally attributed to ligand-field effects: e.g.

Ni Ni Ni Cu

> Co > Cu > Co > Cu > Zn > Co > Cu z Zn > Ni > C o S Z n

for v(M-tpp);,l

for ~ ( M - h f a ) ; ~ ~ for ~(M-tfffa);~~ for v(M-py)

(tpp = tetraphenylporphin; hfa = hexafluoroacetylacetone; ttfaH = 2-thenoyltrifluoroacetone; py = pyridine or 4-methylpyridine). The difference in the two sequences of ref. 85 was attributed to a Jahn-Teller effect in complexes [M(ttfa),(py),]. Linear correlations have been found 93 between M - 0 distances of [M(acac),] complexes and three far4.r. band series; these bands are those which have previously been shown to undergo the largest metal isotopic shifts. For the [MC1J2- ions present in melts of MCI, with alkali-metal chlorides (M = Mn, Co, Ni, Cu, or Zn), v1 is said to correlate with thermodynamic properties of the species.94 Of all the studies listed in Table 8, only two are of real spectroscopic interest (apart from the metal isotope studies), uiz. the detailed investigation of M[Pt(CN),] complexesS and the discussion of [M(en),],+ (M = Cr or CO).'~ In the tris(ethy1enediamine) compounds, studies of electronic spectral data suggest that in each case the vibration responsible for the 280-320cm-1 absorption has at least as much M-N stretching character as that for the 450600cm-l band, despite three reports of Raman studies asserting that the latter is chiefly vaYm(MN)while the former is 8,,,(NMN). A similar situation obtained for bis(ethy1enediamine) complexes of these metals. Differences between the [M(NH3)J3+ and [M(en),I3+ systems are attributed mainly to strong coupling between the M-N modes and internal modes of the en groups.73 O2

O3 0'

M. Goldstein, J. Znorg. Nuclear Chem., 1975, 37, 567. P. Fackler, jun., Inorg. Chem., 1975,14, 2002. K. B. Yatsimirskii, S. V. Volkov, N. P. Evtushenko, and N. 1. Buryak, Fiz. Mar. Merody Koord. Khim., Tczisy Doklady, Vses. Soveshch., Sth, 1974, 32. A. Avdeefand J.

287 Finally are mentioned two reviews which include useful compilations of vibrational spectroscopic data relevant to this Report, i.e. cyanide complexes of the early transition metals D5 and transition-metal complexes of thiosemicarbazide and thiosemicarbazones.ss Vibrational Spectra of Transition-element Cornpounds

3 Scandium and Yttrium 1.r. assignments have been reported for Sc(OH)(S0,),2H2O [v(Sc-0SO3) = 268 ~ m - ~ ] ,a@range ~ of complexes of type ScX3,n(2,6-dimethyl-4-pyrone) [n = 3 (X = SCN), 4 (X = C1 or NO3), or 6 (X = Br, I, SCN, or ClO,); v(Sc0) questionably in the very narrow range 358-363 ~ m - ~ ] and , ~ * KBYF6 [tl, v(YF) = 400 ~ r n - ~ ] . ~ ~

4 Titanium, Zirconium, and Hafnium The most striking aspect to emerge from an i.r. and Raman spectral study (including NCA) of Hf(BH4), was that the intensity of the breathing mode at 552 cm-l (510 cm-l in perdeuteriate), when analysed in terms of bond polarizability derivatives, showed that Hf ...B bonding may be responsible for as much as 25% of the Hf-ligand bondingB Values of v(TiC) were reported last year for [(Me,SiCH,),TiCl,-,] (500 cm-l, n = 1 or 2),loo[(r-pentenyl),Ti] (420 and 465 cm-l),lol and [(Cp)TiX,(S,CNR,)] complexes (R = Me or Et; X = C1 or Br; ca. 340 and ca. 420 cm-l).lo2 Unassigned i.r. data have been given for [(Cp),TiCl,] and [(Cp)TiCl,] species attached to polystyrene,lo3and [(C,H,),Ti] matrix-isolated at 20 K in Ar.lo4 The observation of v(TiN) at 346 cm-l for [Ti(NCS),],- in MeCN solution lo6 affords some support for the assignment of such vibrations in [Ti(RCOCHCOR),(NCX),] [e.g. 361,377 cm-l (X = S) or 405, 428 cm-l (X = 0) for R = Me].lo0 Similarly, there is a measure of consistency about the v(TiN) assignments for [(Me2N),Ti(CSH4R)] (R = H, Et, But, SiMe,Ph, etc.; ca. 560 and ca. 570 cm-l) lo' and [Ti(NMeSi,Me,NMe),] (510 and 538 cm-l).lo8 The quality of published works on oxo-compounds of these elements is remarkably varied. For example, a thorough Raman study has been made of 96

O7

n8

nB

W. P. Griffith, Coordination Chem. Rev., 1975, 17, 177. M. J. M. Campbell, Coordination Chem. Rev., 1975, 15, 279. L. N . Komissarova, V. F. Chuvaev, V. M. Shatskii, B. 1. Bashkov, A. M. Grevtsev, and E. G . Teterin, Russ. J. Inorg. Cheni., 1974, 19, 1423. F. Kuter and B. Dusek, Rum. J . Inorg. Chem., 1974, 19, 1289. L. P. Reshetnikova, 1. B. Shaimuradov, V. A. Efremov, and A. V. Novoselova, Russ. J. Inorg.

Chem., 1974, 19, 647. S. I . Beilin, G. N . Bondarenko, V. M . Vdovin, B. A. Dolgoplosk, I. N . Markevich, N. S. Nametkin, V. A. Poletaev, V. I. Svergum, and M. B. Sergeeva, Doklady Chem., 1975,218,718. lol 0 . N . Yakovleva, 0. K. Sharaev, K. G. Miesserov, T. K. Vydrina, G . N . Bondarenko, E. 1. Tinyakova, and B. A. Dolgoplosk, Doklady Chem., 1975, 218, 664. l o a R. S. P. Coutts and P. C. Wailes, J . Organometallic Chem., 1975, 84, 47. lo3 W. D. Bonds, C. H. Brubaker, E. S. Chandrasekaran, C. Gibbons, R. H. Grubbs, and L. C. Kroll, J . Amer. Chem. SOC.,1975, 97, 2128. lo' M. T. Anthony, M. L. H. Green, and D . Young, 3.C.S. Dalton, 1975, 1419. l o b A. M. Sych and D. G . Bogatyr', Russ. J . Inorg. Chem., 1974, 19, 1470. l o 8 A. F. Lindmark and R. C. Fay, Inorg. Chem., 1975,14,282. l o ) H. Burger and U. Dammgen, J . Organometallic Chem., 1975, 101, 295. log H. Burger, K. Wiegel, U. Thewalt, and D. Schomburg, J . Organometallic Chem., 1975, 87, 301.

loo

288 Spectroscopic. Properties of ltiorgatiic atid Organometullic Conipoiriids the long-wavelength optical phonons of H f 0 2 and ZrO,, and temperature arid uniaxial stress measurenients have been discussed ;lee the sensitivity of v(Ti0) modes in T i 0 2 to changes in the structure of thc surface occurring on adsorption of water molecules has been carefully On a slightly more superficial level, the i.r. and Raman spectra of lanthanoid zirconates and hafnates with the pyrochlore structure, LnM20,, have been shown to be consistent with factorgroup predictions, and the band positions correlate with the unit cell size."' A most unsatisfactory position still obtains, however, regarding assignment of v(M0) for complex compounds of these elements; for the record, the following have been ascribed M - 0 - M bridged structures on the basis of supposed v(M0) band positions : [TiO(o-OC,H,CH= N- CHR1CHR2N=CHCEH,0-o),HX] (R' or R2 = H, Me, etc.; X = C1, C104,or OMe; 800-820 cm-1),112[Ti,o,,(NCS),(chel),], [Ti,O(NCS),(RCOCHCOR>,], and (Et,N),[TiO(NCS),] (chel = phen or bipy; R = Me or Ph; 630-770 c ~ I - ~and ) , [M,O(OH),(arnygdalate),] ~ ~ ~ [M = Zr (740) or Hf (755 C M - ~ ) ] . " Other ~ data on v(Zr0) and v(Hf0) are in refs. 91 and 115. The actual nature of the motion being assigned in most of these cases is notably vague, and the arguments (when presented) are usually subjective, but a paper on the spectra of a series of hafnium sulphates and oxide sulphates is incredibly woolly even on what is being assigned, let alone on the evidence and description.l16 An interesting comparison can be made of two Ti-0-Si systems studied last year. Vitreous Si02 glasses containing Ti show i.r. bands at 940cm-I which are described as vBBlnl(SiO)of terminal silicate groups [vawm(Ti04)at 735 ~ m - ' ] . ~However, ~~ bands in similar positions in spectra of [(Cp),TiCI(OSiMe,Ph,-,)] and [(Cp)Ti(OSiMe,Ph,-,),] (n = 0 - 3 ; 945-951 and 910915 cm-l, respectively) are said to be v(Ti-O-Si).118 1.r. spectroscopy has been used in the characterization of ( a ) Ti(OH)PO, and Ti(HPOq)2,H20,11g(6) H2Ti03,H20, H2[Ti(103)E],2H20,and H,[Ti(OH),(I03)2],H20,120 (c) BaTiO(C20,),4H20, Ba,Ti,O,(CO,)(CO,), and Ba2Ti206and ( d ) the systems MO-AI2O3-TiO2-SiO2 (M = Ba or Cr).122 When Li3TiS, is formed from action of BunLi on TiS,, the polysulphide i.r. mode of the latter (560 cm-l) disappears, and the presence of only two i.r. bands, log E.Anastassakis, 13. Papanicolaou, and 1. M. Asher, J. Phys. and Chem. Solids, 1975, 36, 667. 110

111

11*

Yu. A. Zarif'yants, V. F. Kiselcv, and S. V. Khrustaleva, Suyuzannayu Voda Dispersnykh Sist., 1974, 3, 74. N. V. Gundovin, F. M. Spiridonov, L. N. Komissarova, and K. I. Petrov, Russ. J. Inorg. Cheni., 1975, 20, 325. M. Gullotti and A. Pasini, Inorg. Chin?.Acta, 1975. 15, 129.

J. Sala-Pala and J. E. Guerchais, Z . anorg. Chem., 1975, 412,

llJ

281.

K. F. Karlysheva, A. V. Koshel', I. A. Sheka, and G. S. Semenova, Russ. J. Inorg. Cheni., 1975, 20, 521.

N.S. Biradar and A. L. Locker, J. Inorg. Nuclear Chem., 1975, 37, 1308. M. M. Godnevai, R. F. Okhrimenko, D. L. Motov, R . A. Popova, and S. A. Kobycheva,

l1& 118

'17 119

jZo

IZ1

Russ. J. Inorg. Chmi., 1975, 20,491. C. F. Smith, jun., R. A. Condrate, sen., and W. E. Votava, Applied Specfroscopy, 1975,29,79. H . Suzuki and T. Takiguchi, Bull. Chem. Soc. Japan, 1975, 48, 2460. V. V. Pechkovskii, E. D . Dzyuba, G . I . Salonets, V. N. Yaglov, and A . I. Volkov, Russ. J. Inorg. Cheni., 1975, 20, 329. T. G. Ralicheva, G . A. Petrova, and L. A . Doronina, Koord. Khim., 1975, 1, 457. H . S. Gopalakrishnamurthy, M . S. Rao, and T. R. N. Kutty, J. Inorg. Nuclear Chem., 1975, 31, 89 1.

N.M.Bobkova, L. M. Silich, and L. K. Aksenovich, Steklo, Sitally i silil,PX,] ~l (X = 0 or S, n = 0 or 1) and [{ Mn(C0)3(C5H4))3PMe]I,252 and [{ Mn(CO),(C,H,)),SnR,] (n = 4, in = 0; n = 2, rn = 2; R = Ph or C5H5FeC5H4).253 Compounds for which v(MnN) has been assigned are listed in Table 1 or Table 8.7G v(MnP) = 213 and v(MnAs) = For [(F,C),EMn(CO),] (E = P or 188 cm-l. Values quoted 87 for v(MnS) in [Mn{S,CNH(CH,),NHCS,)] (n = 2 or 6) are ca. 360 cm-I. 243

244

24(8

04’

fa 248

2G1 252 *5.1

p64

I. D. MacLeod, D. Millington, A. Prescott, and D. W. A. Sharp, Inorg. Nuclear Chenz. Letters, 1975, 11, 447. A. Prescott, D. W. A. Sharp, and J. M. Winfield, J.C.S. Dalton, 1975, 934. A. Prescott, D. W. A. Sharp, and J. M. Winfield, J.C.S. Dalton, 1975, 936. K. Mertis, D. H. Williamson, and G. Wilkinson, J.C.S. Dalton, 1975, 607. K. Tanaka, Y. Miya-Uchi, and T. Tanaka, Inorg. Chcm., 1975, 14, 1545. V. N. Setkina, N. I. Pyshnograeva, P. V. Petrovskii, N. E. Kolobova, and D. N. Kursanov, Doklady Clrcm., 1975, 220, 29. J. Grobe and R. Rau, Z. anorg. Chcm., 1975. 414, 19. S. I. Beilin, 1. N. Markevich, S. €3. Gol’shtein, G. N. Bondarenko, and B. A. Dolgoplosk, Doklady Chem., 1975, 218, 671. C. H. Game, M. Green, and F. G. A. Stone, J.C.S. Daf?on, 1975, 2280. A. N. Nesmeyanov, K. N. Ankimov, and %. P. Valueva, Doklady Cheni., 1974. 216, 304. A. N. Nesmeyanov, T. P. Tolstaya, V. V. Korol’kov, a n d A. N. Yarkevich, Dohlarly Chctn., 1975, 221, 267. R. Demuth, J. Grobe, and R. Rau, Z . Naturforsch., 1975, 30b, 539.

300

Spcctroscopic Properties of Inorganic and Organometallic Compounds

As expected, v(M0) and 6(MO) for (Me,N),[MO,] (M = Mn, Tc, or Re) are some l00cm-' lower than in the MV" analogues.266 Unidentate [ReO,]in [Cu(chel)(ReO,)] [chelH = (HONCMeCMe,NHCH,),CH, ; v(Re0) = 898, 902, 908, and 922 cm-l] has been demonstrated crystallographically.266 1.r. data have been given for Ln(TcO,),,nH,O (Ln = La, Ce, Sm, Eu, Tm, or Yb; = 0-4).257-%1 Different v(Re=O) values are shown by the green (988) and violet (968 cm-l) isomers of [ReO(bipy)C13].260The presence of two v(Re=O) bands in the i.r. spectrum of [Re,O,(CH,SiMe,),] (990, 1008 cm-l) points towards the linearbridged structure 0

K\ II

0

Re-0-Re

It /K

K

R

'R

1

(10)

I \K

ring 0 system is found at ca. 650cm-' in [Mn,O,(chel),],nH,O (n = 1 or 2; chelH, = quadridentate Schiff base),261while for a new series of six Mn1"*I V complexes, bridge modes are given at ca. 580, ca. 650, and ca. 690 cm-l. Assignments for v(Mn0) are also available for MMn(IO,), (ca. 525 cm-l, M = Mg, Sr, or Na2),263 [MnX(acac),] (343 cm-l, X = C1, Br, or I),264 and for three series of complexes listed in Table 8.'O* Oxyhalogeno-anions of Re studied last year include [RezOCllo]4-(calculation shows strong vibrational mixing),l8 [ReOC15]- salts [splitting of v(Re0) at 900-968 cm-l attributed to site symmetry effect!],266and [ReOFJ- (from partial hydrolysis of ReF, in aqueous H F ; Cav):20 An i.r. band said to be associated with a vibration of the

v/cm-l: v/cni-l :

700

590

370

330

298

233

v7

5'4

vtl

v6

1008

736

V1

v2

387 v10

v8

v6

575 v3

Metal-halogen modes have been assigned in a very wide range of Mn and Re compounds: ( a ) ReF, (solid at 23 "C) and ReF, [melt and film (- 196 "C); a broad i.r. band at cu. 530 cm-I, attributed to v(ReF)b, is indicative of a polymeric L. Astheimer, J. Ilauk, H. J. Schenk, and K. Schwochau. J . Chem. Phys., 1975, 63, I. B. Liss and E. 0. Schlemper, Znorg. Chem., 1975, 14, 3035. 267 L. L. Zaitseva, M. I. Konarev, A. V. Velichko, A. I. Sukhikh, and N. T. Chebotarev, Inorg. Chem., 1974, 19, 1285. 2SR L. L. Zaitseva, M. I. Konarev, A. V. Velichko, A. I. Sukhikh, and N. T. Chebotarev, Inorg. Chem., 1974, 19, 1461. 2G9 L. L. Zaitseva, M. I. Konarev, A. V. Velichko, A. I. Sukhikh, and N. T. Chebotarev, Inorg. Cheni., 1974, 19, 1625. 2flo M. C. Chakravorti, J . Znorg. Nuclear Chem., 1975, 37, 1991. 261 L. J. Boucher and C. G. Coe, Inorg. Cheni., 1975, 14, 1289. 2e2 R. U s h , V. Riera, and M. Laguna, Transition Metal Chem., 1975, 1,21. 2 ~ 3 A. V. Melezhik and V. L. Pavlov, Rum. J. Znorg. Chem., 1975, 20, 532. K. Isobe and S. Kawaguchi, Bull. Chem. SOC.Japan, 1975, 48, 250. 3eL V. Yatirajam and H. Singh, J. Inorg. Nuclear Chem., 1975, 37,2007.

1988.

Russ. J .

Rum. J. Russ. J .

Vibrational Spectra of Transition-element Compoittids

301 (6) MnC1,-KCI melts (see Chapter 4),267 ( c ) Re,CI, (resonance Ranian study of matrix-isolated species: see Section 2),s2( d ) (py,H)[MnBr,(py),], the formulation proposed for the 1 : 5 adduct of py with HMnBr, [v(MnBr) = 118, 124; v(NH) = 3200 ~ r n - ~ ] (e) , ~ ~[Re,CIn(PR,)8-n] * (n = 4, 5 , or 6; PR3 = PEt,, PhPMe,, etc.), (Et3PCl)2[Re,C14Br21,Re2C14Br2(PEt3)B, e t ~ . (f) , ~ [~MnX(acac),], the spectra of which are very similar to that of [FeCl(acac),], a complex known to be square pyramidal with the halogen atom ( g ) MnX(Pc2-) [(Pc2-) = phthalocyanine dianion; v(MnX) = 269 (CI) or 211 cm-' (Br)],,O ( / I ) [ReCl,(PhN,)(PMe,Ph),(L)], [ReCI,(PhN,H)(PMe,Ph),(NH,)]X, etc. (L = NH,, PMe,Ph, PEt,Ph, or CO; X = C1 or Br),268( i ) [ReX,(Ph2PC2H,PPh2)] (j)fac-[M(CO),ClL] (M = Mn or Re; L = phen, and [ReX3(Ph,PC2H4PPh,)],270 1,s-naphthyridine, or methyl derivative of these),," (k) [M(CO),XL,] [V(MX)~ = 186 (M = Mn, X = Br), 156 (M = Mn, X = I), or 188cm-' (M = Re, X = Br)] and [Re2(CO)6X2L][v(MX)b = 237, 283 (X = Cl) or 149, 161 cm-l (X = Br)], where L is O - ( C N ) , C ~ H and ~,~~ (I)~ [Re(CO),X,]-, the presence of two v(ReX) i.r. bands (X = C1 or Br) being consistent with cis Compounds of these elements feature prominently in Table 7, where metal32* 67 metal vibrations are 51-539

8 Iron, Ruthenium, and Osmium Compounds for which v(MH) assignments involving these elements have been made are as follows : ( a ) [FeH(CO)I(PMe3)3],274 (b) [HFeCH,PMe,(PMe,),], the product of the first established intramolecular CH addition in a trialkyl ] , ~the ~ ~ reaction mixture from metal complex, (1 1),275(c) [ R U H ( C O ) ~ I ( P P ~ , ) ,(d) Me M e \ /

+

( 1 1)

[RuH,(PPh3),] HBr,," ( e ) [MH(OCOCF3)(Ph3P),] and [OsH(OCOR)(CO),(Ph3P)4--n](M = Ru or Os, R = CF3 or C2FS,n = 1 or 2),278 (f)[MH(CO),(NNPh)(Ph,P),] and deuteriates (M = Rii or Os, n = 1 or 2),27'3( g ) [MH(S,CNR,)(CO)(Ph,P),] and [MH(S,COR)(CO)(Ph,P),] (M = Ru or Os, 2Ro 2G7

270 271 a7a

273 274 276

277

279

R. T. Paine and L. B. Asprey, Inorg. Chem., 1975, 14, 1 1 1 1 . K. Tanemoto and T. Nakamura, Cheni. Letters, 1975, 351. E. Lehmann, J. Kouinis, and A. Galois, Monatsh., 1975, 106, 499. P. G. Douglas, A. R. Galbraith, and B. L. Shaw, Transition Metal Chem., 1975, 1, 17. J. A. Jaecker, D . P. Murtha, and R. A. Walton, Inorg. Chin). Acta, 1975, 13, 21. J. R. Wagner and D . G. Hendricker, J. Inorg. Nuclear Chent., 1975, 37, 1375. J. G. Dunn and D . A. Edwards, J . Organometallic Cheni., 1975, 102, 199. R. Colton and J. E. Garrard, Austral. J . Chem., 1975, 28, 1923. M. Pankowski, E. Samuel, and M . Bigorgne, J . Orgaiiometallic Chem., 1975, 97, 105. J . W. Rathke and E. L. Muetterties, f. Amer. Chem. SOC.,1975, 97, 3272. E. F. Magoon, H . C. Volger, W. W. Spooncer, J. L. Van Winkle, and L. H. Slaugh, J . Organometallic Chem., 1975, 99, 135. P. R. Hoffman and K . G. Caulton, J . Amer. Chenr. Soc., 1975, 97, 4221. A. Dobson, S. D. Robinson, and M. F. Uttley, J.C.S. Dalton, 1975, 370. B. L. Haymore and J . A. lbers, Inorg. Chem., 1975, 14, 2784.

302 Spectroscopic Properties of Itiorganic and Organometallic Compounds R = Me or Et),280(h) (Pol)-CC,H4SnBun,0sH(CO),, where (Pol) is a polymer residue,281(i) [OsH(OCOR),(NO)(Ph3P),1 (R = CF3 or C2F6),282 ( j ) [Fe,H3(MeC(CH,PPh,)3)2]PF6,1+CH2Clz, for which v(FeH) at 1048 cm-1 (shifts to 790cm-l on deuteriation) is consistent with bridging H atoms as inferred by a single-crystal X-ray (k) (Ph4As)[R~4H3(CO)l,],284 ( I ) [RU~H~(CO)~,] and d e ~ l t e r i a t e , and ~ ~ ~ (m) [H,Os,(CO),,] and deuteriate [v(OsH)b = 1930, v(0sH)b = 1525 cm-1].28s 1.r. and Raman data obtained for decamethylferricenium (MeloFc+), 1,l ’-dimethylferriceniuni (Me,Fc+), and 1,l ’-trimethyleneferricenium (C3HeFct) cations include the following data for [PF,]- salts :287 v,,,(Fe-ring) ‘Ring torsion’ Sym ring tilt

Fc+ 304

Me2Fc+ 327 242

C&Fc+ 316 218

Me,Fc+ 173 369 cm-I

1.r. data are also available for the parent ferrocene derivatives Me,Fc, C,H,Fc, and M ~ , F C , ~biferrocenylene ~’ and its cationic complexes of M ~ , N C H , F C ,and ~ ~ HO,CCH,C(OH)P~FC.~*~ Metal-olefin assignments have been given for [(C,Ha)Fe(CO),] (250, B2; 301 cm-l, A,) 290 and [(C,H,,)Ru(glycinato),] (388-595 cm-1).2B1 There has been some controversy in the literature regarding which of the i.r. bands of [Fe(CO),] at 474 and 431 cm-l (gas-phase values) is the A,” v(FeC) mode and which is the E’ counterpart. A matrix-isolation study has now been carried out in this spectral region in an attempt to resolve the issue.41 Unfortunately, the study illustrates only too well the difficulties that may arise in matrix studies, but the authors favour the original interpretation: 474 (A2”) 431 cm-’ ( E ) ,rather than that more recently put forward (solid-state values: 480, 434 cm-l, respectively). It is interesting to compare this paper with a study of [64Fe(CO)5],in which v ( ~ ~ F ~ - ~shifts * F ~were ) calculated for three different force fields (with different assignments), but unhappily all were overall i n reasonable agreement with the experimental data.31 A thorough study of the i.r. and Raman spectra of [F~(CO),PBU~~(EM~~),-,J (n = 0 - 3 ; E = Si, Ge, or Sn) has led to the suggestion that the structures are P. B. Critchlow and S. D . Robinson, J.C.S. Dalton, 1975, 1367. J. M. Burlitch and R. C. Winterton, J. Amer. Chem. SOC.,1975, 97, 5605. 282 A. Dobson and S. D. Robinson, J . Organometallic Chem., 1975, 99, C63. 983 P. Dapporto, S. Midollini, and L. Sacconi, Znorg. Chem., 1975, 14, 1643. 2 8 4 J. W. Koepke, J. R. Johnson, S. A. R . Knox, and 13. D . Kaesz, J. Amer. Chem. SOC.,1975,97, 3947. 28b S. A. R. Knox, J. W. Koepke, M. A. Andrews, and H. D. Kaesz, J. Amer. Chem. SOC.,1975, 97,3942. IRR J. R. Shapley, J. B. Keister, M. R. Churchill, and B. G . D e Boer, J. Amer. Chem. Suc., 1975, 97,4145. IH7 D. M. Duggan and D. N. Hendrickson, Znorg. Chem., 1975, 14, 955. 2 8 8 W. H. Morrison,jun. and D . N. Hendrickson, 1nor.q. Chem., 1975,14,2331. A. N. Nesmeyanov, B. A. Surkov, V. A. Sazonova, and T. A. Zaimovskaya, Doklady Chem., 1975, 219, 812. 1. A. Zakharova, Ya. V. Salyn, 1. A. Garhouzova, V. T. Aleksanyan, and M. A. Prianichnicova, J . Organometallic Chem., 1975, 102,227. m 1 C. Potvin, L. Davignon, and G. Pannetier, B d . SOC.chim. France, 1975, 507.

Vibrational Spectra of Tratisition-elenlent Conipoiinds

303

trigonal bipyramidal, with the phosphine in the unusual axial position.292 A fairly full (but confined to solid-state i.r.) investigation has also been made of cis- and trans-isomers of (Bun4N)n[OsX4(CO)2] salts, for which the following data (wavenumbers/cm-l) are typical 294 :2a39

E7A

A2u

v(C0) frans-[OsBr,(CO),]-

2045 1920

frans-[OsBr,(C0),I2-

V(C0) A,

cis-[OsBr,(CO),]-

2025 ~is-[OsBr,(C0),]~- 2005

B2 1948 1910

v(0sC) 309 348

~(OSCO) v(0sBr)

v(0sC) B2 527 511 537 527 A,

594 623

225 212

8( 0 s CO) B1 B2 583 640 598 590 648 603 A,

Less detailed results arc available for compounds such as [TI{Fe(CO),(NO)L},], [T1Fe(CO)3(L)SnPh,], and [TlFe(CO),CN] [L = PR3 or P(OR),; 11 = 1 or 3],295 the first cationic q2-cyclobutadiene complex, [Cp(C0)2Fe(C4H4)]PF6,z96 KJRu(CN)4(N2H4),],2H,0,297 and K3[Fe(CN)6] under high pressures.2u8 An interesting collection of papers on nitrosyls of Ru or 0 s has appeared from the same l a b o r a t ~ r y . ~A~ ~paper - ~ ~ on ~ [Ru(NO)XJ2- species (X = CI, Br, or I) adds nothing to work reported much earlier (M. J. Cleare et al., Spectroclrirn. Actn, 1972, 28A, 2013);,'O assignments for v(Ru-NH,) and ~(Ru-NO) in ~~~~S-[RU(NO)(NH~)~(NCS)](NCS), are given without evidence;30*i.r. band intensities are discussed for [Ru(NO)CI,(N H3)5--n](3-n)+ (n = 0-5);"' ~(OSN) is always between 570 and 630 cm-l for [Os(NO)XJ2- salts (X = CI, Br, or I).302 Other compounds for which v(MN) data are available include the N=MX3L, complexes given in Table 2,29the ammines in Table 1,' several complexes listed in Table 6 39 and Table SY3* 78 [Fe(chel)X,]ClO, [chel = a quinquedentate macrocyclic amino-compound; v(FeX) = 338 (X = NCS) or cn. 400cm-l (X = N3)],303and RU,NX~(H,O)~ [X = C1 or Br; vaspm(Ru2N)= 1050--1080, V,,~(RU,N)= 392-402 cm-l; NCA perf0rmed1.l~ Unassigned data have been vaguely discussed for [ O ~ B r , ( e n ) ] . ~ ~ ~ For [Fe(C0),(PBut3),(EMe,),-,] (12 = 0-3; E = Si, G e , or Sn), v(FeP) may be in the 150-185 cm-l range.*92 039

2112

203 2B6 206

287

29* 208

76p

H. Schumann, L. Rosch, H. J. Kroth, H. Neurnann, and B. Neudert, Chem. Ber., 1975, 108, 2487.

W. Preetz and F. H. Johannsen, J. Organonletallic Chem., 1975, 86, 397. F. H. Johannsen, W. Preetz, and A. ScheWer, J . OrganometalIic Chem., 1975, 102, 527. S. E. Pedersen and W. R. Robinson, Inorg. Chem., 1975, 14, 2365. A. Sanders and W. P. Giering, J. Amer. Chem. SOC.,1975, 97, 921. L. I. Pavlenko, A. P. Okorskaya, and A. N. Sergeeva, Russ. J. Inorg. Chem., 1975, 20, 460. Y. Hara, I. Shirotani, and S. Minomura, Inorg. Chem., 1975,14, 1834. A. B. Nikol'skii, N. V. Ivanova, I. V. Vasilevskii, and S. M. Nikiforov, Rum. J . Inorg. Chem., 1974, 19, 1370.

300

$01 802

303 804

N. M. Sinitsyn, V. V. Borisov, and L. A. Pshenichnikova, Russ. J. Inorg. Chem., 1974, 19,

1667. 0. V. Sizova, N. V. Ivanova, V. I. Baranovskii, and A. €3. Nikol'skii, Koord. K / J ~ 1975, ., 1,

810. V. V. Kravchenko, V. F. Travkin, and N. M. Sinitsyn, Koord. Khim., 1975, 1, 930. M. G. B. Drew, A. H. Othman, P. D. A. McIlroy, and S. M. Nelson, J.C.S. Dalton, 1975, 2507.

M. A. Bolourtschi, H.-J. Deiseroth, and W. Preeti, %. attorg. Chem., 1975, 415, 2 5 .

304

Spectroscopic Properties of Itiorganic arid Organoinetailic Contpouncls

'The detailed studies carried out on KOs0,N were mentioned in Section 2; compared with OsO,, there is considerable reduction in the 0 s - 0 force constant (from 8.32 to 6.79 mdyn A-l) with strong 0s-N bondi11g.l~ The spectra of OsO,,py and deuteriate are suggestive of C , , or C, skeletal symmetry; a band at 204 cm-' is thought to be v(OSN).~O~ Diiners Os&,4py and Os2O8,2bipy are thought to have306 vss,,(OsO)t = 870, v,8y,(OsO)t = ca. 830, with v ( O s 0 ) ~= ca. 590, ca. 640cm-l. Consistent with this is the assignment of v,,,,,(OsO2) at 828-839 cm-' in some 0x0-osmium(v1) nucleoside sugar Assignments of v(Fe0Fe) noted during 1975 are moderately consistent: 870 cm-l in [(D20),FeOFe(OD2),]~+(believed to be formed on hydrolysis i n D 2 0 of FeX, species),3o*757 and 81 1 cm-l in [(chel),Fe20], where chel is a porphyrin-type m a c r o ~ y c l eand , ~ ~ 720 ~ cm-l in Fe,O(NO,),, the same band being stated to be present also in Fe203 and FeON03.310 The FeOFe angle would be an important factor in determining the band position. 1.r. data are now available for five lanthanoid o r t h o f e r r i t e ~ ,Gd ~ ~ ~and Y and phosphorus(rr1) oxoacid salts such as Fe2(HP03),,9H,0, Fe4H33P16045,6H20,etc.313 Values for v(Fe0) in six-co-ordinate Fe"' complexes of 0x0-ligands vary from 280 to 375 cm-l for [Fe(4-RC5H4N0)6](C104).L (R = v a r i o u ~ )315 , ~ ~to~ 410, ~ 431 cm-' for [Fe(Me2SO)8](C10,),.315 See also Table 8.23p81

-

For [(CH2CH2XCH2CH2NCS2)*FeY] (X = NMe, CH2, S , or 0; Y = C1, Br, or I), v(FeS) has been given, without evidence, as being in the 3 5 s 370 cm-l range.316 Compounds for which v(MX) assignments have been made are given in Table 16-11,18, 22, 29, 30, 78, 81, 268, 279, 299, 301-303, 309, 818-333 Many of the data arising a 0s 8110

807

aon JOB

810

A. B. Nikol'skii and Yu. 1. D'yachenko, Rum. J . Inorg. Chem., 1974, 19, 1031. A. B. Nikol'skii, Yu. I. D'yachenko, and L. A. Myund, Russ. J. Inorg. Chcttr., 1974, 19, 1368. F. B. Daniel and E. J. Behrman, J. Amcr. Cfictn. SOC.,1975, 97, 7352. J. M. Knudsen, E. Larsen, J. E. Moreira, and 0. F. Nielsen, Acta Chem. Scatid ( A ) , 1975,29, 833.

J. W. Buchler and K. L. Lay, Z. Natut-forscfi.,1975, 30b, 385. C. C. Addison, P. G. Harrison, N. Logan, L. Blackwell, and D. H. Jones, J.C.S. Dalfon, 1975,

830.

Y11

31s

513 814

YIG Y10

317

sin Y1S

320

$21

azz 323 Y24 926 1)28

827

T. B. Smith, J. Yamamoto, and E. E. Bell, J . Opt. Soc. Amer., 1975, 65, 605. E. L. Smirnova, E. F. Efes, Yu. N. Volgin, and Yu. I. Ukhanov, Poluprouoriti. Elekfron., 1974, 1,45.

M. Ebert and L. Kavan, Monatsh., 1975, 106, 1499. Y. Maeda, Y. Sasaki, and Y. Takashima, Inorg. v(UCl,),, (b2u) > v(UCl&,a (bSu)> V ( U C ~ (63u)],568 ~ ) ~ ~ ( e ) [(indenyl),AnX] [An = Th or U ; X = C1 or Br; v(AnC1) = ca. 270, v(AnBr) = ca. 180 ~ m - ~ ] , and ~~' (f)uranium(1v) poly(pyrazol-l-yl)borate.570 684 686

SEE S67 688

670

S. P. Tandon and P. P. Vaishnava, ref. 536, p. 511. K. W. Bagnall, A. M. Bhandari, D. Brown, P. E. Lidster, and B. Whittaker, J.C.S. Dalton, 1975, 1249. R. Oyamada and S. Yoshida, J . Phys. SOC. Japan, 1975, 38, 1786. W. Von der Ohe, Diss. Abs. Internat. ( B ) , 1975, 35, 4601. W. Kolitsch and U. Muller, Z . anorg. Chcm., 1975, 418, 235. J. Groffart, J. Fuger, B. Gilbert, L. Hocks, and G . Duyckaerts, Znorg. Nuclear Chem. Letters, 1975, 11, 569. K, W. Bagnall, J. Edwards, J. G . H. du Preez, and R. F. Warren, J.C.S. Dalton, 1975, 140.

7

Vibrational Spectra of some Co-ordinated Ligands ~

BY

G. DAVIDSON ~~~~

The arrangement of this chapter follows the pattern set in previous years and, as before, each paper is referred to only once. Thus it will be necessary for a reader interested in a complex containing several ligands to check through all of the sections in which it might be mentioned.

1 Carbon Donors The theory has been presented for the activity of electronic Raman transitions between electronic states arising from the ground electronic configuration of some sandwich compounds containing transition meta1s.l Only a few such systems seem to be candidates for significant development of the effect. v(C=O) in the metallo-esters [Me,C( M)CO,Et] is assigned as follows: M =: Li, 1689; Na, 1663; K, 1651 ; and Cs, 1647 cm-I, conipared to the value for the free ester of 1736 c171-l.~ The characteristic i.r. bands of Cp in [(OC),CrC(OTiCp,Cl>X] (X = NMe, or Ph) are in almost the same positions as in [Cp,TiCI,] and [Cp,Ti(a~ac)]+.~ Thus there is very little dependence upon the nature of other groups attached to the Ti. [(/z6-C6H,)(h4-C4H6)(/z3-l -MeC,H,)Ti] gives i.r. bands in the characteristic regions for all three l i g a n d ~ . ~ [(Indenyl)Ti(C,H,)] shows no bands due to unco-ordinated C=C, therefore suggesting that the CBHB is co-ordinated i n the .rr-complex by using all four double bonds.6 [MCI,{C(CI)=NBut}(CNBut)l, (M = Ti or Hf), [M{C(CI)=NMe),] (M = Ti, Zr, or Hf), and [VCl{C(Cl)=NMe},] all give v(N=C) between 1620 and 1650 cm-1.6 1.r. data, together with those from n.m.r. spectra, indicate that Zr and Hf ally1 complexes can be grouped into six types: n-,u-, and a/n-, and, for each of these, ‘dynamic’ or ‘static’, these being differentiated by n.1n.r. parameters. Thus [Zr(allyl),] is n-dynamic in toluene at 0 “C but n-static at -80 “C, [(cot)Zr(methylallyl),l is a-dynamic in toluene at 35 “C, [(~ot)Hf(allyl)~] is

IJ

B. F. GBchter, T. Parameswaran, and J. A. Koningstein, J . Mof. Spectroscopy, 1975, 54, 215. L. Lochmann and J. Trekoval, J . Organonietullir Chem., 1975, 99, 329. H . G . Raubenheimer and E. 0. Fischer, J . Orgnnotiwtallic Chem., 1975, 91, C23. A. Zwijnenburg, H . 0. van Oven, C. J. Groenenboom and H. J. de Liefde Meijer, J. Organometallic Chem., 1975, 94, 23. J. Goffart and G. Duyckaerts, J . Orgnnotncrallic C’hem., 1975, 94, 29. B. Crociani, M. Nicolini, and R. L. Richards, J . Clrganomefullic Chein., 1975, 101, C1.

322

Vibrational Spectra of Some Co-ordinated Ligands 323 o-static in T H F at -90 "C, [(c~t)Zr(allyl)~] is o/v-dynamic in THF at -80 "C, and, finally, [(cot)Hf(crotyl),] is oln-static in toluene at - 70 "C.' [(h3-C,H,)V(C0),(diars)] (diars = o-phenylenebisdimethylarsine)has v(CH) at 3046, 2987, and 2912 cni-l, and v(CC) at 1485 and 1444 cm-l from the triliaptoally1 ligand.8 Data on the u(C0) wavenumbers of some derivatives of [CpV(CO),] (see Table 1) suggest that the method of 'local symmetry' is of limited app1icability.O

Table 1 v(C0) spectra of (h5-C6H5)v(Co)4and (h5-AcC5H4)V(C0),,in iz-hexane solution

a1

bl

e

2029.9 2035.5

1965.5

-

1933.2 1947.2 1934.7

Assignment under C,, : Compound

[(h6-C,H6)V(co)41 [(h6-AcC,H,)V(CO)4]

( 1 3 ~ 0 )

1901.6 19 10.3 1902.5

The paper adds little to knowledge of the reasons for the range of applicability of the local-symmetry approximation. Hexamethylbenzene cluster compounds [(Me6C16)3M3X6]f (M = Nb, X = CI or Br; M = Ta, X = Cl) can be oxidized to give [(Me6C6)6M6X12]'' as the PF6- or NCS- salts.lo The i.r. spectra of all these products are essentially identical in the region 400&-600 cm-*. v(CN) for the carbene ligand is in the range 1520-1578 cm-', and v(CC1) is between 779 and 860 cni-l in the complexes [ML,{C(Cl)NMe,)],,,, where ML, = Mn(CO),'-, nz = 1; Cr(CO),, ni = 1 ; RhCI,(PEt,),, m = 1; or Rh(CO)Cl,, rn = 2." The following assignments have been proposed for the complex (1): v(C=C) 1640cm-', v(C-N) 1510cm-', when R, = H, RB = Me; v(C=C) 1614cm-l, v(C=N) 1510cm-l, when R, = Me, RB = Ph.I2

NI

1,

Compound (2) gives characteristic i.r. bands due to the Cp ligand at 1425,

1 110, 1008, and 785 C I I I - ~ . ~ ~

' *

lo

l1 la l3

E. G . Hoffmann, R. Kallweit, G. Schroth, K. Seevogel, W. Stemple, and G. Wilke, J . Orgunometullic Chem., 1975, 97, 183. J. E. Ellis and R. A. Faltynek, J . Organometallic Chem., 1975, 93, 205. G. Palyi and R. B. King, Inorg. Chim. Acfa, 1975, 15, L23. R. B. King, D. M. Braitsch, and P. N. Kapoor, J . Anter. Chem. Soc., 1975, 97, 60. A. J. Hartshorn, M. F. Lappert, and K. Turner, J.C.S. Chem. Comm., 1975, 929. K. H. Dotz and C. G. Kreiter, J . Organometallic Chem., 1975, 99, 309. K. H. Dotz and C, G, Kreiter, J . Organometallic Chem., 1975, 99, 309. J. Miiller and H . Menig, J . Organometallic Chem., 1975, 96, 83.

3 24

Spectroscopic Properties of Itiorgauic aiid Organometnllic. Coinppoimls

1.r. wavenumbers down to 250 cn-’ have been listed for [M(CO),L] (M = Cr, Mo, or W ; L = 2,2-paracyclophane).14 Apart from v(CH) and v(CO), the authors also suggest outline assignments for most of the bands. Analysis of empirical relationships between selected substituent parameters (UI, up, allP,up’, q t 0 ) and the C-0 force constant in 28 mono- and polysubstituted arenechromium tricarbonyl complexes suggests that the overall electronic substituent effect transmitted to the Cr(CO), depends upon both mesomeric and inductive niechanisms.I5 An approximate vibrational analysis has been reported for the complete [(CsHo)Cr(CO),] molecule and its deuteriate.’, Previous studies of the vibrational spectra of this system are in disagreement with each other i n several respects, Further, it has not always been possible to determine the extent to which wavenuniber shifts on co-ordination of C8H, arise from changes of force constant or kinematic effects. The present work shows that kinematic coupling is generally insufficient to explain the shifts which occur on co-ordination, although agreement between observed and calculated wavenumbers was still not good. The potential-energy distributions were calculated and discussed, and the wavenumbers calculated for the inactive modes were reported. Values for the C-0 stretching force constants were determined for [(C,H,)Cr(CO),], using i.r. wavenumbers and intensities, together with ‘ T O data.” An approximate force field has also been calculated for [(methyl benzoateCr(CO),], based upon those for methyl benzoate itself, and for [Cr(CO),].18 The paper also gives what is claimed to be the first ‘full’ assignment for this complex, previous work being ignored. The i.r. spectra of solid [(n-thiophen)Cr(CO)J, together with i.r. and Raman data for solutions, have been reported.lg The spectra were very similar to those of the benzene analogue. Tri- and penta-niethylpyridine react directly with [Cr(CO),] to produce the n-complexes [LCr(CO),]. v(C0) wavenumbers were reported for these and the complete absence of the ring-breathing mode was noted. A new band is seen for the complexes at about 1630 cm-1.2n Some complexes of a-chloro-enamines and metal carbonyl anions have been prepared. Acyl v(C=O), and v(C=C)/v(C=N) wavenumbers are shown i n Table 2.21 Miscellaneous group-frequency data, e.g. v(CH), v(OH), v(NH), v(CO), v(C=N), v(C=C), and v(C=N), have been listed, and used in structural diagnoses, for several new cyanocarbon complexes of M o and W. Some examples l4 l6

l8

l7

F. Cristiani, D. de Filippo, P. Deplano, F. Devillanova, A. Diaz, E. F. Trogu, and G. Verani, Inorg. Chiiii. Acta, 1975, 12, 119. E. W. Neuse, J . Organonwtallic Chem., 1975, 99, 287. D . M. Adams, R . E. Christopher, and D. C. Stevens, Znorg. Chem., 1975, 14, 1562. M . Bigorgne, 0. Kahn, M. F. Koenig, and A. Loutellier, Specfrochin? A m , 1975, 31A, 741.

P. Caillet, J . Organometallic Chem., 1975, 102, 481. B. V. Lokshin, E. B. Rusach, and Ya. D. Konovalov, Izvest. Akad. Nauk. S.S.S.R.,ser. Xhim., 1975, 84. H . G . Riedermann, K. Ofele, N. Schuhbauer, and D . J. Tajtelbaum, Angew. Chem. Internat. Edn., 1975, 14, 639. R. B. King and K . C. Hodges, J . Amer. Chenr. Soc., 1975, 97, 2702.

lH

2o

’L1

Vibratiotial Spectra oj’Sotile Co-ordinated Ligciirds

Table 2

325 Some i.r. spectral data for complexes of a-chloro-enamines and metal carbonyl nriiotts

Conip 1e.r [ Me,NCCMe,COW(CO),Cp] [Me,C=C(N Me,)COMn(CO),] [Me,C= C( NC6H,,)C0 M n(CO),]

[Me,NCCMe,CORe(CO),] [C,H,,NCCMe,CORe(CO),]

v(C=O)(acyl) 1617 I635 1650 1659, 1642 1647

’

v(C=C)/v(C=N) __ . 1607 1603 1592 1571

All wavenunibers/cni-’.

are: [C3(CN)zNH2Mo(CO)2Cp1, [C3(CN),NH2W(CO)(PPh3)Cpl, [C,H(CN)(0H)N H M o ( C O ) ~ C P ] . ~ ~ Values of Y,, and Y, of the C 2 0 unit are at 2084 and 1311 cm-’, respectively, in the i.r. spectrum Of [(OC),W-c(PPh3)C0].23 v(C==C) in the complex (3; M = Si) is at 1845 cm-l, while in (3; M = Ge) ~ ~ wavenumbers are about 300 cm-l lower than in the it is at 1856 ~ m - ’ . These free acetylenes.

The co-ordinated acyl group in (4) is at about 1465 cm-I, while in the related systems ( 5 ; M = Mn or Re; R = Me or aryl; X = H, Me, OMe, C1, or F) v(C=O) is between 1501 and 1530cm-’, again showing that it is co-ordinated 28 as Wavenumbers of v(C0) have been listed for the aminomethyl complexes [(1i2-R2NCH2)M(C0),](M = Mn or Re). The aminomethyl ligand functions as a formal three-electron donor.,’ The complex (6) shows v(C=O) at 1525 cm-I, i.e. some 50 cm-l lower than in [AI(acac),] .28 Irradiation of [(h6-C,H,)Mn(CO),] can be used to replace CO groups by cycloheptatriene. 1.r. spectra in the v(C0) region were used to obtain evidence for the intermediate (7a) or the isomeric form (7b).20 When a mixture of [Mn(CO),(NO)] and butadiene is irradiated, one, unexpected, product is the paramagnetic complex [(C,H,),Mn(CO)], for which v(C0) is at 1968 cm-l, with no evidence for delocalization of the unpaired 2“

23 24

O6

ao 57

2n

K. B. King, and M. S. Saran, Inorg. Chem., 1975, 14, 1018.

E. Lindner, J . Organometallic Chem., 1975, 94, 229. A. N. Nesmayanov, N. E. Kolobova, A. C. Antonova, and K. N. Anisimov, Doklady Chent., 1975, 220, 12. R. J . McKinney and H. D. Kaesz, J. Amer. Chem. Soc., 1975,97, 3066. R. J. McKinney, G . Firestein, and 13. D. Kaesz, Inorg. Chem., 1975, 14, 2057. E. W. Abel and R. J. Rowley, J.C.S. Dalton, 1975, 1096. C . M. Lukehart, G. P. Torrance, and J. V. Zeile, J . Amer. Chem. SOC.,1975, 97, 6903. P. L. Pauson and T. A. Segal, J.C.S. Dalton, 1975, 2387.

326

and Organometallic Compounds

0 : I I 0'

(0)

( 7.1)

electron on to the butadiene ligands30 [(C,H,)Mn(CO),(NO)] was also formed, for which v(C0) was at 2045 and 1994 cni-l, with v(N0) at 1751 cm-l. v(C=O) and v(C=O) (ketonic) have been determined for a number of (benzoylcyclopentadieny1)manganese tricarbonyls [{XC,H4COC,,H,(Y))Mn(CO),] (see Table 3).31 The following conclusions could be drawn: (i) Me substituents

Table 3

X H

o-Me nr-Me p-Me p-OMe

0-CI p-c1

0-F in-F P-F

-

Cnrhonyl stretc'fiirig ~i~aceiiirmbersfc~ii-~ for [XC6H4COC5H,(Y)MnY = a-Me 7

A,

Ketonic

2034

1661

2029

1665

2030

1655

2031

1655

2033

I649

2029

1673

2031

1657

2029

1666

--

E 1962, 1953 2034 1960, 1952 2032 1956, 1950 2033 1959, 1948 2034 1959, 1947 2034 1958, 1952 2031 1961, 1952 2032 1963, 1954 2032 1960, 1951 2034 1960, 1951

A,

1660

2030

1656

-

E 1953, I949 1952, 1949 1951, 1947 1953, 1948 1953, 1946 1948 1950 1955, 1950 I

1954, 1951 -

Ketonic

Y = 19-Me

A,

1659

2030

1663

2031

1653

2029

1656

2030

1650

2030

1663

2031

1660

2028

-

-

E 1954, 1945 1957, 1947 1955, 1946 1957, 1944 1955, 1946 1955, 1947 1959, 1948

Ketoriic

1955, 1946

1655

-

1659 1665

1655 1655 1648 1669 1656 -

1660

-

2028

on the Cp ring lead to a small but definite increase in the v(C=O)'s, (ii) substitution on the phenyl group is too far from the Mn(CO), group to have any effect, and (iii) the ketonic v(C=O) is affected more by phenyl than by Cp substitution. For the former the effects are in the order: 0-Cl > o-F N" o-Me > H z m-F > m-Me x p-C1 N" p-F N" p-Me > p-OMe. Characteristic group-frequency modes have been listed for the rr-bonded C6CI4X(X = C1 or Br) groups in [M(C,CI,X)L,], where M = Mn, L, = (CO),; 30 31

M. Herberhold and A. Razavi, Angcw. Chetn. Internat. Edn., 1975, 14, 351. N. J . tiogan and C.-K. Chu, J . Organonietallic Ch~wi.,1975, 93, 363.

Vibrational Spectra of Some Co-ordiitated Ligands 327 M = Fe, Ln r= C,CI,; or M = Rh, L n = cod, and for o-bonded C,Cl,X (X = C1 or Br) in [Mn(C5C14X)(CO)5].32 The complex (8) contains unsymmetrically co-ordinated 1,4-diazabutadiene (R = But or neopentyl). v(C-C) is 1680--1690cm-1. Other R groups give more symmetrical bonding, and no observable v(C-C) in the i.r.33 [CpFe(CO)(COMe)L] (L = PPh,, AsPh,, or SbPh,) give rise to acetyl v(C=O) bands between 1582 and 1598 ~ 1 1 1 - l . ~ ~

v(C0) of the carbamoyl ligand is at 1518 cm-1 in the complex [C(NMe,),]-+ [Fe(CO),CONMe,]-. This is a lower wavenumber than in the neutral carbamoyl ligand because of the greater negative charge on the 0 atom, and decreased C-0 bond [Fe,(CO)lo(C2H2)]has carbonyl stretching wavenumbers at 2095, 2054, 2036, 2028, 2009, and 1984 cm-l due to terminal CO groups, and at 1877 cm-1 due to bridging CO groups. From these data one cannot distinguish between the possible structures (9a) and (9b).38 The vibration v(C=C) has been reported for some acetylide complexes of Fe, Ru, and Re; in some cases CU' was also co-ordinated to the triple bond.,' Force-field calculations have been carried out on the (C2H4)-M fragment (M = Fe or Pt), using vibrational data from [(C,H,)Fe(CO),] and [(C2H,)PtCI3]-. The perturbation of the original olefin force field is much greater for the Pt than for the Fe system, showing that the extent of metal-ligand bonding is in that order. Since the normal modes are nearly all derived from more than one type of internal co-ordinate, the vibrational wavenumbers in this type of complex are of very limited value in discussions of bonding.38 v(C=O) for the carboxylate is seen at 1725 cm-1 in (lOa), and at 1737 cm-l in A conformational study of n-tetracarbonyl(niono-o1efin)iron complexes has been attempted, using i.r. spectra. The results were inconclusive, owing to decomposition, but some assignments of conformers were 33 :I:$

34

:I 6

s6 17

:in 31) 40

K. J. Reimer and A. Shaver, Inorg. Chem., 1975, 14, 2707. 11. tom Dieck and A. Orlopp, Angew. Chem. Internat. E h . , 1975, 14, 251. A. C. Gingell and A. J. Rest, J. Organometallic Chem., 1975, 99, C27. W. Petz, J. Orgunometullic Chem., 1975, 90, 223. F.-W. Grevels, D. Schul/, E. Koerner von Gustorf, and I). St. P. Bunbury, J. Organometallic Chem., 1975, 91, 431. 0.M. Abu Salah and M. I. Bruce, J.C.S. Dalton, 1975, 2311. D. C. Andrews, G. Davidson, and D. A. Duce, J. Orgnnomctallic Chent., 1975, 101, 113. J. Kagan, W.-L. Sin, S. M. Cohen, and R. N. Schwartz, J. Organometallic Clleni., 1975, 90, 67. S. Sorriso and G. Cardaci, J.C.S. Dalton, 1975, 1041.

328

Spwtroscopic Properties of Inorgarlic and Organornetallic Compounds

The complex (1 1) has a v(C=O) band at 1720 cm-l and v ( C 5 0 ) features at 2003 and 1 9 4 6 ~ m - l . ' ~For (12), v(C=O) is at 1702cm-', and v ( C ~ 0 )at 1969 ~ m - l . ~ ~ A normal-co-ordinate analysis for [C(CH2)3]Fe(CO)3 shows that the C- C stretching force constant is 4.41 mdyn A-l. This low value suggests a considerable donation of ligand n-electron density on to the metal. There are

significant interactions not only between the 'central' C atom and the Fe (stretching force constant 2.83 mdyn A-l) but also between the 'terminal' C atoms and the Fe (stretching force constant 1.16 mdyn A-1).43 The Fe complex (13) gives i.r. bands at 1713 cm-l due to v(C=O) and at 2058 and 1981 cm-1 due to v ( C = O ) . ~ ~ Assignment of the A l g v(CH) mode of ferrocene, which is very weak, depends upon good polarization evidence. This has now been supplied; previously it had only been available for R u C ~ The ~ . ~authors ~ also found that a weak line at 1106 cm-l is polarized: it has been suggested that this is an overtone of the v28 fundamental, and not the ~24(&7) fundamental. Polarization data for OsCp, have been given for the first time, and the authors consider that the skeletal assignment given in Table 4 is the most consistent with all the facts now known, and have corrected one or two previous anomalies.

Table 4 Assignment of some low-wavenumberfundamentals of [FeCp, 1, [RuCp,], and [OsCp,] (all waoenumbers/cm-') M Fe Ru 0s dl 42 43

u 4b

vdA1,)

303 329 356

vld&,)

478 385 353

vlB(&g)

388 402 41 5

vzl(EIu) 492 446 428

vZz(&J 170 162/172 160/166

k(M--Cp)/mdyn 3.04 3.33 3.83

A-l

A. Albini and H . Kisch, J . Organonirtnllic Chem., 1975, 101, 231. D . W. Lichtenberg and A. J. Wojcicki, J . Organometallic Chenr., 1975, 94. 31 1. D. C. Andrews, G. Davidson, and D . A. Duce, J . Organometallic Chew., 1975, 97, 9 5 . H . Alper, J . Organotnctollic Cheni., 1975, 96, 95. B. V. Lokshin, V. T. Aleksanyan, and E. B. Rusach, J. Orgnnometnllic Chetn., 1975, 86, 253.

Vibrational Spectra of’Some Co-orditinted Ligands

329 Raman shifts have been reported and assigned for [Cp,Fe]+, as BF4-, FeC1,-, 13-, and picolinate salts, and for C P , C O . ~Only ~ slight frequency shifts from [Cp,Fe] are observed for the ferriceniuni salts. The main interest, however, is the observation of the low-lying electronic transition ( E ( t ) s ( 2 A 2+ g )E , l , , ( 2 ~ , , ) ) in the ferriceniuni ion. For the I,- salt this is at 310 cm-’. The Raman and i.r. spectra (together with electronic and e.s.r. spectral data) of the following ferriceniuni systems have been discussed in a detailed study of the electronic structure: decamethylferriceniuni ion, [MeloFc]+;1 , l ’-dimethylferricenium ion, [Me,Fc]+; and 1 , l ’-triniethyleneferricenium ion, [(C,H,)FC]+.~~ Resonance enhancement of the v,(ring-Fe-ring) mode was observed. Vibrational fine structure was detected on the 2El,L+ 2E2,electronic transition from a lowtemperature study, and this was used i n a discussion of the relative metal-ring bonding characteristics of the elrr(potentially the metal 4p, + 4p,) orbital. The following conclusions were drawn: (i) the spectra were consistent with little e2, M-ring bonding in Fc and Fc+ systems, yet observable contributions from e,, bonding were found for [(C,H,)Fc]+ and [Me,Fc]+. This agrees with an increased (dz8-,*, cl,,)-ring overlap as the ring tilts, (ii) different vibrational modes in each case are probably coupled to the ,Elu *E2, ring-metal C.T. transition, (iii) vibrational wavenumbers were obtained for the ,E,,, excited state of each molecular system by measurement of the vibrational structure on the 2Elu+- 2E,, visible band at 20 K . Comparison of these with the values for the 1A,, neutral species shows that ( a ) in the Fc+ system there is no or e,, orbital participation in the M-ring bonding, (b) [ Me,FcIi [CCI,CO,]-,CCI,CO,H, with parallel rings, has n o e,, or el, contributions, ( c ) [Me,Fc]+PF,- has a small esn contribution, but the e l , contribution strengthens M-ring bonding, ( J ) [(C,H,)Fc]+ salts show substantial e2, bonding and similar e,, effects to (c), (e) [MeloFc]+ salts have small but seeniingly nearly equal e,, and elu bonding contributions to the potential surface for the tilting vibration of the rings.47 1.r. group-frequency assignments have been given for [(C,H,)Fe(C,ll,)], made by comparison with [(C,H,)M(C,H,)] ( M = Mn or Cr). Local symmetries were assumed for each ring; see Table 5.48 f-

Table 5

Some vibrational assignments for [(C,&)Fe(C,H,)] cm -l)

C,H, ring: C6H6 ring:

p(CH), A1 780 762

p(CH), E1

-

857

PCClI),

998 998

(all waveniinibersl A, 1108 969

Vriiig,

v(CC), Ei 1430 1430

The compound anaiysing as ‘[Fe(C,Ph,H)(CO),]’ gives C-0 stretching It is therefore formulated as (14). bands at 2019, 1979, and 1644 [Cp,Fe,(CO),(p-CO)(p-CN{H}R)]+ (R = Me, Et, or CH,Ph) all give characteristic v(C=N) bands from the bridging C=N(H)R ligands (15) at about 66 47

4u

B. F. Ggchter, J. A. Koningstein, and V. T. Aleksanyan, J . Chem. Phys., 1975, 62, 4628. D . M. Duggan and D. N . Hendrickson, Inorg. Chpm., 1975, 14, 955. A. N.Nesmayanov, N.A. Vol’kenau, V. A . Pctrakova. L. S. Kotova, and L. I . Denisovitch, Doklutly Chenr., 1974, 217, 475. K . J. Reimer and A. Shaver, J . Organornetullir Cheni., 1975, 93, 239.

3 30

Spectroscopic Properties of Inorganic and Organometallic Contpounds

1600 cm-l. Similar complexes were also obtained for some C=N(R1)R2 ligands (R1 = Me or Et).60 The dimeric ferrocene derivative (16) gives v(C=C) at 2160 cm-l, as does the trimer (17).61 The bridging species (1 S), however, produces an ‘acetylenic’ CC stretch at 1765 cm-I.

A few i.r. assignments have been proposed for a number of ferrocene derivati~es.~~-~~ The osmium complex (19) has i.r. bands at 1300 and 1140 cni-I due to the SO2 group, together with v ( C 0 ) at 2025 and 1955 ~rn-’.~’ Pll:{I,’ CO

/

\

C=NK u PI1 PI1

RN=C

Compound (20; R = aryl) gives an i.r. band at 1700 cm-l assigned to v(CN). This suggests that the C=N group is exo in the strained ring. This is confirmed by an X-ray structural 61

63

64 65

67

S. Willis and A. R. Manning, J. Organometallic Chem., 1975, 97, C49. C. V. Pittman and L. R . Smith, J. Organonwtallic (:hem., 1975, 90,203.

K. Yamakawa, M. Hisatorne, Y . Sako, and S . Ichida, J . Organometallic Chem., 1975,93,219. A. N. Nesmayanov, M. I. Rybinskaya, G. B. Shul’pin, and A. A. Pogrebnyak, J . Organonietnllic Chern.. 1975, 92, 341. M . Hisatome, T. Namiki, and K. Yamakawa, J . Organometallic Cllern., 1975, 96, C55. A. Ratajcak and B. Misterkiewicz, J . Organomctnllic Chem., 1975, 91, 73. A. N. Nesmayanov, N. N. Sedova, V. A. Sazonova, I. F. Leshcheva, and I. S. Rogozhin, Doklady Chem., 1975, 218, 647. K. R. Grundy and W. R. Roper, J . Organomrtallic Chem., 1975, 91, C61. A. Yamazaki, K . Aoki, Y . Yamamoto, and Y. Wakatsuki.J. Amer. Chem. Suc., 1975,97, 3456.

Vibrational Spectra of Some Co-ordinated Ligands

33 1

The formulation of [HC=CCo(chel)H,O], where chel = A"'-ethylenebis(7,7'-dimethylsalicylideneiminato), has been confirmed by the observation of v(=CH) at 3260 cm-' and v(C=C) at 1982 Seyferth et al. have studied the Friedel-Crafts acetylation of diarylacetylenedicobalt hexacarbonyl. Extensive data have been given for the carbonyl bands of the products, and drawings illustrating the progress of the substitution. Acyl v ( C 0 ) wavenumbers have also been listed.60 The patterns of v ( C ~ 0bands ) in the i.r. for [LCo(CO)J, where L = n-C,F, [v,,(C-C-C) 1425 cm-l] or n-F,CCF=CF [v(C=C) 1640 cm-I], are consistent with effective C,,symmetry for the Co(CO), fragment.61 1.r. wavenumbers have been listed for the characterization of [Co(n-ally1)(PF,),(PPh,)], where the n-ally1 ligands are syn- and anti-1-Me-n-allyl, 1,l -dimethyl-n-allyl, anti- 1,2-diniethyl-rr-allyl, syn,syn-1,3-dimethyl-rr-allyl, 2-et hyln-allyl, n-cyclo-octenyl, and h3-~-cyclohexadienyl.62 The Raman spectra of the intermediate products of the reaction of [HCo(CN),I3with buta-1,3-diene have been studied.s3 In an excess of CN-, o-(but-2-enyl)pentacyanocobaltate(ii1) is present, as both cis- and trans-isomers, (21a) and (21 b). In a deficiency of CN-, syn-n-( 1 -methylallyl)tetracyanocobaltate(Ilr) (22) alone is present. If [CN] : [Co] = 5, a mixture of the 0-and n-complexes results.

(72)

( 2 11.)

Compound (23) gives an i.r. band due to the complexed cyclopentatiienoiie at 1630 ern-'. v(C'C) (complexed) is at 17 15 cm -l.'j The complexes (24; M = Co, R = Me, Ph, or CsFb; M = Rh, R = Ph or C,F,) all give v(C=O) in the range 1570--1615crn-'. The action of HCl or HBFl converts these into hydroxycyclopentadienyl derivatives, with u ( C - 0 )

(33)

(33)

(25)

C i . Mestroni, G. Zassinovich, A. Camus, and Ci. Costa, J . Orgcitionictallic Clienr., 1975,92, C35. D. Seyferth, M. 0. Nestle, anti A. T. Wehmann, J . Arner. C l ~ e tSOC., ~ . 1975, 97, 7417.

lbH

Rn

nL gJ

64

K . Stanley and D . W. McBride, C u t i d . J . C'lienr., 1975, 53, 2537. M. A. Cairns and J . F. Nixon, J . Orgunomrtullrc Clretn., 1975, 87, 109. H . J. Clase, A. J. Cleland, and M. J . Newlands, J . Organometallic Clieni., 1975, 93, 231. R . S. Dickson and L. J . Michel, Awtral. J . Clwn., 1975, 28, 1957.

332

Spectroscopic Properties of Irtorganic and Orgnnometciliic Compounds

1430-1485 cm-l, i.e. there is still some double-bond character in the C-0 bond.s5 The vibration v(C=O) for the complex (25) is at 1735 cm-1.66 But-3-enyldiphenylphosphine (= mbp) and diphenylpent-4-enylphosphine (= mpp) form complexes with Rh'; [RhX(mbp),] shows no bands due to free C=C in the solid, only v(C=C) at 1505 cm-l and S(CH) at 1252 and 1231 cm-', from coniplexed C=C (the absence of free C=C was confirmed by an X-ray study). In CH2C12solution, however, a band at 1642 cm-l must be assigned to a free olefinic bond. The ligands mpp and nibp both also form dimeric complexes [Rh2X,L,], with no sign of free C=C in the solid or in s ~ l u t i o n68. ~ ~ ~ 1.r. wavenumbers have been listed for the characterization of [RhCI(PF3),(diene)],, which are thermally unstable (diene = buta-l,3-diene, 2-Me-buta1,3-diene, or penta-1 ,3-diene).6D Two crystallographic modifications of [(norbornadiene)RhCl], have been prepared.'O The solids show clear differences in the regions associated with stretching and bending modes of the bridging CH,, although no specific assignments were proposed. [Rh,(CO)(nbd),(C,H,O)] has been shown by X-ray crystallography to be (26). The bridging carbonyl group gives v ( C 0 ) at 1830 cm-*, while the co-ordinated acyl group stretching wavenumber is 1650-1 610 ~ m - l . ~ l [Rh,(CO),C12(cis,trans-l,3-cod),] gives v(C==C) bands due to the co-ordinated cod at 1610 and 1650 cm-l. This is consistent with the cod acting as a bridging ligand, with a free C=C.72

(26) E6 B6

E7

E8

EB

70

(27)

J. E. Sheats, W. Miller, M. D. Rausch, S. A. Gardner, P. S. Andrews, and F. A. Higbie J . Organonicrallic Chenl., 1975, 96, 1 15. P. G . Gassmann and J. A. Nikora, J. Organonretdlic Chem., 1975, 92, 81. P. W. Clark and G. E. Hartwell, J. Orgunonwtallic*Cheni., 1975, 102, 387. R . R. Ryan, R. Schaeffer, P. Clark, and G. Hartwell, Inorg. Chem., 1975, 14, 3039. J . F. Nixon and 11. Wilkins, J. Organon~ctallicChmt., 1975, 87, 341. 13. Denise, D. Brodzki, and G. Pannetier, Bull. Soc. chini. France, 1975, 1034. J . A. J . Jarcis and R. Whyman, J.C.S. Cheni. Comm., 1975, 562. H. A. Tayini and F. T. Mahmoud, J. Organontc~tallicChcm., 1975, 92, 107.

Vibra t ionnl Spectra oj ' Some Co -0rditin t ed L ignnds

333 [lr(chel)(cod)(C==CR)] show v(C=C) in the 1930-2090 cm-l range, where chel = phen or 3,4,7,8-Me4phen and R = H or Phei3{IrCl(cod)[F,CC=CCF,)1), has a v(C=C) band at 1860 ~ m - ' . ~ , The reaction between Ni, Pd, or Pt atoms and acetylene compounds at low temperatures affords uncharacterized n--complexes. The chief evidence for their existence comes from lowering of the v(C=C) and v(CH) wave number^.^^ The fluxional and catalytically active cluster compound [Ni4CNCMe3l7shows v(CN) at 1605 and 1610 cm-l. These very low values suggest that the ligand is facially bridging. The structure as determined by X-ray diffraction is (27).70 Co-condensation of Pd vapour with C2H4 at low temperatures appears to afford [Pd(C,H,),], with v(C=C) at 1513 and 1522cm-l, compared to the literature value of 1510 cm-' for the Ni ana10gue.~' Some re-assignments have been proposed for the vibrational wavenumbers of [(T-C,H,)MX], ( M = Pd or Ni, X = CI, Br, or There appeared to be little justification for the new assignments, although sonic evidence was found for extensive mixing of internal co-ordinates. Compounds (28), uhere M = Pd or Pt; L = PPh3, PPh,Me, or AsPh,; R1 and R2 = H, Me, or Et, all show v(CN) at about 2220cni-', for M = Pt, or at about 2200cm-l for M = Pd. These compare with the wavenumber for the free cyclopropane derivative, which has v(CN) at 2260 CM-'.'~

The lowering of v,,(NCO) of the aniido-group from 1662cm-l in (p-toly1)NHCOMe to 161Oc1ii-~in the complex (29) is consistent with O-bonding in the ortho-metallated compound.80 Some fairly detailed assignments have been given for the norbornadiene (= L) complexes [LPtXJ (X = C1, Br, or I), [LPdX2] (X = C1 or Br), [(LRhCl),], and [LFe(CO),]. No account was taken of any possible coupling between v(C=C) and 6(CH2) modes, however. The extent of metal-ligand interaction appears to be in the order Pd < Pt .c Rh; and for the halides, C1 < Br .c I.s1 73 i4

76

iE 77

'13

is "I'

"l

G. Mestroni, G . Zassinovitch, and A. Camus, Inorg. Nuclear Chem. Letters, 1975, 11, 359. D. A. Clarke, R. D. W. Kemmitt, D. R. Russell, and P. A. Tucker, J . Organomerallic Chem., 1975, 93, C37. V. T. Aleksanyan, G. M. Kuz'yats. and T. S. Kurtikyan, Doklady Chem., 1974, 216, 331. V. W. Day, R. 0. Day, J. S. Kristoff, F. J . Hirsekorn, and E. L. Muetterties, J . Amer. Chem. SOC.,1975, 97, 2571.

R . M. Atkins, R. Mackenzie, P. L.Timms, and T. W.Turney, J.C.S. Chem. Comm., 1975, 764. G . N. Bondarenko and A. V. Kotov, Doklady Phys. Chem., 1974, 219, 1159. M. Graziani, M . Lenarda, R. Ros, and U. Belluco, Coordination Cheni. Rei)., 1975, 16, 35. N. D. Cameron and M. Kilner, J.C.S. Chem. Comm., 1975, 687. I . A. Zakharova. Ya. V. Salyn, I . A. Garbuzova, V. T. Aleksanyan, and M. A. Prianichnicova, J . Organumetallic Chenr., 1975, 102, 227.

334

Spectroscopic Properties of Inorganic and Organometallic Compounds

v(C=O) in the complexes (30) is related to the base strength of L; as this increases, Av(C0) [ = v(CO)free - ~(CO),,plexed] increases also. Thus Av(C0) is in the sequence P(OPh), < (p-CIC6H,),P % PPh, < ( J I - M ~ O C ~ H , ) P(OR), > P(NR2), > PR3.140 Various C180-substituted species in the series cis-[Mn(CO),LBr], where L = PPh,, AsPh,, or SbPh3, have been prepared and their i.r. spectra [v(CO)] recorded.141 The resulting data have been used in some approximate CO-only force-field calculations. The spectra show that the initial enrichment of C1*O occurs preferentially in the axial position, although eventually all four CO's are replaced. 1.r. spectra have been given in the v(C0) region for [LMn(CO),COCH,Ph], where L = phosphine or phosphite. Both cis- and trans-isomers were obtained in some cases.142 The i.r. spectra of the first examples of organolead manganese carbonyls of the type [R,-,Pb(Mn(CO),(PPh,)},J (R = Me or Ph; n = 1 or 2) show that the PPh, ligands are trans to the Pb.143 Mn atoms react with CO at 10-15 K to form square-pyramidal [Mn(CO),]. Cotton-Kraihanzel force constants were evaluated, and i.r. intensities used to estimate the apical-equatorial angle.144 +-

lS7

lSn 140

141

1 4

144

R. Colton and J. E. Garrard, Ausfral. J . Chem., 1975, 28, 1923. R . B. King, K. H. Reimann, and D . J . Darensbourg, J. Organornetallic C'hein., 1975, 93, C23. D . Drew, D. J. Darensbourg, and M . Y . Darensbourg, Znorg. Cheni., 1975, 14, 1579. J . R . Wagner and D . J . Hendricker, J . Organornetallic Cheni., 1975, 91, 321. I. S. Butler and H. K . Spendjian, J . Organomcfallic Chent., 1975, 101, 97. ~D. Drew, M. Y . Darensbourg, and D . J. Darensbourg, J. Organoinctallic Chem., 1973, 85, 73. W. Schubert, H.-J. Haupt, and F. Huber, Z . anorg. Chenr., 1975, 412, 77. H . Huber, E. P. Kundig, G . A. Ozin, and A. J. Poe,J. Amer. Chen7. Sor., 1975, 97, 308.

Vihrtrtiorini Spectra of Some Co-ordinated Ligands

343 An approximately linear relationship has been found between the square-root of the absolute intensity of the symmetric CO stretching mode in the i.r. and the occupancy of the 27-r orbitals on the cis-CO groups in [Mn(CO),X] (X = CI, Br, or I).145 Rather detailed assignments have been given for the gas-phase i.r. and liquidphase i.r. and Raman spectra of [(CF,),EMn(CO)J (E = P or Many of the assignments were based on a normal-co-ordinate analysis using a force field from other (CF,),E systems and from [XMn(CO),]. The solvated complex [Mn2(CO)5(dpm)2],CH2C1,,C6H14,where dpm = Ph2PCH2PPh2,contains a unique type of bridging carbonyl ligand (42). This is analogous to M-CC.,H,l r-bonding, and it gives v(C0) the anomalously low value of 1645 c ~ i i - ~ . ~ " ~ (Et4N)[Mn2(C0),(pX),] give two v(C0) bands, at 2029 and 1928 cm-l for X = C1 and at 2025, 1936 cm-l for X = Br.14HThis is consistent with D,, geometry, and the bands were assigned to A $ and E" modes, respectively.

An attempt has been made to correlate v(C0) wavenumbers in [Mn,(CO),,] and [Mn2(CO)8L2]with the Hildebrand-Scott solvent parameter sa derived from regular solution theory. The relationship is linear for non-polar solvents, but deviations occur in polar ~ o l v e n t s . ~ ~ ~ Two differing detailed assignments have been proposed for the v(C0) bands of [MnRe(CO),,]. 150-150 The work of Bor et al. appears to be preferable, as particular attention was paid to weak isotope bands. The spectra were fully analysed using a CO-factored force field.15' The complex (43), containing a formal Fe=Fe bond, has v ( C 0 ) values of 2051, 1980, and 1861 cm-1.153 The v(C0) values in the following series shift to lower wavenuniber with increasing Me substitution, consistent with greater electron release by the Me groups: [(ArH)Ru(CO)(GeCl,),] (Ar = Ph, MeC,H,, o-, m-, or p-Me2C6H3,or s-M~~C~H~).'~~ M. S. A. Abd-el-Mottaleb, J . Mol. Strirctrirc, 1975, 25, 435. R. Demuth, J. Grobe, and R. Rau, Z. NuturJilrsch., 197.5, 30b, 539. 14i C . J. Commons and H. F. Hoskins, Austral. J . Chem., 1975, 28, 1663. Inn J . L. Cihonski, M . L. Walker, and R. A . Levenson, J . Orgunometallic Cheni., 1975, 102, 335. I 4 O N. J. Could and D. J. Parker, Specrrochim. A m , 1975, 31A, 1785. W. T. Wozniak, G . 0. Evans, and R. K. Sheline, Znorg. Chem. A d a , 1975, 14, L53. 151 W. T. Wozniak, G . 0. Evans, and R. K. Sheline. J. Znorg. Nuclear Chem., 1975, 37, 105. G . Sbrignadello, G. Rattiston, and G . Bor, Inorg. Chim. Acta, 1975, 14, 69. lG:l I . Fischler, K . Hildenbrand, and E. Koerner von Gustorf, Angew. Chem. Infernat. Edn., 1975, 14, 54. l S 4 K. K. Pomeroy and W. A. G . Graham, Canud. J . Client., 1975, 53, 2985.

14:'

Idti

344

Spectrmcopic Piwperties of Iiiorgnnic mid Orgnnometnllic (bmpoirnds

[RuC1,(CO)(CSe)(PPh3),1 has been prepared for the first time; v(CSe) is at 1125 C I Y I - ~Similar . ~ ~ ~ values were found for a number of other CSe complexes of Ru. Quite detailed assignnicnts havc been made for the v ( C 0 ) modes of some iron a n d rut hen i u m complexes con t a i n i n g d i phenyI - , d i met hy I-, or d iet h y 1-f u I ve nc (dpf, dmf, and def) as a ligand.lS6 [(def),Fe(CO),] gives A l and B1 modes at 1993 and 1937 cm-l, respectively, while in [(dmf),Ru(CO),] they are at 2004 and 1941 cm-l. CO modes were also assigned for the newly prepared complexes cis[0sX4(CO)J2- as the NEt,+ salts: see Table 12.15' These were used to calculate

Table 12 v ( C 0 ) ~vnoenrrntberslcni-1 for cis-[OsX4(CO)z]zX Wavenuntberslcm-l CI Br I

2003 ( A , ) 2008 2008

1905 ( B J 1918 1926

Cotton-Kraihanzel force constants. S(OsC0) modes were also assigned, although these are doubtless heavily mixed with v(0sC:). All possible complexes [(diene)Fe(CO),_,(PF,),] (x = 0, 1, or 2) have been prepared, and their v ( C 0 ) wavenumbers assigned (diene = buta-l,3-diene and a large number of methyl-substituted derivatives),lS8 The values of v ( C 0 ) are altered in an additive way, depending on the methyl position. On substitution, the PF3 group seems to prefer the apical position. The K1 force constants for the unique apical CO groups show a good correlation with the Hiickel MO $z and $,I diene orbital populations. 1.r. spectra in the v ( C 0 ) region have been recorded for the complexes (44a) and (44b). Two rotamers are thought to be present in the solid BPh4- salt of (44b) .l6I) The first report has been made of the Ranian spectra of [H,M(CO),] (M = Fe, Ru, or 0s) as solid films deposited at low temperatures. Owing to its high thermal stability, it was also possible to obtain the spectrum of [H,Os(CO),] (liquid). The v(MH) modes are very intense, in contrast to their feeble i.r.

(43;t)

(44h)

(35)

absorptions, and confirm the cis configuration for all three compounds in the solid state. For liquid [H,Os(CO),], v(0sH) are at 1970 (p) and 1940 (dp) cm-l, with v(C0) at 2140 (p), 2063 ( ? dp), 2039 (dp) cm-l. ls6 15R

G . R. Clark, K. R. Grundy, R. 0. Harris, S. M. James, and W. R. Roper, J . Organometaffic Chem., 1975, 90, C37. U. Behrens and E. Weiss, J . Organomrtallic Chem., 1975, 96, 399, 435. F. H. Johannesen, W. Preetz, and A. Scheffler, J . Organonietallic Chem., 1975, 102, 527. M. A. Busch and K. J. Clark, lnorg. Chent., 1975, 14, 219. D. C. Harris and H. B. Gray, lnorg. Chem., 1975, 14, 1215.

345 [H,Ru(CO),] (solid) shows v(RuH) at 1916 and 1897 cm-l; therefore the weak i.r. band at 1980 cm-l is not v(RuH). The v(MH) values in this series follow the order Fe < Ru < Os, and appear to correlate with the trend in the thermal stabili ties.lso The i.r. spectra of the neutral carbene complexes (45; M = Fe or 0 s ) show four i.r. bands due to v(C0). This is consistent with trigonal-bipyramidal M co-ordination, with equatorial L.16' A review has appeared on the vibrational spectra and bonding in the series of compounds [Fe,(CO),(p-Y),] and [co,(co)6(px)2], where X = CO, P, As, or CR; Y = S, SR, Se, PR1R2, Br, or I.162 v ( C 0 ) i.r. spectra have been used to diagnose the presence of Sn-Fe-Sn or Fe-CO-Fe bridges in the dimeric species [(X,Sn)Fe(CO)4],.1s3 Pyrolysis of [ R U ~ ( C O )and ~ ~ ][Os,(CO),,] leads to the species [Os,(CO),,], ~ ~ S ~ ( ~[Os6(cO>ial, ~ ) i ~ [oS7(co)2il, ~ l , [oSa(co)z3l, and [OS~(~0)21c1.N o bridging carbonyl bands were observed in the i.r. v ( C 0 ) spectra, although simple electron counts suggest that they might be present in some of these The use of high-pressure i.r. to study the mechanism of the hydroformylation of olefins, catalysed by Co carbonyls, has been reviewed.lBS A matrix-isolation study of the products of the reactions between Co atoms and CO leads to the v(C0) values for [Co(CO),] (n = 1 - 4 ) listed in Table 13. Vibrational Spectra of Some Co-ordinated Ligarrds

Table 13 CurbonyZ stretching wauenumbers/cm-' for [Co(CO),] i1:

Mufrix: Xe Kr Ar

1 1947.0/1941.0 1952.0/1944.0 1956.0/1949.0

2 191 1.0 1914.0 1919.0

3 1971.0 1977.0 1982.0

4 2019.0, 2008.0 2020.8, 2010.6 2024.0, 2014.4

Rarnan and e.s.r. data were also reported. Co(CO), apparently has C,,symmetry. Cotton-Kraihanzel force constants for the Co carbonyls are consistently lower than the values for the Ni analogues.166 The presence of v(C0) at 1986 and 1971 cm-l (with comparable i.r. intensities) in solid [RhC1(CO)(PPhMe,),12 agrees with the cis geometry determined crystallographically. In solution, three bands are seen; these are due to the cis(1 996 and 198 1 cm-') and the trans- (I 990 and 198 1 cm-') isomers being present.lS7 [Cp,Rh,(CO){(C,F,H)C,(C,H,))I gives a v ( C 0 ) band at 1725 cm-l ; the structure probably involves a triply bridging carbonyl, as shown in (46).lS8 There is a linear correlation between v(C0) of [IrH,C1,-,(PPh3),(C0)], where n = 3, 2, 1, or 0,and the half-wave potentials (Ed) for the electrochemical G. F. Bradley and S. R. Stobart, J.C.S. Chem. Comm., 1975, 325. M. Green, F. G. A. Stone, and M. Underhill, J.C.S. Dalton, 1975, 939. I n 3 G. Bor, J . Organometullic Chem., 1975, 94, 180. Ins A. B. Cornwell and P. G. Harrison, J.C.S. Dalton, 1975, 2017. lfi4 C . R. Eady, B. F. G. Johnson, and J. Lewis, J.C.S. Dalton, 1975, 2606. 1 6 5 R . Whyman, J. Organnntctallic Chem., 1975, 94, 303. I a R L. A. Hanlan. H . Huber, E. P. Kundig. B. R. McGarvey, and G. A. Ozin, J . Amer. Chem. SOC.,

Iao

In*

le1

1975, 97, 7054. R. Poilblanc. J . Organornetallic Cheni., 1975, 94, 241. R . S. Dickson and L. J. Michel, Austral. J . Cheni., 1975, 28, 1943.

346

Spectroscopic Properties of Inorganic and Orgunometuliic Compounds I,Ni(PhNNPb)] gives rise to several i.r. band shifts, but none is of the magnitude expected for v(NN); therefore the modes are highly coupled. Similarly, the Raman spectrum of (55) gives a shift for only one band (876 to 855 cm-l), but this is so far from the v(NN) wavenumber in free PhN2Ph (by nearly 600cm-l) that it too must be For [Ni(2,2’-azapyridine)Io, all four N atoms are thought to be co-ordinated, with v(N=N) at the low value of 1380cm-l; the structure (56) has been postulated, with tetrahedral co-ordination at the Ni. lop *On 201 203

208

J. F. van Baar, K. Vrieze, and J. D. Stufkens, J . Organometallic Chem., 1975, 97, 461. B. L. Haymore, J. A. Ibers, and D. W. Meek, Inorg. Chem., 1975, 14, 541. J. F. van Baar, K. Vrieze, and D. J. Stufkens, J . Organometallic Chem., 1975, 85, 249. W. Klotzbucher and G. A. Ozin, J . Amer. Chem. SOC.,1975, 97, 2692. M. Aresta, C. F. Nobile, and A. Sacco, Znorg. Chim. Acra, 1975, 12, 167. S. D. Ittel and J. A. Ibers, Znorg. Chem., 1975, 14, 1183.

351

Vibrational Spectra of Some Co-ordinated Ligands m

(55)

(56)

v,,(N,) is in the range 2050-2070cm-1, with v,(N3) between 1267 and 1340 cm-l in the azido-bridged complexes [(dieneOMe)MN,], (M = Pd or Pt) and [(~-allyl)PdN,]~.It is not known whether the co-ordination involves the unit (57a) or (57b).,04 N I N

I

N

MC \ M

Y’

N

I N

(57a)

A very few bands characteristic of the triazenido-ligand have been listed for [(1,3-r)-CSH5)Pd(p-XC6H4N=N-NC6H4X-p)la(X = Me, H, or Cl).,05 v(N3) is at 2045 cm-l in ~~~~S-[P~(L)~CI(N~)]CI~,H,O, when (L), = (NH,),, and at 2040 c n r l when (L)4 = [L2Pt(N3),] (L = various phosphines) adopt the cis-configuration, and no isomerization occurs in solution, unlike the Pd analogues. The v,,(N3) values, in CH,Clp solution, are given in Table 16.207 Table 16

Valires for the v,,(Ns) wavenumbers/cni-l in the complexes [L,Pt(N,),] L PBuns PhPBunz Ph,PBun Ph3P

A1 2059 2058 2057 2057

4

2042 2043 2044 2042

[Pt(C=CPh)(HN=NAr)(PPh,),]+ gives v(C=C) at about 21 24 cm-l. Several bands were seen in the range 1600-1400cm-1, but no detailed assignment to v(C= N) was at temp

207 208

L. Bussetto, A. Palazzi, and R. Ros, Inorg. Chim. Acta., 1975, 13, 233. S. C. de Sanctis, L. Toniolo, T. Boschi, and G . Deganello, Inorg. Chim. Acta, 1975,12, 251. H. A. Bryan, N. S. Pantaleo, W. L. Dickinson, and R. C . Johnson, Inorg. Chem., 1975, 14, 1336. P. H. Kreutzer, K . T. Schorpp, and W. Beck, 2. Naturforsch., 1975, 30b, 544. U. Croatto, L. Toniolo, A. Irnmirzi, and G. Bombieri, J. Organometallic Chem., 1975, 102, C31.

352

Spectroscopic Properties of Inorganic niid Organonretnllic Coinpouncis

The isolation of N,H-bridged complexes after the reduction of cis[Pt(PR,),CI,] with N,H, has been The compounds are of the type ( 5 8 ) , with L = PPh,, PPh,Me, or P(tol),. Three bands are seen in the v(NH) region (3300-3200 cm-l), which shift on deuteriation; one of these is probably due to a combination. v(N-N) is at ca. 1580 cm-l, and unshifted on deuteriation. An azide-bridged structure has been proposed for [Cu2(dien),X2](BPh,),, where X = N3, because va8(N3) is at 2070 cm-l, and v8(N3) at 1345 cm-I. X Me \ / C u t N

( 59)

(58)

X-Bridging is also suggested for X = NCO or NCS [dim = (H,NCH,CH,),NH].210 The i.r. spectrum of [(MeN=N),Cu,CI,] contains features probably due to the N=N unit between 1550 and 1630 cm-1.211 Y,, (1350 cm-l) and v, (1220cm-I) have been assigned for the triazenidocomplexes (59; X = C1, Br, or I ; M = Rh or Ir).212 Group-frequency assignments from the i.r. spectra of the Hg and Cu complexes of (2,4,5-trihalogenophenyl)-(2,4,6-trihalogenopheny~)triazene suggest coordination of the type (60).*13 vas(N3)and a few other bands were assigned in [M(OH),N,],H,O, where M = Pr, Nd, or Sm.214a The i.r. and Raman spectra of [C(N,),]+MCl,- (M = Sb or U) show the cation to have C , symmetry. Force constants have been calculated for the N II

11 N

(61)

triazido-carbonium ion, of 640 N m-' for the N-N stretch and 2040 N m-f for the N = N stretch. The v(N=N) wavenumbers were 2234 and 2209 cm-l, while those for v(N-N) were 1228 and 1076 ~n1-'."~* 208

210 211 212 213 214

M. Keubler, R. Ugo, S. Cenini, and F. Conti, J.C.S. Dalton, 1975, 1081. G. R. Hall, D. M. Duggan, and D. N. Hendrickson, Znorg. Chem., 1975,14, 1956. J. L. Boehm, A. L. Balch, K. F. Bizot, and J. H. Enemark,J. Amer. Chem. SOC.,1975,97,501. J. Kuyper, P. I. van Vliet, and K. Vrieze, J . Organomefallic Chem., 1975, 96, 289. R. E. Zaitsev, V. A. Zaitseva, A. Batista, and A. 1. Ezhov, Rum. J. Inorg. Chem., 1975, 20, 397. (u) M. S. El-Ezaby and I . E. Abdul-Aziz, J . Inorg. Nuclear Chem., 1975, 37, 2013; (h) IJ. Mullcr and W. Kolitsch, Spectrochim. Ac.ru, 1975. 31A, 1455.

Vibratiorzrrl Spectru of Some Co-orditiuted Ligunds 353 v,,(N,) values were listed for the Ph,As+ salts of the following: [Me,Sn(N,),]2-, [Ph,Sn(N,),]-, [Ph,Sn(N,)(NCS)]-, and [Ph,Sn(N,)2(NCS),]2-.215 1.r. and Raman spectra show that dimethyldichloroantimony azide and cyanate are bridged diniers (61). The assignments on which this conclusion is based are shown in Table 17.,16

-

Table 17 Some vibrational assignmentsfor [Me,Cl2SbXI2(all wavenumbers/cm-l) X = N,

1.r.

-

R

-

-

2090 -

1250 -

1243

-

653

2102

-

-

-

-

-

-

-

X = NCO

I.r. 2205 1305

-

665 612

R 2205 2195 1374

-

-

662 -

Amines and Related Ligands.-The solid-state i.r. and Raman spectra of bis(ethy1enediamine) complexes whose ring conformations had previously been determined by X-ray crystallography have been examined, particularly in the 2500-3400 cm-1 region, and between 800 and 1100 cm-l. Complexes (of A metal configuration) having 668 (eight compounds), 6hX (three compounds), 86h (one compound), and hXA (one compound) ring conformations were studied. It was shown that the solid-state data might be used to identify the presence of mixed ring c ~ n f o r m a t i o n s .For ~~~ example, for the 666 conformation ( D 8 symmetry): rcc-c) = A , ( R ) + E(i.r., R), whereas for 88X or 6hh(C2): rcc-c) = 2A(i.r., R) + B(i.r., R).

The compounds studied conformed to these selection rules. A study has been made of the effect on the v(NH) bands of PhNH, of Na+, Li+, Sr2+, Ca2+, or Ag+ perchlorates, or of NaI, in MeCN solution. Both PhHzN-.* Mu+and PhNHz I- interactions were observed.218 The trimeric [Be2(0H),(O,CMe),(NH,)1, gives v(NH,) at 3352 (E) and 3220 (A,) cm-l, and G(NH,)(A,) at 1308 cm-1.219 Many i.r. and Raman data have been tabulated, and approximately assigned, for [(Me,N),Ti(C,H,R)], where R = H, Me, Et, CHMe,, CHEt,, CMe,, SiMe,, SiMe,Ph, or GeMe,.220 21s

2 1 217

21p 220

R. Barbieri, N . Bertazzi, C. Tomarchio, and R. H. Herber, J. Organonlefallic Chem., 1975, 84, 39. ~H. G . Nadler and K. Dehnicke, J . Organometallic Chem., 1975, 90, 291. R. E. Cramer and J. T. Huneke, Inorg. Chem., 1975, 14,2565. U. Stolarczyk, Roczniki Chem., 1975, 49, 329. A. I. Grigo'ev and L. N. Reshetova, Russ. J . Znorg. Chem., 1974, 19, 1426. H. Burger and U. Dammgen, J . Organometallic Chem., 1975, 101,295.

354

Spectroscopic Properties o j Inorganic and Organometallic Conlpounds

VO(C204),2N2H4,2H20apparently contains unidentate hydrazine ligands, since v(N-N) of the hydrazine is at 910 cm-1.221 The observed shifts in v(C=N) and v(C=C) modes on co-ordination of phen or bipy to give [M(O-O)F3(L)] (M = Nb, Ta, or WO; L = phen) or [M,0(O-O),F4(bop~)21 (M = Nb or Ta) are characteristic of chelating NN-co-ordination by the ligands, Thus v(C=N) is at 1630 cm-l and v(C=C) are at 1525 and 1430cm-’ in [Nb(O-O)F,(phen)], compared with 1618, and 1503 and 1425 cm-l in the free ligand.222 [MeCrCI,L,] (L = NH,Prrl or NH,Bur*) complexes may be obtained by ligand-exchange reactions with [MeCrCI,(THF),].223 They show shifts to lower wavenumber for both v,, and v, of NH, (13@--200cm-l). They are probably [ MeCrCl L,]+CI-. Group-frequency assignments of ligand modes purport to show that in [Cr,(C204)3],4N2H4,4H20 there are both unidentate and bridging N2H4groups, while in the adduct with seven N2H, molecules and one H 2 0 there are four unidentate and two (?) bridging N2H4groups.224 A number of assignments of ligand modes due to both unidentate and bridging hydrazine ligands have also been made for [Mo(CO),L], [L{Mo(CO),),] (L = NpH4or N2D4), and for some ligand modes in [L’{Mo(CO),),] (L’ = N,H, or N2D2).225 The behaviour of i.r. bands due to bipy or phen on co-ordination is typical of NN-chelation in [W02F2L].22strans-[WCl,(NHNH,)(PMePh,),] gives v(NH) at 3123, 3197, and 3356 ~ r n - * . ~ ~ ’ The i.r. and Ranian spectra of [M(NCO),L] (L = isonicotinic acid hydrazide) have been assigned, for M = Mn, Co, Zn, or Cd. Bridging structures were indicated.228 The NH3 modes have been listed for [MScF,],12NH3 (M = Mn, Co, Ni, Cu, Zn, or Cd); their structures are Group-frequency assignments of i.r. data on the complexes [FeCI,L,], where L = phenylhydrazine, m-X-phenylhydrazine (X = C1, Br, or I), p-bromophenylhydrazine, and p-nitrophenylhydrazine, indicate that they are polymeric, with bridging hydrazine ligands. O-nitrophenylhydrazine, on the other hand, forms a chelate containing (62).230 v(NH) and v(CN) have been listed for salts of [Fe(ms-CRH)]”+, where n = 2 or 3 and (ms-CRH) = (63).231 Unidentate NzH4 ligands are suggested for the complex K2[Ru(CN)4(N,H4)2],2H,0 by the observation of v(N-N) at 930 cm-1.232 821 222

223 22s 226

227 28a

220 2so

231

N. V. Povarova, E. I. Krylov, and V. A. Sharov, Russ. J . Inorg. Chem., 1975, 20, 61. J.-Y. Calves, J. Sala-Pala, J.-E. Guerchais, A. J. Edwards, and D. R. Slim, Bull. SOC. chim. France, 1975, 517. A. Yamamoto, Y. Kano, and T. Yamamoto, J. Organometallic Chem., 1975, 102, 57. M. G . Lyapilina, E. I. Krylov, and V. A. Sharov, Russ. J . Inorg. Chem., 1975, 20, 216. D. Sellmann, A. Brandl, and R. Endell, J . Orgonometallic Chem., 1975, 97, 229. Yu. A. Buslaev, Yu. V. Kokunov, and V. A. Bochkareva, Russ. J . Inorg. Chem., 1975,20,495. J . Chatt, A. J. Pearrnan, and R. L. Richards, J . Organometallic Chem., 1975, 101, C45. A. Yu. Tsivadze, Yu. Ya. Kharitonov, G . V. Tsintsadze, and Zh. D. Petriashvili, Koord. Khim. 1975, 1, 525. K. C. Patil and E. A. Secco, Canad. J . Chern., 1975, 53, 2426. M. S. Novakovskii, V. A. Starodub, and E. V. Golovinova, Rum. J . Inorg. Chem., 1974, 19, 1800. D. P. Riley, P. H. Merrell, J . A. Stone, and D. H. Busch, Inorg. Chem., 1975, 14, 490. L. 1. Pavlenko, A. P. Okorskaya, and A. N. Sergeeva, Russ. J . Inorg. Chem., 1975, 20,460.

Vibrationid Spectra of Some Co-ordinated Ligatzds

355

The i.r. and Ranian spectra of the adducts Os04,C6H6Nand OsO,,C,D,N in solution give some bands due to the free pyridine. Thus some dissociation has occurred, and measurements of band intensities have allowed an estimate to be made of the instability constant at 20 "C (3 x 10-2).233 The i.r. spectrum of some internal (en) modes in the ranges 1120-1150, 850--900, and 455-620 cm-l for [Os(en),C1,]C1,H20 suggests trans-co-ordination of the Os, by analogy with correlations mentioned in the 1iteratu1-e.~~~ 1.r. bands due to co-ordinated NH, were identified in a study of the catalytic effect of [CO"'(NH,),(NO)]~+ within a Y-type zeolite, in the conversion of N O and NH, into N 2 and H,0.235 [C~Br,(en),(m-toluidine)]~+ gives v(NH) of the co-ordinated amino-ligands at 3240, 3140, and 3090 cm-', some 200-250 cm-l lower than in the free ligands. p(CH2) of the en ligand is at 895 and 877 cm-1.23s Shifts in the bands due to v(NH,), v(NH), and v ( S 0 , ) on complexing in the dioximato-complexes of Co"' with sulphanilido-2-pyridine (sd), [Co(NCX)(dioximato),(sd)] (X = 0, S , or Se), suggest that the sd ligand is co-ordinated via the N atom of the N H 2 group on the benzene ring, i.e. (64), the NCX group is co-ordinated via the N in all cases.237 NCX

N t 1.C, H, SO, N H-2 -C,H,N A few group frequencies, e.g. internal modes of the substituted py ring, v(NH), have been given for complexes of the quinquedentate macrocycle (65), typically [Fe1I1(L)X2]Y,[Co'"(L)X]Y,, [Ni"(L)L']Y,, and [Ni"(L)X]Y, where L' = MeCN, etc. and X, Y = halide or p s e ~ d o h a l i d e . ~ ~ ~ 2s3 234 23a 2y 6

237

23M

A. B. Nikol'skii and Yu. I. Dy'achenko, Russ. J . Inorg. Chem., 1974, 19, 031. A. L. Coelho and J. M. Malin, Inorg. Chim. Acra., 1975, 14, L41. K . A. Windhorst and J. H. Lunsford, J.C.S. Chem. Comnt., 1975, 852. C. Varhelyi, J. Zsako and 1. Gergel-Kis, Russ. J. Inorg. Chem., 1974, 19, 004. V. N. Shafranskii and 1. L. Fusu, Russ. J. Inorg. Chenz., 1975, 19, 1202. M. C. Rakowski, M. Rycheck, and D . H . Busch, Inorg. Chem., 1975, 14, 1194.

356

Spectroscopic Properties of'Inorgnnic and Orgirnonietailic Compounds

Fairly dctailed assignments have been given for the following complexes : rir- and trans-[Ir(cn),X,] (X = CI, Br, or T), trans-[Rh(en),X,] (X = C1 or Br), [Ni(en),X21 and [Ni(en),XJ (X = C1 or Br), N-deuteriated [Ir(en),Cl,]Cl, trans-[Co(en),C1,]C1, and [Ni(en),X,]; and C-deuteriated [Ni(en),Cl,]. The Nil" complexes apparently possess the t r a n s - ~ o n f i g u r a t i o n . ~ ~ ~ Some assignments have been given for internal N H3/ND3 modes in some complexes containing [Ni(NH3)J2 I or [Ni(ND,),]*+; see Table 18.240

Table 18 Internal ligarzd uibrations in [Ni(NH,)J2+ and [Ni(ND3)$+ Mlatienitnibers/cm-') [Ni(NHs)e]2-1a 3405 3320 3205 1220 1100 a

PF,- salt;

[Ni(NH3)e]2+ 3400 3320 3205 1625 1210 1 100

[Ni(NH3),J2+-

-

BF,- salt;

3390 3303 3 200 1615 1215 1 loo -

'-

[N i (N D,)J2

2523 2430 2350 1100

-

-

(all

Assignnien I

4NH,), OH,), 4NH,), WH,), a(NH3), &NH,), p(NH,),

T2,

A,

E, T2u

Eg

AlU

T20

C10,- salt.

Pyridine internal modes were listed for [Ni(py),(NO,),], [Ni(NO,),(py),], and [Ni(NO,),(py),], as well as NO,- bands.241 N o definite structural conclusions were drawn. The values of some py ring wavenumbers have been used to suggest that [ML(ClO,),] (M = Ni, Cu, or Hg) contain two co-ordinated N atoms [L = (66)]. In [HgLBrIBr only one py N atom is co-ordinated; however, in AgL(C10,) the L ligand is unco-ordinated.242

NCS

The new complex (67) shows a strong band at 1668 cm-' typical of co-ordinated imino-groups, plus two v(C=N) absorptions, which are assigned to cis-SCN groups.243 23D zpl

242

243

1. B. Baranovskii and G . Ya. Mazo, Huss. J . Inorg. Chent., 1975. 20, 244. J . M . Janik, J. A. Janik, and G. Pytasz, J . Rarnan Spectroscopy, 1975, 4, 13. M . Prost, P.-C. Versaud, and P. Pichat, Cotnpt. rend., 1975, 280, C , 451. G. Anderegg, N. G . Podder, P. Bhuenstein, M . Hangartner, and H. Stunzi, J . Coordination Chrtn., 1975, 4, 267. N. F. Curtis, J.C.S. Dalton, 1975, 91.

Vibrational Spectra of'Some C'o-ordinated Ligands

357 Shifts in the amide-I and -11 bands in the complexes [Cu(ppa)CI] and [Ni(ppaH),X,] [X = Br or NO3; ppaH = N-(:2'-picolyl)-2-pyridylacetamide] suggest N-co-ordination for the Cu, and 0-co-ordination for the Ni complexes ; see (68) and (69).244

1.r. spectra of Ni complexes containing oxalodihydrazide or malondihydrazide, and amino-acid residues of glycine, serine, or methionine, show coo-) at 1400-1590 cm-l and p(NH2) of amino-acid at 880 cm-l. Thus all are shifted to lower wavenumbers with respect to the free l i g a n d ~ . , ~ ~ A selection of characteristic bands due to the chelating amino-ligands were assigned in [CI(C,F,),Pd(chel)l, where chel = en, bipy, phen, or propylene1,2-diarni11e.~~" Thus en gave bands at 3360, 3285. and 1580 cm-l, due to v(NH) and 6(NH2). v(NH) in K,[Pt(NH,),] are at 3230 and 3310 cm-l in the i.r,, compared to 3060 and 3160cm-l in [Pt(NH3)6]C14.247 A number of assignments have been given for the co-ordinated hydroxylamine in tran~-[Pt(NH,OH),Cl,].~~8 A group-frequency assignment has been made for the complex [Pt{NH(Me)OH},] [PtCl,]. 248 Force-constant calculations on free NH3 and [Zn(NH,),]2+ showed that kinematic coupling effects alone could not give reasonable results. Modifications to the NH3 force field were necessary.25o [Cd(C204)],N2H4,&H,0 gave v(N-N) at 980 cm-l, believed to be indicative of bridging N2H4. The C 2 0 4ligand was apparently bidentate.251 The amide-I1 and -111 bands in the salicylhydrazide complexes MLs (M = La, Pr, Nd, Sm, Er, or Y) are at 1520 and 1249 cm-l, respectively.262Group-frequency assignments were made for the lanthanide (except Ce, Pm, and Lu) complexes of dipivaloylmethane and pyrazine, i.e. [ L n ( d p m ) & ~ ) ] . ~ ~ ~ The i.r. spectra of [Al(BH4)3],4N2H4show that the BH4 is ionic in character, with the N2H4co-ordinated weakly to the A1 [v(N-N) at 920cm-ll. For the hydrazine adduct [AI(BH,),],l .1N2H4, the BH, is mainly covalent, and the 044

m 246 247 248 240 260 251 262 2~

M. Nonoyama, J . Inorg. Nuclear Chem., 1975, 37, 1897. Ya. D . Fridman, 0. P. Svanidze, N. V. Dolgashova, and P. V. Gogorishvili, R i m . J . Inorg. Chem., 1974, 19, 1809. R. Uson, J. Fornies, and R. Navarro, J. Organomerallic Chem., 1975, 96, 307. B. Klein and L. Heck, Z . anorg. Chem., 1975, 416, 269. M.A. Sarukhanov, M. E. Bedrina, and N. A. Parpiev, Huss. J . Inorg. Chpm., 1974, 19, 1362. M. A. Sarukhanov and A. I. Stetsenko, Russ. J . Inorg. Cheni., 1975, 20, 118. S. J. Cyvin, B. N . Cyvin, R. Andreassen, and A. Miiller, J . MoI. Structure, 1975, 25, 141. E. A. Nikonenko, E. I. Krylov, and V. A. Sharov, Russ. J . Inurg. Chenl., 1975, 20, 484. A. Sengupta and N . K . Dutt, J . Inorg. Nuclaar Chem., 1975, 37, 270. M. S . Ansari and N . Ahmad, J . Inorg. Niic,lt.ar Chcm., 1975, 37, 2099.

358

Spectroscopic Properties of Inorganic and Organometaflic Coinpouiids t

equilibrium (70) was suggested. v(NN) in the latter is at 910cm-*; no v(AIN) can be detected.254 Some approximate assignments have been made for the GeCI, adducts of benzoyl-, nicotinoyl-, and pic~linoyl-hydrazide.~~~ An i.r. study [v(NH)] of the H-bonding in [Me,SnX,],nDMP (n = 1 or 2; X = C1 or Br) and [Me,SnCI],DMP, where DMP = 3,5-dimethylpyrazole, has been

+

0ximes.-v(NH), v(OH), and v(C-N) v(C=C) wavenumbers have been listed for some Fe, Co, and Ni complexes of the types [Fe"(H2R1R2L)](CI0,),, [CO'~'(H,R~R~L)](CIO,)~, [ C O ~ ~ ' ( R ~ R ~ L ) ] ( C I[Ni(H2R1R2L)](C10J2, O~), and [NiLv(R1R2L)](C1O4),.H,R1R2L is the sexidentate oxime ligand (71), where R1 and R2are Me, Et, or Ph.257 Some group-frequency assignments have been made in [Co(NCO)(dmgH),(amine)], where dmgH = dimethylglyoximato and amine = p-NH2C6H4X (X = H, OMe, OEt, Me, C1, Br, or I), o-NH,C,H,OMe, or rn-NH2C6H40Me.268 Group-frequency i.r. assignments have been given for K[CoX(NCO)(dmgH),] and [Co(NCO)(dmgH),A] (X = CI, Br, I, NO2, NCO, or OH; A = NH, or

H20); dmgH, = dimethylglyoxime).26DSimilar data were also reported for Co"' complexes containing both dimethylglyoxime and nicotinamide. The nicotinamide is possibly co-ordinated via the N atom.260Many, scarcely assigned, i.r. data have been listed for bis(diniethylg1yoxiniato) complexes of CO"' and Rh"' also containing Dubious group-frequency assignments have been made for the bis(dimethy1glyoximato)cobalt(m) complexes [CoX(dingH),L] (X = C1, Br, or I ; L = MeCN 2sL

z67 268

P6B

z60

J. Samanos and S. J. Teichner, Bull. SOC.chiin. France, 1975, 87. G . V. Tsintsadze, E. A. Kvezereli, and A. P. Lezhava, Rum. J . Inorg. Chein., 1975, 20, 524. R. Ettorre and G . Plazzogna, Inorg. Chiin. A d a , 1975, 15, 21. J. G . Mohanty, R. P. Singh, and A. Chakravorty, Inorg. Chem., 1975, 14, 2178. A. A. Popova, V. N. Shafranskii, and Yu. Ya. Kharitonov, Russ. J. Inorg. Chenr., 1975, 20, 562. V. N. Shafranskii and A. A. Popova, Zhur. obshchei Khim., 1975,45, 116. D. G . Batyr, M . P. Starysh, V. N. Shafranskii, and Yu. Ya. Kharitonov, Russ. J. Inorg. Chenz., 1974, 19, 1517. G . P. Syrtsova, V. D. Brega, L. N. Istru, T. S. Holgar, and Yu. Ya. Kharitonov, Rum. J . Inorg. Chem., 1974, 19, 1348.

Vibrational Spectra of Some Co-ordinated Ligands

359

or C6HllCN; and dmgH = dimethylglyoximato).262Sundry ligand wavenumbers were listed for the characterization of some protonated alkylcobaloximes [Co(dmgH)(dmgH2>(R)CI],H20 (R = Me, Et, Prn, Pri, or C6H11).203 The i.r. spectra (300-4000 cm-l) of Ni" and Ni"' complexes with dimethylglyoxime or a-benzyldioxime, containing py or its C1- or Br-substituted derivatives, have been partially assigned, compared, and possible structures Benzoylacetone dioxime [bado, (72)] forms a complex Cu(bado),, in which v(C=N) is at 1600 cm-l, compared to the value for the free ligand of 1620 cm-1.z6h Ligands containing >C=N- Groups.-Shifts in v(C=N) of PhCH=NC6H4R on complexing to TiCI, or SnCI, may be related to the electronic properties of the group R (= H, p-Me, p-OMe, p-Br, p- I , or m-NO,), showing that these are transmitted to the azoniethine group CH=N,266 Adducts of TiC14 and SnCI, with saiicylideneanilines (73; K = H, p-Me, p-OMe, p-C1, p-Br, p-I, m-NO,, o-Me, 2,3-Me2, or 2,4,6-Me3) all show a characteristic shift of v(C=N) to higher wavenumber on co-ordination. This is typical behaviour for Schiff-base a d d u c t ~ . ~ ~ ~ Group-frequency i.r. assignments have been listed for [(MeC(NH,),}TaX,],2MeCN (X = Cl or NCS) and [Ta(NCS)(N=C(NH,)Me),{ MeC(NH)(NH,)}],.268 The complexes [{M)N=C=C(CN)C(CN),R] show two bands due to the N=C=C unit at cn. 2150 cm-l and ca. 1300 cm-l in the i.r. [(MI = CpFe(CO),, CpMo(CO),(PPh,), or CpFe(CO)(PPh,); R = alkyl or aryl].260

The pyridine ring-stretching wavenumber (1 570-1595 cm-l) has been listed for a series [Mn(L)X,] (X = Cl, Br, C104, or BPh,), [Mn(L),]X, (X = C104 or BPh,), and [Mn,(L),]X, (X = CIO, or BPh,), where L is a quadridentate nitrogenous ligand, typically [74;R = (CH,),, (CH,),, or o - p h e n y l e ~ ~ e ] . ~ ~ ~ [Mn(tetraphenylporphine dianion)(4-methylpiperidine)(NO)] shows v(N0) at 1740cm-l in the i.r.271(75; R = C6HI1) gives a u(C=N) band at 1632, another at 1592 crn-', and v(C0) at 1919 D G . Ratyr, M. P. Starysh, V. N. Shafranskii, and Yu. Ya. Kharitonov, Russ.J. Inorg. Chem.,

lea

2a3 264

2116 2(i6

267

2770

271

1974, 19, 704. A. L. Crumbliss and P. L. Gans, Znorg. Chem., 1975, 14, 486. D. G. Batyr, V. D. Brega, L. Ya. Kistruga, and Yu. Ya. Kharitonov, Koord. Khirn., 1975, 1, 129. A. H. I. Ben-Bassat, I . Adato, and S. Sarel, J . Inorg. Nuclear Chem., 1975, 37. 2349. V. A. Kogan, A. S. Egorov, and 0. A. Osipov, Russ. J . Inorg. Chenz., 1974, 19, 980. A. S. Egorov, V. A. Kogan, 0.A. Osipov, and I. G. Strizhkova, Russ. J . Znorg. Chem., 1975, 20, 365. H. Bohland and E. Harke, Z . anorg. Chcwi., 1975, 413, 102. R. Ruei Su and A. J. Wojcicki, Inorg. Chon., 1975, 14, 89. B. Chiswell, Znorg. Chim. A d a , 1975, 12, 195. P. L. Piciulo and W. R. Scheidt, Inorg. Nuclear Chetn. Letters, 1975, 11, 309. Y. Yamamoto and H. Yamazaki, J. Organometallic Chem., 1975, 90, 329.

360

Spectroscopic Properties of Inorganic and Organometallic Compouncls

In the course of the preparation of new complexes of Fe"' with tris-

(4-[6-R-2-pyridyl]-3-azabut-3-enyl)amine(76), i.r. spectroscopy was used as a sensitive test of purity in partially methylated

\

/

Compound (77) gives four characteristic bands (860, 1000, 1200, and 1620 cm-l) of the ring system. When X = OMe, v(CH) is at 2783 cm-l; when X = OAc, v,, Y,, of the COO group are at 1348 and 1600cm-l (therefore the acetate is unidentate); when X = NO, v ( N 0 ) is at 1685 Resonance Raman spectra have proved to be very useful in studying porphyrin and related complexes. Thus, resonance Raman spectra of FeS+ and Pd2+ octaethylporphyrins, and their a'-, /?-, f-, and 8'-deuterio-derivatives havc been The bands at 1594 (p) and 1567 (dp) cm-l were insensitive to deuteriation of the methine hydrogens, and were therefore assigned to modes of the pyrrolic ring. Resonance Raman spectra have also been reported for nitric oxide haemoglobin in the presence and absence of inositol h e x a p h o ~ p h a t e .The ~ ~ ~behaviour of the depolarized band at 1643 cm-', and that at 1633 crn-', showed the sensitivity of this region to the quaternary structure of the protein. Similar data were obtained for metalloporphyrins of Ni2+,Co2+,Co3+,Pd2+, Fe3+, Cu2+,and Zn2+. Since the electronic transition involved is mainly localized on the ring system, the enhanced bands are mainly those of the ligand.277 Preliminary normal-co-ordinate analyses have been based on resonance Raman data from haem protein ~ctamethylporphyrin.~~~ 1.r. wavenumbers were listed for the characterization of Co, Ni, Cu, and Zn complexes of Schiff-bases derived from salicylaldehyde and 4-phenyl-2-aminothia~ole.~~~ v(C=C) were reported for complexes of Co, Cu, Ag, and Zn with N-alkylpyrazole derivatives (78; R = H, Me, or Br).280 The complexes where R = H or Me generally show v(C=C) in the same region as the free ligand, but when M = Cu, and when R = Br, this mode is at 1540-1545 cm-l, i.e. the ally1

9i6

2i7 27M 27@

280

M. A. Hoselton, L. J. Wilson, and R. S. Drago, J. Amer. Chem. Soc., 1975, 97, 1722. J. W. Buchler and K. L. Lay, Z. Naturforsch., 1975, 30B, 385. M. Kitagawa, Chem. Phys. Letters, 1975, 30, 451. A. Szabo and L. D. Barron, J. Amer. Chem. SOC., 1975, 97, 660. T. Kitagawa, H. Ogoshi, E. Watanabe, and Z. Yoshida, J. Phys. Chem., 1975, 79, 2629. P. Stein, J. M. Burke, and T. G. Spiro, J. Amer. Chem. Soc., 1975, 97, 2304. B. Dash and S. K. Mahapatra, J. Inorg. Nuclear Chem., 1975, 37, 271. K. Fukushima, T. Miyamoto, and Y . Sasaki, Inorg. Chim. Acra., 1975, 15, 105.

Vibrational Spectra of Some Co-ordinated Ligands

361

group as well as the ring N is co-ordinated. N.m.r. spectra were unable to confirm this, however. Resonance Raman spectra of Co"-imidazole complexes have been taken as models for the behaviour of metalloproteins. The resonant enhancement is small compared to that observed in haem protein and carotenoid complexes.281

(78)

(794

(79b)

(79c)

In-plane ring modes in the resonance Raman spectra of Co myoglobins and porphyrins are insensitive to the nature of the solvent (py, pip, D M F , Me,CO), as also are those due to the axial ligand.282 Group-frequency assignments were made for K[IrLCl,] and K[IrL'CI,] (L = HN=CH-CH=NH, L' = DN=CH-CHZND).~'~ v(C=N) is at 1506 cm-l for the H species. Selective deuteriation of the four complexes (79a; X = H or HCO), (79b), and (79c) gives i.r. spectra which reveal similarities to those of p-diketonates, indicating similarities of bonding.284 v(NH) is between 3170 and 3213 cm-l and v(C=N) between 1647 and 1668 cmin the polyalkyl-l,4,8,11-tetra-azacyclotetradeca-4,11 -dienenickel(ii) perchlorates, e.g. (80).285

1.r. spectroscopy has been used to characterize several Ni" and Cu" complexes of neutral quadridentate Schiff bases derived from condensation of 1,3-diarninopropane or 1,3-diaminopropan-2-01 with 2-formylpyridine or 2-a~etylpyridine.~~~ Resonance Raman spectra of 1,2,3,4,5,6,7,8-0ctamethylporphyrin,1,3,5,7tetramethylporphyrin, and niesotetraphenylporphyrin and its Ni, Pd, and C u 281

2R6 28e

C. M . Yoshida, T. B. Freedman, and T. M. Loehr, J . Artier. Chem. Suc., 1975, 97, 1028. W. H. Woodruff, D. H. Adarns, T. G . Spiro, and T. Yonetani, J . Amer. Cheni. Suc., 1975, 97, 1695. I. B. Baranovskii, R . E. Sevast'yanova, G. Ya. Mazo, and V.I. Nefedov, Russ.J. Inurg. Chem., 1974, 19, 1535. W. H. Elfring and N. J . Rose, Inorg. Chem., 1975, 14, 2759. R. A. Kolinski and €3. Korybut-Daszkiewicz, Inorg. Chim. Acta, 1975, 14, 237. K . Dey and S. K . Sen, J . Indim Chem. Soc., 1975, 52, 261.

3 62

Spec f roscopic Properties of Inorganic and Organometallic Compounds

chelates have been reported.287 Several anomalously polarized vibrations ( p > 2) were found for nickel tetraphenylporphyrin in CS2 solution. From these it was deduced that the symmetry of the molecule in solution is reduced from Ddh. The resonance Raman spectra of the Dlh and Dzaforms of octaethylporphinatonickel(I1) show bands at 1660, 1609, 1581, and 1552 cm-l which are structuresensitive. An empirical correlation between the position of the anomalously polarized line at about 1590 cm-’ and the distance of the centre of the porphyrin ring from the pyrrole nitrogen was applied to haem protein resonance Raman data.288 Bands due to the bridging formamidido ligands have been assigned as follows in the complexes [(l ,3-7-C3H6)PdXI2,where X = p-RC6H4N=CH-NC6H4R-p; R = Me, 1612, 1573, 1354, 1228cm-l; R == H, 1608, 1554, 1358, 1225cm-I; and R = CI, 1603, 1554, 1363, and 1228 1.r. bands characteristic of the NN’-diarylformamidido ligand were listed for [Pd(PPh,),(p-RC6H4NCH=NC6H4R-p)CI] (R = H, Me, MeO, or CI) and [Pd(p-MeC,H,N =CH =NC,H4Me-p),],.2Q0 Raman spectra of the solid haematoporphyrin free base H,hem, the diacid [H4hemI2+, the species [H,heni]2+[PtC1,]2-, the ‘sitting atop’ complex cisPt(H,hem)CI,, and platino-haematoporphyrin Pt(hem) have been compared. Diagnostic bands for the different species were noted in the 1300-1650cn~-1 region [v(C=C), v(C=N)]. The spectra provided confirmatory evidence for the existence of the ‘sitting atop’ complex.2Q1 Some high-quality resonance Raman spectra have been obtained for the complexes Cu-aetioporphyrin-I and -1V in dilute solution. Several anomalously polarized bands ( p > $) show dispersion, interpreted as arising from reduction of the chroniophore symmetry from the idealized D4,. Solution data for the two species are consistent with C,, and Ctersymmetries, respectively. Definite assignments await the results of a normal-co-ordinate analysis.2Qz Resonance Raman data for Cu-l,3,5.7-tetramethylporphyrin and Cu1,2,3,4,5,6,7,8-0ctamethylporphyrinshow that in solution their spectra are consistent with the symmetries C,, and Dlh, respectively. A band ca. 343 cni-* is sensitive to Me substitution, and may be due to S(CCC) in the pyrrole rings of the porphyrin; another cn. 1372 cm-l is found in all these and related compounds. I t is probably a ring A few ligand bands have been listed for the characterization of: L,Agk, L2AgN03, L,ZnBr2, L,CdBr,, L3Cd2Br4,LIIgCI2, L,CoCI,, [LH],[CoCl,], and cis-[Rh(CO),Cl(L)], where L = (p-MeC6H,NH)(p-MeC6H4N=)CH.2Q4 2n7

28D 2*0

?Oa

*04

R. Mendelsohn, S. Sunder, and H. J. Bernstein, J . Raman Spectroscopy, 1975, 3, 303. L. D. Spaulding, C. C. Chang, N.-Y. Yu, and R. H. Fenton, J . Amer. Chem. SOC.,1975, 97, 2517. L. Toniolo, T. Boschi, and G . Deganello, J . Orgunometaffic Chem., 1975, 93, 405. L. Toniolo, G . Deganello, P. L. S a n d h i , and G. Bombieri, Inorg. Chim. Acta, 1975, 15, 11. M. Berjot, L. Bernard, J. P. Macquct, and T. Theophanides, J. Ranian Spectroscopy, 1975, 4, 3. R . Mendelsohn, S. Sunder, A. L. Verrna, and H. J. Rernstein, J . Chem. Phys., 1975, 62, 37. S. Sunder, R. Mendelsohn, and H. J. Bernstein, J . Chem. Phys., 1975, 63, 573. G . Minghetti, G . Banditelli, and F. Bonati, Inorg. Chim. Acra, 1975, 12, 85.

Vibrational Spectra of Some Co-ordinated Ligands

363 Partial Raman and i.r. data, plus some assorted assignments, have been reported for HgC12,2(uracil), and for 5-mercuri-uridine 5 ’ - t r i p h o s ~ h a t e . ~ ~ ~ A variety of possible structures were discussed, and electrophilic attack at N-3 postulated. Neutral 3 : 1 adducts of N-alkylsalicylideneirnines, L = (sal-R)H, with YCI, show v(C-0) at 1525-1530, v(C=N) at 1635-1640, and v(O.-H.-N) at 3050-3100 C M - ’ . ~ ~ ~ v(C=N) is at about 1620 cm-l in the Schiff-base complexes [Ln(aaH-R),NO,](NO,), and [Ln’(aaH-RR),NO,](NO,), [Ln = La, Pr, or Nd; Ln’ = Yb; aaH-R = 2,4-pentanedioneanil (R = Ph) or 2,4-pentanedionebenzylimine ( R = CH2Ph)].2g7

Cyanides and 1socyanides.- A review on cyanide complexes of the early transition metals includes a compilation of and discussion on pertinent i.r. and Raman data.298 1.r. bands were found in the region 2068--2102cni--’ for Lit derivatives of phenylacetonitrile and acetonitrile. These were assigned to v(C=N) of the species [RCH=CH=N]-Li I- (R = Ph or H). Some higher-wavenumber features are thought to be due to ‘dimeric’ anions, e.g. (81).299 In the adduct MgCI,,ZNCCI, v(C=N) gives only one band, at 2245 cm-l, showing the equivalence of the ClCN molecular sites in the lattice. This situation differs from that in MgCl,,NCCl, where site-spliiting gives features at 2246 and 2257 cm-l. The v(C=N) wavenumbers, together with the very weak feature due to v(CC1) (765, 766 respectively), suggest that these adducts have a polymeric v(CN) in [MCI,(NCCI),] (M = Zr or Hf, n = 1 or 2) is in the region expected for M-NCCI co-ordination (Table 19).301

Table 19 u(CN) wai~ertumbers/cm-lirr [ MCI,(NCCI),] n 1 2 1 2

M Zr Zr Hf Hf

V(CN)

G(CICN)

2250,2258 2249, 2257 2250, 2260 2251, 2261

424 43 2 426 427

Trends in v(CN) and u(MC), and the CN and MC bond lengths have been compared and discussed in terms of CT- and n-bonding in a number of d 3 , d 4 , P , and d e complexes of CN with V, Cr, Mn, Fe, and CO.~O~ u(CN) in crystalline K4[V(CN)7],2H20is at 2100 and 2065 cm-l. These values are close to those for K,[V(CN),], the combined effects of increasing the oxidation state and co-ordination number cancelling each other 20R 207 298

209

aoo 3oL :Io2

303

S. Mansy and R. S. Tobias, Inorg. Chem., 1975, 14, 287. 11. Kuma and S. Yamada, Inorg. Chim. Acta, 1975, 15, 213. S. K. Agarwal and J. P. Tandon, J. Inorg. Nuclear Chent., 1975, 37, 1994. W. P. Griffith, Coordination Chcm. Rev., 1975, 17, 177. I. N. Juchnovski and I. A. Binev, J. Organometallic Chrm., 1975, 99, 1. J. Maccordick, Bull. SOC.chim. France, 1975, 107. J. Maccordick and A. Westland, Bull. Soc. chim. Frtinc.~,1975, 1117. S. Jagner, Acta Chenr. Scand. ( A ) , 1975, 29, 255. V. V. Dovgei, A. N. Sergeeva, and K. N. Mikhalevich, Russ. J. Inorg. Che~n.,1974, 19, 832.

3 64

Spectroscopic Properties of Inorganic and Organometallic Compounds Me0 I (OC),Cr -NC-C-H

I

I'll (82)

(81)

[V(C6H6)2(C6HllNC)2]BPh4gives v(NC) bands at 2120 and 2150 cm-l i n the i.r.,04 Octacyano-complexes of Nb'", Nb'", Mo", and Wv have been investigated by i.r. and Raman spectroscopy. The presence of only one polarized Ranian band in aqueous solution due to v(CN) is indicative of a D4dstructure."O" Compound (82) gives v(NC) as a weak, broad i.r. band at 2265 cm-1.3n08 v(NC) was also listed for the isomers (83a) and (83b).,07

F,,C

F,C'

/

'X

i'F, (831)

c F3 8317)

A large number of new complexes of nitriles have been prepared by substitution with an aromatic or an a@-substituted nitrile, giving compounds with the formulae [Mo(CO),(PR,),(nitrile),l (R = Ph or Bu) and [Mo(CO),(PBu,),(nitrile)]. A full study, including solvent effects, was made of the v(C=N) modes. These are substantially lowered in the cis-dinitrile series by m - e f f e c t ~ . ~ ~ ~ ~~U~S-[M(M~NC),(P~~PCH~CH~PP~~)~] (M = M o or W) show v(NC) 221331 cm-l lower than in MeNC itself, these being the largest shifts reported so far.30e v(CN) bands in the nitrile complexes [MoCl,(NCR)(PR,),] lie in the range 2260-2280 crn-l.,l0 The i.r. spectra of metal complexes of the nitroprusside ion, [MFe(CN),(NO)], where M" = Mn, Fe, Co, Ni, Cu, or Zn, support the interpretation of X-ray structural data, in providing evidence for the presence of a bridging nitrosyl group.311 Two v(CN) bands are seen in the i.r. spectra of [M(CO),XL,], where M = Mn, X = Br or I ; M = Re, X = Br; L = u-CBH4(CN),. One band is at a higher G. Fachinetti and C. Floriani, J.C.S. Chem. Comm., 1975, 548. P. M . Kiernan and W. P. Grifiith, J.C.S. Dalton, 1975, 2489. 306 E. 0. Fischer, S. Fontana, and U. Schubert, J. Organomerafiic Chem., 1975, 91, C7. J. L. Davidson, M. Green, J. A. K. Howard, S. A. Mann, J. 2. Nyathi, F. G . A. Stone, and P. Woodward, J.C.S. Cheni. Comm., 1975, 803. F. Hohmann and H. tom Dieck, J . Organornetallic Chem., 1975, 85, 47. 308 J. Chatt. A. J. L. Pombeiro, R. L. Richards, G . H. Royston, K. W. Muir, and R. Walker, J.C.S. C ~ P I IComm., I. 1975, 708. 310 M. W. Auber, J . Chatt, G . J . Leigh, and A. G . Wedd, J.C.S. Dalton, 1975, 2639. m D. B. Brown, Znorg. Chem., 1975, 14, 2582. 304

30s

Vibrutional Spectra of Some Co-ordinated Ligands 365 wavenumber than in the free ligand, the other is unshifted. Thus the complexes contain one co-ordinated and one unco-ordinated CN group.312 [Re,(CO),X,L] (X = CI or I) give only the feature due to the co-ordinated CN; they are therefore formulated as (84).

v(CN) in the i.r. spectra of M,[Fe(CN),] (M = H, Li, or Na) shows a splitting which is directly related to the observed Mossbauer quadrupole splitting (A&)) for these, due to the interaction of the Li+ and Na+ ions with the CN- ligands of octahedral Fe(CN),3-. These are similar to those with H+, which is, in fact, hydrogen-bonded. The larger alkali-metal ions cause no splitting of v ( C N ) . ~ ~ ~ Displacement of v(CN) by 30cm-l to higher wavenumber on passing from K,[Fe(CN),] to Eu[Fe(CN),] indicates the existence of a bridging interaction Fe-C=N-Eli. A similar shift was seen in v(FeC), although 8(FeCN) was little altered.314 Similar shifts were also seen in all of the Ln[Fe(CN),] species, except when Ln = Pm or Y ; these compounds were not CN wavenumbers have been listed for [FeCl(cis-CNR),L3]C104 and [FeCI( ~ ~ C - ~ - M ~ C ~ H , N C ) ~ (where P P ~ ~R) ~=] substituted +, phenyl and L = diethylp henylphosp honi te.sls The reaction of MeCN with trans-[FeCl,(depe),] gives trans-[FeCl(MeCN)(depe),]+, where depe = Et2P(CH,),PEt2. This has v(CN) lower by 12 cm-l than for the free ligand. [Fe(MeCN),(depe),I2+ gives a higher v(CN), due to the higher formal charge on the metal. Malononitrile forms [FeCIL(depe),]+, for which a reduction of 121 cm-l in v(CN) was reported. This very large reduction suggests unusual bondingS3l7 [Ru(NH3)J3+ reacts with aldehydes to give nitrile complexes [(NH,),Ruof (NCR)],+ (R = Me or Ph). 4CN) is at about 2 2 0 0 ~ m - l . lnteraction ~~~ HCN with [ R U ( N H ~ ) ~ ( H ~ Oaffords ) ] ~ + [Ru(NH,),(NCH)]~+,having v(CN) at 2085 cm-’, compared to the value of 1998 cm-l for [ R U ( N H , ) ~ ( C N ) ] + . ~ ~ ~ Mixed valence, bridging cyanogen complexes [(NHS),RuNCCNRu(NH,),l”$ have been synthesized. When n = 4,v(CN) is at 1960 (i.r.), 2185 (Raman) cm-l. Much higher i.r. values were found when n = 5 or 6.320 512 314 316 316

317

31H :i20

J. G. Dunn and D. A. Edwards, J. Organometallic Chrm., 1975, 102, 199. A. N. Garg, Z . Nnturforsch., 1975, 30b, 96. M. C. Bonnet and R. A. Piris, Bull. Sac. chim. France, 1975, 1062. M. C. Bonnet and R. A. Piiris, Bull. SOC.chim. France, 1975, 1067. G. Albertini, E. Bordignon, A. A. Orio, and G . Troilo, Inorg. Chem., 1975, 14, 238. J. M. Bellerby and M . J. Mays, J.C.S. Dalton, 1975, 1281. K. Schug and C. P. Guergerich, J . Amrr. Chem. Soc., 1975, 97, 4135. S. S. Isied and H. Taube, Znorg. Chem., 1975, 14, 2561. G . M. Tom and H. Taube, J . Arner. Chem. Soc., 1975, 97, 5311.

3 66

Spectroscopic. Properties of Inorganic and Organometaiiic Conipourzds

[Co(CN),(H,O)]'- and CiS-[cO(cN),-,(H,o),]'3-"'(n - = 2 or 3) all give terminal v(CN) (ca. 2140 cm-l) initially, but, in addition, bridged species [v(CN) at about 2210 cm-'1 are formed by p o l y m e r i ~ a t i o n . ~ ~ ~ An i.r. study in the v(N=C) region has established the existence of a fourth isomeric structure for [Co(ArNC),]X, where Ar = 2,4,6-Me,C6H,; X -- C104 or BF4.,** When [Co(CNPh),]CIO, is recrystallized from CHCI, solution, conformational isoinerisni is shown. This work has been extended to include para-substituted isocyanides p-XC,H,NC (X = F, C1, Br, I, or Me). Using v(C=N) as the primary indicator, only one geometry is found for these complexes, but three for those of PhCN, as shown by the differences in the v(C=N) p a t t e ~ n s . 3 ~ ~ A complex containing r-bonded benzonitrile was postulated from thc observation of a band at 2123 cm-l in the reaction product of [Co(POctrl,),H(N,)] with benzonitrile, i n addition to a feature a t 2205 cn1-I due to [Co(POctn3),H(NCPh)]. This could not be identified positively, but a possible formulation is [(OC~"ZP)~CO(V-N ~Cph)].~,~ v(CN) data were used to show the unidentate co-ordination of (dinitrile) i n [M"(dinitrile)B2+][SbCI,-], (M = Co or Ni; dinitrile = p-NCCBH4CN) but bidentate in [M"(dinitri~e)32+][sbC~6-],[M = Co, Ni, or Cu; dinitrile = NC(CH,),CN; n = 2 or Trigonal-bipyramidal geometry, with the CN groups in apical positions, has been deduced from the observation of only one i.r. band due to v(CN) i n the i.r. spectra of [Ni(CN),L,], where L = PMe,, Me,P(OMe), MeP(OMe),, or P(OMe),. For [Ni(CN),L,], v(CN) gives 1 4 bands in the range 21032 149 v(CN) is given at 2095-21 15 cm-l in [Ni(CN)(L),]CIO,, [Ni(CN),(L),], [Ni(CN),(Ph,PEt),], and Ni(CN),(L'),, where L = Ph2PCH2CH,SR (R = Me, Et, or Ph), L' = (85). The last three groups have trans-geometry for the CN groups.327

Reduction of K,[Pd(CN),] in liquid ammonia produces a variety of PdO compounds, salts of [Pd(CN),I2-. v(CN) is in the range 2028-2055 cm-l, with the lower values found for the largest cations. Linear, Dmh,co-ordination was suggested. The decreased v(CN) compared to Pd" analogues was rationalized 321

323

333 324

921

920

327

L. Viaene, J. D'Olieslager, and G. de Jaegere, J . Znorg. Nuclear Cheni., 1975, 37, 2435. C. A. L. Becker, Inorg. Nuclear Cheni. Letters, 1975, 11, 295. C. A. L. Becker, J . Inorg. Nuclear Chetir., 1975, 37, 703. W. R. McWhinnie, J. D. Miller, J. B. Watts, and D. Y . Waddan, J . Inorg. Nuclear Cheni., 1975, 37, 2329. A. P. Zuur, P. L. A. Eversteijn, and W. L. Groeneveld, Inorg. Nuclear Chem. Letfers, 1975, 11, 35. E. J. Lukosius and K. J. Coskran, Inorg. Chem.. 1975, 14, 1922. P. Rigo and M. Bressan, Znorg. Cheni., 1975, 14, 1491.

Vibrationnl Spectra o j Sonte Co-ordinnted Ligaiids

367

in terms of increased back-bonding. In the presence of phosphonium salts at temperatures below - 40 "C [PdPh(CN),]*- is formed; i.r. and Raman wavenumbers were [Pt(CNR1),(CNRz)),][Pt(CN),] and [Pt(CNRl),][Pt(CN),] (R' = Ph, 4-Et- or 4-MeO-CeH4, 2,3-Me,C,H3, or cyclohexyl ; R2 = 4-EtC,H4, 2,6-Me,C,H3, azobenzene-4, But, or Ph) all give solution i.r. spectra with the expected numbers of v(CN) bands and v(C=NR) bands. Their solid-phase spectra were much more complicated.32D Linkage isomers [HPt(PEt3),(X=YBPh3)], where X=Y = C=N or N=C, were prepared. Both complexes gave v(CN) at 2192 cm-l. The complexes were differentiated by the values of v(PtH), however, the Pt-C species being at 2082 and the Pt-N at 2236 cm-l, consistent with its lower t r a n s - i n f l ~ e n c e . ~ ~ ~ Oxidative addition of cyanogen halides to [Pt(PPh,),] yields niixed trans[Pt(PPh,),(X)CN] complexes (X = halide), although it can be replaced by N3, CNO, NCS, or NC0.331 Some isocyanide complexes of PtO of the type [Pt(CNBut),AB] have been prepared. v(CN) is 50-100 cni-l below the value for the free ligand, compared with 60-85 cm-l higher for the Pt" complexes. Most of the observations had to be made in solution because of isolation v(NC) has been listed for the following new isocyanide complexes: [(p-MeC,H,NC)AgCI] 2160 cin-l, [(CBHIINC)AgCl] 2180 cm-l, [(C6Hl1NC)AuCI] 2241 The shift of v(C=N) from 2275 to 2200cm-1 on the formation of the Cd complex of malononitrile, [Cd(NCCH2CN)2]C12,6H20, was used as evidence for the chelating interaction (86). For complexes with NC(CH2),CN (n = 3, 4,or 5 )

{ClCd[NC(CH,),CN]CdCl}Cl,, v(C=N) is at about 2300 cm-l, consistent with linear bridging Cd-NC(CH2),,CN-Cd.334 Nitrosy1s.-1.r. spectroscopy has been used, with other techniques, in a study of the reaction of NO and N 2 0 with surface Cr". In the case of NO, a very stable dark brown diamagnetic surface complex )Cr(N0)2 is formed, v(N0) being at 1745, 1680 cm-1.336 v(N0) is found between 1725 and 1695 cm-l in nitrosyl complexes of Cr3+ containing salicylaldoxime, a-nitroso-/3-naphthoI, 8-hydroxyquinoline, and x8 sL'8

YBo

331 354

y33 y:io

535

R. Nast, J. Bulck, and R. Kramolowsky. Chenr. Ber., 1975, 108, 3461. H. J. Keller and R. Lorentz, J . Organometallic Chem., 1975, 102, 119. L. E. Manzer and W. C. Seidel, J . Amer. Chem. Soc., 1975, 97, 1956. W. Beck and K. Schorpp, Chem. Ber., 1975, 108, 3319. G . A. Larkin, R. Mason, and M. G. H. Wallbridge, J. C. S. Dalton, 1975, 2305. G. Monghetti, F. Bonati, and M. Massobrio. Znorg. Cheni., 1975, 14, 1974. N. J. Ali, M. Y . Al-Janabi, and M. Shanshal, 2. Nafurforsch., 1974, 29a, 1787. H. L. Krauss and B. Weisser, Z . anorg. Chem., 1975, 412, 82.

368

Spectroscopic Properties of Inorganic a i d Organometallic Cottipoiincis

8-niercaptoqi1inolii~oI.~~~ 'Thus it is fornially co-ordinated as a cation, and the bonding alters very little within this sequence of ligands. Solid-phase and solution i.r. and Raman spectra of W(CO),(NO)Br have been assigned. For the v ( C 0 ) and v(N0) region, calculations suggest the assignment (C4,,): Al 2140.7, B1 2079.6, E 2064.8, v ( C 0 ) ; A, 1674.0 v(N0). Other assignments of note are v(W-NO) 580, 6(WNO) 540 cm-l.,,' The multiplicity of v(N0) bands in the i.r. spectra of [MoCI,(NO),] suggests the non-equivalence of the NO groups in the complex. [MoCI,(NO)L,], where L, = Ph,PO, phen, or (dmf),, were also cis-[ReCl,(NO)(NCMe)] gives v(N0) at 1810 and 1912 cm-l, apparently a very large crystal-field splitting. Characteristic bands of the co-ordinated MeCN-M were at 2292, 1060, 1020, and 920 A series of thionitrosyl complexes has been characterized and v(NS) values listed (Table 2O).,,O

Table 20 v(NS) wauenumberslcm-l in some thionitrosyl complexes of Re and 0 s Compound [ReCI,(NS)(PMe,Ph),] [ReCl,(NS)(PMePh,),] [ReCI( NS)(Ph,PCH2CH,PPh,],C1 [ ReCI,( N S)(P Me, Ph), ) [ReCI,(NS)(PMePh,),] [OsClJN S)(P Me,P h 1 [OsCI,(NS)(AsPh,),]

V"S) 1180 1172 1185 1228 1220 1285 1282

Nitrosyl-apyG-tetraphenylporphinatoiron(Ii)is square-pyramidal, with bent M-N-0, and v(N0) at 1670 ~ r n - l . ~ * l v(N0) was given for [Et4N][Co(N0)L,(SnC1,)] and [Et,N],[Fe(NO),(SnC1,),1. The data, by comparison with literature results, suggest that SnC1,- is at least as good a n-acceptor as PC13.342 v(N0) may be correlated with redox potentials in [Ru(bipy)(NO)X] (X and NO cis).343 The NO stretching wavenumber is 188 1 cm-l in [RuCI,(NO)(PPh,),], shifting to 1848 cm-l in the 16Nanalogue. v(N0) is at 1709 cm-l in [(NO)(Ph,PCH2CH2PPh,),lr](PF,),, and at 171 7 cm-l in [(NO)(Ph,PCH,CH,PPh,),Rh](PF,),. By examining data on several hundred nitrosyl complexes in the literature, and with the aid of structural work (included in this paper), a set of empirical rules has been developed which attempts to correlate v(N0) values in even-electron complexes with the M-N-0 geometry, and with electronic influences. The rules given are an elaboration of those presented earlier (J. Amer. Chem. SOC.,1973, 95, 6859). Thus, correction factors are applied to the observed v(N0) values 3:m 337

3R8

snB

y40

341 342

849

S. A. Luchkina and A. A. Egorova, Russ. J. Inorg. Chem., 1974, 19, 700. I. S. Butler and C. F. Shaw, J. Raman Spectroscopy, 1975, 3, 65. N. A. Ovchinnikova and M. A. Glushkova, Koord. Khim., 1975, 1, 280. T. S. Khodashova, V. S. Sergienko, N. A. Ovchinnikova, M. A. Glushkova, and M. A. Porai-Koshits, Russ. J . Inorg. Clrem., 1975. 20, 409. M. W. Bishop, J. Chatt, and J. R. Dilworth, J.C.S. Chem. Comm., 1975, 780. W. R. Scheidt and M. E. Frisse. J . Amer. Chem. SOC.,1975, 97, 17. T. Kruck and W. Molls, Z . anorg. Chem., 1975, 411, 54. R. C. Callahan G . M. Brown, and T. J. Meyer, J . Amer. Chem. SOC.,1975, 97. 894.

l'ihrationtrl Spectra of Some Co-ordiiinted Liyanth

3 69 (for the Group and Period of M, the charge, arid the other ligands L) with the result that the v' values obtained fall into at least two groups. Thus bent M - N- 0 have v(N0) below 1610--1620 cm-l, while linear M - N - 0 have v(N0) above this value.3i4 The effects of ligands and the central metal atoms on the integral intensity of v(N0) i.r. bands have been studied for [Ru(NO)XJ2- (X = CI, Br, or I), [Ru(NO)(NH,),Y]"+ (Y = NH, or OH-), and IM(NO)(CN)J2- (M = Fey Ru, or 0s). Samples in aqueous solution, non-aqueous solutions, and KBr discs were studied. With increase in the negative charge on the complex, the n-component of the M-N-0 bond increases, in agreement with LCAO calculations.~45 v(N0) in [Ru(OCORF),(NO)(PP~,),~is ca. 1905 cm-l, i.e. this is a Rul'-NO+ has v(N0) at species, where RF = CF, or C2F6.348[OSH(OCORF)(NO)(PP~,)~] 1820 cni-l, while in [O~(OCOR~)(NO),(PP~,),I(OCORE.) they are at 1820 and 1610 cni-l. Bands in the range 553-601 cm-' were attributed to v(Ru-NO) and s(RuN0) in [Ru(acac),L] (L = hydroxyiminoacetonato), cis-[RuCl(NO)(acac),1, and [Ru(NO)(acac),], on the basis of 15N s u b s t i t ~ t i o n . ~ ~ ' Radiolysis of [Ru(NH,),N0I3+ in aqueous Bu'OH gave [Ru(NH,),-N(= 0)CH2CMe,(0H)l2++, a nitroxide. Compared with the parent nitrosyl, there is no v(N0) band at 1900, and a new band at 3520 cm-l. New bands were also seen at 1370, 1365, 1340, 1305, and 1318 cm-l. From 15N0 substitution, shifts in the 1370 and 1365 cm-l bands were seen. An assignment was discussed, but no definite conclusions were drawn, mainly because 13Ph,- obscures much of the spectrum .348 v(N0) features at 1778 and 1731 cm-l were attributed to NO+ bound to 0s" in the acetylenic derivatives [OS(CO)(NO)(PR,),(~~)]+.~~* Compound (87) gives v(N0) for the triply bridging nitrosyl group at 1405 cm-I. This is only the second such species to be NO

(87)

According to previously published correlations between l5N/I4N isotopic shifts for v(N0) and the oxidation state for the NO group (i.e. 36-44 cm-' for the NO+, 25-28cni-l for NO-), the complex [Rh(NO)(PPh,),] has an N O + B. L. Haymore and J. A. Ibers, Inorg. Chem., 1975, 14, 3060. A. B. Nikol'skii, N. V. Ivanova, and N. B. Batalova, Fiz. Mat. Metody Koord. Khim. Tezisy Doklady, Vses. Soueshch., 5rh, 1974, 36. A. Dobson and S. D. Robinson, J . Organometallic Chem., 1975, 99, C63. st' M. Mukaida, T. Nomura, and I. Ishimori. Bull. Chem. Sac. Japan, 1975, 48, 1443. 3 ' n J. N . Armor, R. Furman, and M. Z . Hoffman, J. Amer. Chem. SOC.,1975, 97, 1737. 9d!' J. A. Segal and B. F. G. Johnson, J.C.S. Dalron, 1975. 1990. m' J . Miiller and S. Schmitt, J . Orgonometallic Chet7t.. 1974, 97, (254.

370

Spectroscopic Properties of Itiorgutiic arid Organometullic Compounds

ligand. [RhX,(NO)(PPhJ,l and [RhX(NO,)(NO)(PPh,),], where X = CI or Br, a pear to behave as though NO- is present, however."I A class of iridium nitrosyl complexes [lr(PPh3),(C0)C1(X)(NO)] (X = I, Br, C1, NCS, NCO, or N3) has been prepared, izhich give v(N0) between 1520 and 1560 cm-l. This is almost the lowest yet reported for metal non-bridging nitrosyls. The NO- character was also indicated by the facile oxidation by O2 to give co-ordinated

4 Phosphorus, Arsenic, and Antimony Ligands A complex of the new ligand P213has been prepared: [(OC)4Cr(P213)],in which

v(P1) is at 320, 340 cm-', compared to values of 300 and 325 cm-l in P214.353 The structures of (88; M = Cr, Mo, or W ; R = Ph) have been deduced from their i.r. spectra, together with e.s.r. spectra of their oxidation A number of vibrational bands due to the Me-Sb unit were listed, together with v ( C 0 ) data, for (88), where M , M' = Cr(CO),Cp, and its Mo and W analogues, R = Me, PhCH2, or Et.355 Similar data were also given for (89), where M, M', M" = Cr, Mo, or W.35G

v(C= C ) bands were assigned for the newly prepared complexes [Ni(CO),L], [Cr(CO),L], and [ Mo(CO),L], where L = 2,3-bis(diphenylphosphino)maleic anhydride. The Group V1 derivatives were assigned the structure (90), where X = 0, S, CH2, NMe, or NPh.357 [(MeCp)Mn(CO),(PPhXY)] (X = H, Y = Li or D; X = Y = D) gave the following ligand bands : v(PH) 2233 ; v(PH) 2298/2282, v(PD) 1671 /1663; v(PD) 1671/1663 cm-l, The phosphinidene complex PhP[Mn(CO),Cp12 contains trigonal planar phosphorus, and six v(C0) bands in toluene solution, implying the presence of rotamer~.~~~ Raman polarization studies in the v ( C 0 ) region for [Co(CO),(tdpme)]f, where tdpme = MeC(CH,PPh,),, suggest that the tetragonal form (91a) is preferred to the trigonal isomer (91 b).360 351

363 354 365

357

35n

31D 360

E. Miki, K. Mizumachi, and T. Ishimori, Bull. Chem. SOC.Japan, 1975, 48, 2975. M. Kubota and D. A. Phillips, J. Amer. Chem. Soc., 1975, 97, 5637. G. Schmidt and H.-P. Kempny, Z. anorg. Chem.. 1975, 418, 243. C. Elschenbroich and F. Stohler, Angew. Chem. Internut. Edn., 1975, 14, 174. W. Malisch and P. Panster, Chem. Ber-, 1975, 108, 700. W. Malisch and P. Panster, Chem. Ber., 1975, 108, 716. D. Fenske and H. J. Becher, Chem. Ber., 1975,108, 1975. G. Huttner and H.-D. Muller, Z. Narurforsch., 1975, 30b, 235. G. Huttner, H.D. Muller, A. Frank, and H. Lorenz, Angew. Chem. Internut. Edn., 1975, 14, 705. J. Ellermann and J. F. Schindler, 2. Naturforsok., 1975, 30b, 914.

Vibrational Spectra oj’ Some Co-orditinied Ligunds P P

I

/Fy+ co P

co

(9 la)

37 I I’ p, 1 ,Fe--CO P I

co

(914

1.r. spectra were used to differentiate isomers of [CO,(CO)~(P~,ECH,CH,EPh,)] (E = P) which involve either CO or ligand bridges. When E = As, only the ligand-bridged form is Wavenumbers were listed and tentative assignments given for [CoXL,] (X = CI, Br, or I ; L = PMeJ and [CoL,]+, as well as for [CoX(CO)L,], [CoX(CO)L,], and [CoX(CO),L,] types.3s2 Several Rh complexes of bis(but-3-enyl)phenylphosphine, PhP(CH,CH2CH=CH2),, have been prepared, in which the ligand is terdentate, i.e. the P atom and two C=C. Thus the band at 1634 cni-’ in the free ligand is replaced by one at 1477 in [Rh,CI,L2], 1500 in [Rh2Br2L2],and 1499 cm-l in [Rhl(CO)L]. The proposed structure for the last of these is shown in (92).363

X (92)

(93)

[IrCl(cod)],(PCI,) (93) gives v(PCl,) bands, mixed with v(Ir-olefin), at 515, 500, 483, and 463 cm-l. 6,(PCl,) is thought to be at 350 The presence of v(PF,) bands at 890 and 855 cm-l in [Ni(PF,),L], where L = PF,NR(SiMe,), compares with values of 904 and 864cm-l for v(PF,) in [Ni(PFS),,]. This suggests that L is a stronger donor than PF,.3s5 Bis[ 1,2-bis(difluorophosphino)cyclohexane]nickeI(O) shows v(PF) at 779 and 770 cm-l. This shows that the PF2 groups are co-ordinated, since the analogous feature in the free ligand is at 799 ~ m - ~ . ~ ~ ~ 1.r. spectra were assigned, for a few internal modes of Ar,As only, for MX2[As(C6H40Me-p),], (M = Pd or Pt; X = Br).3s7 5 Oxygen Donors

Molecular Oxygen, Peroxo- and Hydroxy-complexes.-The position of the i.r. band in the 400-900 cm-l range assigned to an H,O libration mode correlates 3a1

383 366 3au ya7

J. Ellermann and N. Geheeb, Z . Naturforsch., 1975, 30b, 566. H. F. Klein and H. H. Karsch, Inorg. Chem., 1975, 14, 473. P. W. Clark and G. E. Hartwell, J . Organometallic Chem., 1975, 96, 451. B. Denise and G . Pannetier, J . Organometallic Chem., 1975, 99, 455. T. Kruck, G . Miineler, and G . Schmidgen, Z . anorg. Chem., 1975, 412, 239. N. R. Zack, K. W. Morse, and J. G. Morse, Inorg. Chem., 1975, 14, 3131. P. Spacu, F. Popen, C. I. Lepadatu, A. C. Banciu, E. Ivan, S. Plostinaru, Z . Torna, and C. RLISU,Rev. Rounrtiinr Chim., 1974, 19, 1861.

13

372

Spectroscopic Properties of Inorganic and Orgariornetallic Compounds

with the cation radius in MX,,nH,O, where M = Mg, Ca, Sr, or Ba; X = NO3 or Cl.368 v(N0) is at 1610 cm-l in [(ON)CpCr(OH),CrCp(NO)], together with a band characteristic of the bridging OH at 1060 cm-l. v(0H) of the p-OH ligand is at 3480 cm-1.36Q Table 21 summarizes some vibrational assignments for the new oxo-peroxocomplexes [MO(O-O)(C7H3N04)(H20)].370

Table 21 Some vibrational assignments for some Group VI oxo-peroxo-complexes (waoenumbers/cm-')

Compound ~

~

~

~

(

~

-

~

WO(O- O)(C7H&O4)(H@)I

)

(

~

977 ~ 983

~

0

~(0-0)

v(M=O) 3

~903~

875

~

)

598 ( ~ 602

0

~

~

)5721

575

Rb2W06,2H20,and Rb2W08both give a band at about 840 cm-l, due to the ~(0-0)band of the p e r ~ x o - l i g a n d . ~ ~ ~ Photolysis of [Re,(CO),,] in aqueous ether leads to the distorted cubanetype tetramer [Re(CO),(OH)],. This has v ( C 0 ) at 2021 and 1919 cm-l in T H F (i.r.) and v(0H) at 3550 cm-', shifting to 2515 cm-l on deuteriation. The OH groups bridge faces of the Re, tetrahedr~n.~', BaOsO,,H,O gives a series of i.r. bands at 1025, 1120, and 1170 cm-' which disappear on deuteriation. They were assigned as ~ ( O S - 0 - H ) , suggesting that the anion is [OSO,(OH)~]~-.The Sr analogue behaves in exactly the same way. Higher hydrates show 6(HOH) at about 1600cm-l. For CaOs0,,2H20, the 6(0s-O-H) bands were seen, but no 6(HOH), so it is presumably C~[OSO,(OH),].~~~ ~(00) bands were identified in the resonance Raman spectra of some superoxide-bridged dinuclear complexes, i.e. [(Nc),co(02)co(cN),]6-, 1104 cni-l ; [(NHs)6Co(02)Co(NH3)6]5+, 1108 c11l-l.~~~ 1.r. spectra were used to determine the state of the H 2 0 molecules in the series of hydrates CoSeO,,nH,O (n = 2, 1, or +). The monohydrate gave significantly different spectra to the other t*o.375 6(H20) is seen in the complexes [M(OH,),X2],C6H12N4,2HX(M = Co or Ni; X = C1 or Br) at 1625 k 5 cm-1 as a single i.r. band. p(H20) is also a single feature, at 610 _+ 10 ~ m - ~ . ~ ~ ~ Ni, Pd, and Pt, when co-condensed at 6-10 K in Ar matrices with 02-Nz mixtures, form mixed complexes (02)zM(N2)v.A great deal of i.r. data was a*8 a80

370

G . S. Karetnikov, 0. V. Bazileva, and T. V. Gerzha, Zhur. fiz. Khim., 1975, 49, 815. G. Hoch, H.-E. Sasse, and M. L. Ziegler, 2. Nuturforsch., 1975, 30b, 704. D. Westlake, R. Kergoat, and J.-E. Guerchais, Compt. rend, 1975, 280, C, 113. L. I. Kozlova, N. A. Korotchenko, and G. A. Bogdanov, Russ. J . Inorg. Chem., 1974, 19, 1661.

37a

a7a 374

a76

376

M. Herberhold and G. Suss, Angew. Chenz. Internut. Edn., 1975, 14, 700. J.-C. Bavay, Rev. Chim. mindrule, 1975, 12, 24. T. C. Strekas and T. G. Spiro, Inorg. Chem., 1975, 14, 1421. R. Ya. Mel'nikova, V. N. Makatun, and V. V. Pechkovskii, Russ. J . Inorg. Chem., 1974, 19, 1017. T. G. Balicheva, I. V. Pologikh, D. I. Kovachev, and A. T. Statelova, Russ. J . Inorg. Chcm., 1975, 20, 86.

Vibrational Spectra of Sonie Co-ordinated Ligands 373 reported, while a normal-co-ordinate analysis, using a modified valence force field, suggests that the 0, is bonded side-on. This bonding appears to be stronger than that for N,,and consistent with the formulation M8+028-.377 v(0H) in Na,[Pd(OH),] appears as a strong, very broad band in the range 2800-3500cm-1. G(Pd-0-H) bands are at 1110 and 7 9 0 ~ m - l . ~ I n~ ~ [Pd(L-L)(OH)],(BPh,), the bridging (OH) group is responsible for a sharp i.r, band at 3450 cm-l (2578 cm-l in the deuteriate). The complex has the structure (94), where L- L = N-alkyl-substituted ethane-l,2- or propane1,3-diamine.s7@

(95 a)

(94)

The reaction of O2with CuCl i n the presence of py yields the novel Cu' peroxide complex, forniulated as Q ~ y ) ~ C u 0 O C u ( p where y ) ~ , n 2 1. ~ ( 0 0is) at 876 cni-I in the Raman spectrum.3Ho v(0H) for the bridging OH group is at 3300 cm-I in (95a), where chel = (95b), R', R2 = Me or Ph.381 The cyclohexanol clathrate (Ph,PH),[U(OH)CI,],CBHllOH has overlapping v(0H) bands due to the ligand (3600-3700 cni-I) and the cyclohexanol (3400-3700 C I I I - ~ ) . ~ ~ ~

Acetylacetonates and Related Complexes.-Studies of solvent shifts in the 12501700cm-l region for the complexes [M(acac),] ( M = Cr, Mn, Fe, or Co) have led to the assignments, described as 'definitive', listed in Table 22. Sotne weak bands were ascribed to the existence of Jahn-Teller distortions, even for d3.:IH3 Table 22

Vibrational assignnients for [ M(acac),] (wat.eizuniDers/cii1-') M: v(C=O) v( c- c- C ) Me degenerate def. v(C-0) V(C... c 1zLC )

Mn 1594 1514 1425 1390 1260

Cr 1582 1535 1429 1389 1281

Fe 1583 1532 1428 1385 1279

co 1587 1523 1430 1390 1284

[{Re(CO),(acac)},(MeCOCH,CH,COMe)] shows v(CC) at 1580, v(C0) at 1528 cm-l for the co-ordinated a ~ a c . ~ ~ , a77 878

579 8*0

881

sMa aMb

G. A. Ozin and W. E. Klotzbucher, J . Amcr. Chem. SOC.,1975, 97, 3965. B. N. Ivanov-Emin, L. D. Borzova, D. Sudzhben, N. N. ivanova, and A. I. Ezhov, Rum. J. Inorg. Chem., 1974, 19, 1026. J. H. Setchfield and R. S. Vinal, J. Inorg. Nuclear Chem.. 1975, 37, 1046. C.E. Kramer, G. Davies, R. B. Davis, and R. W. Slaven, J.C.S. Chem. Comnr., 1975, 606. J. C. Danilewicz, R. D. Gillard, and R. Wootton, Inorg. Chim. Acta, 1975, 15, L5. R. G. Bhattacharyya, J. Inorg. Nuclear Chenr., 1975, 37,579. J. Y. H. Chau and P. Hanprasopwattana, Austral. J . Chem., 1975, 28, 1689. G. Doyle, Inorg. Chem., 1975, 14, 2998.

374

Spectroscopic Properties of' Inorganic and Orgctrtometniiic Conipolrrds

v(C0) and v(C=O) wavenumbers were listed for the following complexes : [Re2(CO)BL2](L = acac, dibenzoylmethanate, 4,4,4-trifluoro-1-phenylbutaneI ,3-dionate, tri- and hexa-fluoroacetylacetonate), [Re(CO),L], and [Re(CO),L'L"] (L' = dbm; L" = py or PPh,).385 The complex [(Hfacac)Ir(C,H,),], containing hexafluoroacetylacetonate and a tetramer of allene bonded via two h3-allyl units, gives bands due to v(C=O) and v(C-C), respectively, at 1630 and 1550 cm-'. The @-diketonato-group is therefore bonded uia two 0 v(C0) wavenumbers were listed for (96), where C2local symmetry appeared to be adequate to interpret the spectrum due to the M(C0)5 group (M = Cr, Mo, or W).jS7 Similar data were also given for (97).38s

Carbon Dioxide and Carbonato-complexes.--v(NH), 8(NH), and v(CH) wavenumbers were tabulated for some Co"' complexes of 3,7-dithianonane1,9-diamine (98). Bands at 1655, 1630, 1610, and 823cm-' in the carbonatocomplex were assigned to the CO, ligand.38Q I

A single-crystal X-ray study of [Ni(CO,)(PCy,),],~(C,H,) shows the carbon dioxide to be co-ordinated through one 0 atom and the C atom (99). v ( C 0 , ) bands were seen at 1740, 1698, and 1150 cm-1 in a Nujol Modes of the CO, unit in [(C6H&h]2C03 are consistent with effective CZu symmetry for the carbonato-ligand. The probable structure is (

Carboxylato-complexes.-The splitting of v ( C 0 ) and v(CH) modes in 10 bivalent metal dichloro-acetates has been interpreted as being due to 386 s8e

387 388

3B0

3D1

M. C. Fredette and C. J. L. Lock, Cunad. J. Cliem., 1975, 53, 2481. P. Diversi, G. Ingrosso, A. Immirzi, and M . Zocchi,J. OrganonietufficCIwni., 1975, 102, C49. A, B. Cornwell and P. G. Harrison, J.C.S. Daltcin, 1975, 1486. A. B. Cornwell and P. G. Harrison, J.C.S. Dalton, 1975, 1722. R. W. Hay, P. M. Gidney, and G. A. Lawrence, J.C.S. Dalton, 1975, 779. M. Aresta, C. F. Nobile, V. G. Albano, E. Forni, and M. Manassero, J.C.S. Clieni. Cotrim., 1975, 636. B, Y . K . tio and J . J. Zutkerman, J. Ot-girnonii~taflicChem., 1975, 96, 41.

Vibrutiorinl Spectra of’Sonic Co-ordinated Ligiinds

375

dimerization;392the metals concerned were Be, Mg, Ca, Sr, Ba, Co, Ni, Cu, Zn, and Pb. The i.r. spectra of bivalent metal tribromoacetates suggest that the carboxyl is bound in the same way as in the trichloroacetates. v(CC) was lowered significantly by the mass and steric effects of the CBr3 group, however.3s3 The i.r. and Rarnan spectra of [Be,O,(O,CMe),(NH,),] contained bands due to v(CC) at 961 and 942 cm-l. The latter was said to be due to unidentate, the former to bidentate acetato ligands. The v,, and v,(CO,) modes, the more usual criterion, were at 1591 and 1457/1392 c ~ i i - ~ respectively.394 , In the series of nitrilotriacetates K[MN(CH,CO,),] (M = Be, Mg, Ca, or Sr), only for M = Be does the M - 0 bond become sufficiently covalent to break down the equivalence of the C-0 bonds of the carboxy-group. This is shown by the larger value for v,,(CO,) - v,(CO,), as well as by X-ray spectral data.3s6 [TiCI,(OAc)] and [TiCI,(OAc),] give i.r. bands in the range 1650-1400 cm-I due to v,, and v,(COz) of the bidentate carboxylate l i g a n d ~ . ~ ~ ~ v, and v,,(CO,) were found and assigned for [TiCl,(HCO,)] and [TiC13(Cl,CH,-,CO,)] (see Table 23).397 Group-frequency assignments for the i.r. spectra of a number of Zr and Hf amygdalato-complexes, e.g. (101), were given.39s

Table 23 COa mode assignments for [TiCl,(HCO,)] and [TiCl,(CI nCH3-nC02)] (wauer~umbers/~rn-~) Compo uitd [TiCI,(HCO,)] [TiCl,( MeCO,)] [TiCI3(CH2CICO2)] [TiCI,(CC1,CO2)]

van

1579 1542, 1640 1558, 1593, 1683 1628

v.9 1373 1420 1421 1410

The bidentate nature of the oxalato ligand in [VOF(C,O,)(H,O),]- is clear from the i.r. spectrum. Thus S(OC0) is below 800 cm-’, which is never the case for quadridentate C204. vaa,v,(CO) are at 1660 and 1462 cm-l,

J. A. Faniran, K. S. Patel, and M. A. Mesubi, Spectrochim. Acta, 1975, 31A, 117. K. S. Patel and J. A . Faniran, Spectrochim. Acta, 1975, 31A, 123. A. I. Grigor’ev, L. N. Reshetova, and A. V. Novoselova, Russ. J . Inorg. Chem., 1974,19, 1093. A. I. Grigor’ev, V. 1. Nefedov, N. I. Voronezhova, and Ya. V. Salyn’, Russ.J. Inorg. Chem., 1974,19, 1406. J . Amadraut and C. Devin, Bull. SOC.cltim. France, 1975, 1933. Yu. A. Lysenko and L. I. Khokhlova, Russ. J . Inorg. Chem., 1974, 19, 690. K. F. Karlysheva, A. V. Koshel’, I. A. Sheka, and G. S. Semenova, Russ. J. Inorg. Chem., 1975, 20, 521. A. J. Edwards, D. R. Slim, J . Sala-Pala, and J.-E. Guerchais, Bull. SOC.chim. France, 1975, 2015.

3 ~ 3

301

396

3u0

su7 3un

376

Spectroscopic Properties of Inorganic and Organometallic Compounds

The oxalato wavenumbers in [V202C1,(C204)(H20)2]2and in [Sn,X8(C,04)]2(X = C1, Br, or I) are consistent with the presence of bridging, quadridentate C204units, giving octahedral co-ordination at the V or Sn.400 The adduct [Mo(O)F2(0Ac),],(HOAc) gives an i.r. spectrum containing v,,(COO) of the OAc ligand at 1630cm-l, v(C=O) and v(OH) of the HOAc at 1705, 3410 cm-l, respectively.401 Trifluoroacetate complexes of M o containing the ligand dppe ( = Ph2PCH2CH2PPh2)have been characterized by their i.r. spectra. Thus [Mo(O,CCF,),(dppe),] gives v,,(CO,) at 1705/1690 cm-I. v,(CO,) at 1400 cm-l, i.e. the carboxylate is unidentate. [Mo(O,CCF,)(dppe)]+, however, has v,, at 1580 (a very low value) and v, at 1425 cm-', more consistent with bidentate co-~rdination.~~~ 1.r. spectra down to 400cm-l have been shown for K2[M(C204)2],nHz0 and K,[M(C,O,),] (M = Mn, Co, Ni, Cu, or Zn).ao3 The substantial differences between the hydrated and anhydrous forms indicate different structures, uiz. polynuclear octahedral with bridging oxalate for M = Mn, Co, and Zn, when anhydrous, but monomeric for M = Ni and Zn. Values of v(C-0) have been listed for [FeL(OMe),] (L = benzoate or one of six other aromatic acids), e.g. v,,(OCO) 1525, u,(OCO) 1415, v(CC) 1040 cm-l for the benzoate.404 v,, and v,(CO,) modes for Co(m-hydrazinebenzoato),,2.5H20 are typical of symmetrically bidentate co-ordination by the benzoate (thought to form polymeric units by bridging). Dehydration to the monohydrate leads to the appearance of bands from a unidentate carboxylato-ligand. I t was therefore suggested that there was one bi- and one uni-dentate c a r b o ~ y l a t e . ~ ~ ~ The presence of v,,(CO) of the oxalate ligand at 1680, 1650 cm-l, respectively, in the complexes [Co(phen)(ox)] and [Co(phen),(ox)] suggests that the oxalatoligand is more covalently bound in these species than in cobalt oxalate itself [v,,(CO) at 1630 ~ m - l ] . ~ O ~ v,, - v, of the OCO unit is 130-235 cni-' in the i.r. spectra of [Co(O,CR),], [LCo(O,CR),],, and [L,Co(O,CR),], where R = aryl or fury], n = 1 or 0.8. Bridging carboxylato ligands are therefore Six- (1560-1612 cn-*) and five-membered (1618-1685 c1ii-l) rings have been detected from the positions of v(C0,) mode vibrations in, e.g., Na[Co(edta)],2H20 and Na[Co(S,S-edds)],H,O (S,S-H,edds is S,S-ethylenedii in ine-N,N-disuccinic A mixed trinuclear complex of Co"' and Rh"' containing oxalate as a terdentate bridging ligand has been given the structure (102) on the basis of the v(C0) bands in the i.r.409 F. Le Floch, J. Sala-Pala, and J.-E. Guerchais, Bull. Soc. chirn. France, 1975, 120. Yu. A. Buslaev, Yu. V. Kokunov, V. A. Bochkareva, M. P. Gustyakova, and D . N. Suglobov, Russ. J . Inorg. Chcm., 1974, 19, 652. roa T. Ito and A . Yamamoto, J.C.S. Dalton, 1975, 1398. '03 K. Nagase. K . Sato, and N . Tanaka, Bull. Chem. Soc. Japan, 1975,48, 868. 401 E. Kokot, G. M. Mockler, and G . L. Sefton, Artstrul. J . Chem., 1975, 28, 299. '05 V. A. Starodub and M . S. Novakovskii, Russ. J . Znorg. Chem., 1975, 20, 381. 4 0 a 1 i. P. lyer, P. S. Ramanathan, and C. Venkateswarlu, J . Inorg. Nuclear Chem., 1975,37, 23 16. '07 A. A. Pasynskii, T. C h . Idrisov, K . M. Suvorova. V. M. Novotortsev, V. V. Zelentsov, and V. T. Kalinnikov, D o X l u ~ vPhys. Chetn., 1975, 220, 97. '08 D. J. Raponovic and B. E. Douglas, J . Coordination Chem., 1975, 4, 191. 'O9 K. Wieghardt, 2. Nuturforsch., 1974, 29b, 809.

'OD

401

Vibrational Spectra of Some Co-ordinated Ligands

377

Some new Ir" complexes, found to have bidentate carboxylate ligands, have been prepared, e.g. [Ir(PPh3)(CNCBH4Me-p)(OzCR),1have v,, at about 1540, v,(COz) at about 1395 ~ r n - l . ~ ~ O Dimeric tertiary phosphine carboxylate complexes [(R1,P)Pd(OZCR2),],have been characterized using i.r. spectroscopy, which showed the presence (in CHCI, solutions) of both unidentate and bridging carboxylato-groups ; Rl, = Me,Ph, MePh,, or Et,; R2 = Me, CH,Cl, or CF,."l the v,, - v,(CO) In the unidentate oxalato-complex K4[Pt(C204)2(SCN)z],4H20, difference (210 cm-l) is about the same as for the free ~ x a l a t o - l i g a n d . ~ ~ ~ , ~ H , the O Sc to be eight-co-ordinate. The crystal structure of [ S C ~ ( C ~ O ~ ) ~ ]shows The related complex [ S C , ( C ~ O ~ ) ~ ] , ~ N ~gives H~,~ bands H ~ Oin the i.r. due to oxalato-groups which are characteristic of quadridentate and/or ionic C2042-. It was therefore suggested that two of the oxalato-groups are quadridentate, with one ionic, preserving the eight-co-ordination of the The i.r. spectra of the scandium anthranilates and p-aminobenzoates [ScR,] show no band due to u(C=O), but two from v, and vas(COz). The ligands are therefore co-ordinated as c a r b o x y l a t e ~ . ~ ~ ~ Quite detailed assignments were given for solid-phase spectra of the lanthanide formates [Ln(HCO,),] (Ln = Ce, Pr, Nd, Sm, Eu, or Gd). The assignments were mostly based on those for analogous acetato-c~mplexes.~~~ The i.r. spectra of [Ln,(C2Od),],nH2O(Ln = Tb, Ho, Y, Tm, Yb, or Lu; n = various) are said to be consistent with the presence of quadridentate oxalato - l i g a n d ~ . ~ ~ ~ The separation of v,(OCO) and v,,(OCO) is nearly 400 cm-l in K2[U02(C20d)z(H20)],2H,0, in which the oxalate is bidentate. This is larger than in the case of [UO2(C2O4)(Hz0)],H2O,in which the oxalato-ligand is quadridentate and bridging (ca. 300 ~ m - 9 . ~ ~ ' 41 0 4 11 412

dl3 414

416

4lU 41 7

A. Araneo, F. Morazzoni, and T. Napoletano, J.C.S. Dalton, 1975, 2039. T. R. Jack and J. Powell, Canad. J . Chem., 1975, 53, 2558. A. C. Villa, A. G. Manfredotti, A. Giacomelli, C. Guastini, and A. Indelli, Inorg. Chem., 1975, 14, 1654. G. V. Bezdenezhnykh, E. I. Krylov, V. A . Sharov, and E. A. Nikonenko, Russ.J. Inorg. Chem., 1975, 20, 177. T. V. Shestakova, Z. N. Prozorovskaya, and L. N. Komissarova, Russ. J . Inorg. Chem., 1974, 19, 1459. 3. T. M. de Hosson, J . Inorg. Nuclear Chern., 1975, 37, 2350. G . V. Bczdenezhnykh, V. A . Sharov, and E. I. Krylov, Russ. J. Inorg. Chem., 1974, 19, 1122. R. N. Shcheloliov and V. E. Karasev, Rum. J. Inorg. Chem., 1974, 19, 776.

378

Spectroscopic Properties of Inorganic and OrganometaNic Coniporriids

The i.r. spectra of M,[UO,(mal),(H,O)],nH,O (A) and [UO,(mal)(H,0)],2H2O (B) could be interpreted similarly, (A) being formed by bidentate chelating ma1 (= malonato), (B) by quadridentate ma1 (M = K , Rb, or C S ) . ~ ~ ~ [Ge(C204)J2-gives v(C=O) at 1750 and 1680cm-l, and v,(C-0) at 1360, 1255, and 1215 cm-l, characteristic of bidentate o ~ a l a t o - l i g a n d s . ~ ~ ~ The benzoato-complexes of lead [Me,PbX,], where X = OCOC6H,Y; Y = H, o-Me, p-Me, or p-MeO, retain bidentate co-ordination of the benzoatoligand even in strongly donating solvents, such as hexamethylphosphoraniide, as shown by the separation of vus and v, of the CO, group.42o v,,(CO,), vs(C02), v(CF,), v(CC), S(OCO), and S(CF,) wavenumbers were listed for [M(O,CCF,),] (M = P, As, Sb, or Bi). When M = P or As, unidentate CF3C02- ligands are likely, while for M = Sb or Bi they are probably bidentate and bridging.421 Ph,Sbv and Ph,BiV complexes of alkylthioacetato and arylthioacetato ligands (PhCH,, Me, Et, Prn, Pr’) have been prepared. All gave i.r. bands characteristic of unidentate carboxylate complexes. The Sb- or Bi-carboxylate bond seems to be more covalent than in transition-metal analogues.42e The presence of v(C=O) at 1729 and 1620 cm-l in [Sb(C,O,)OH] shows that there is one free C=O in the oxalate ligand, which is therefore not acting as a quadridentate ligand.423 Keto, Alkoxy, Phenoxy, and Ether Ligands.-Although the i.r. spectra of benzo-15-crown-5 complexes with K+ and Na+ salts are very complex, they can be grouped according to the known structures of at least one member of the series. The v(0H) region is of particular use, as the occurrence of sharp v ( 0 H ) bands clearly indicates co-ordination to Mf by the OH of the crown ligand, whereas broad bands indicate H-bonding to other c ~ n s t i t u e n t s . ~ ? ~ ~ 1.r. and Raman spectra of ‘EtMgCl,OEt,’ as a liquid at 300 K are consistent with the dimeric formulation (103); the wavenumbers were very close to those reported previously for the Br and I analogues. At 90 K, in the solid, there is the possible formation of an isomer with bridging OEt, l i g a n d ~ . ~ , ~ The i.r. and Raman spectra of MeMgX,2Et20 (X = Br or 1) and CD,MgBr,2Et20 suggest that the basic structures are very similar to the Et analogues. Two forms of crystalline MeMgBr,2Et20, at low temperatures, seem to differ in the conformations of the ether ethyl groups.42s The compounds [RMI(THF).] (M = Sr or Ba; n = 1-3; R = various alkyls) all give an i.r. band at 1033 cm-l due to the co-ordinated THF.427 TiOCI2,2MeCOCIgives a band at 1750 cm-l due to the acetyl chloride molecule co-ordinated to the Ti via the 0.428 ‘I8 419

421 423

p24 425

426 427

V. E. Karasev, 1. M. Orlova, and R. N. Shchelokov, Kood. Khim., 1975, 1, 234. T. B. Shkodina, E. 1. Krylov, and V. A. Sharov, R u n . J . Inorg. Chem., 1974, 19, 1595. M. Aritomi, K. Hashimoto, and Y. Kawasaki, J . Urganometallic Chem., 1975, 93, 181. C. D. Garner and B. Hughes, Inorg. Chem., 1975, 14, 1722. A. Ouchi, H. Honda, and S. Kitazima, J . Inorg. ,YucIear Chcm., 1975, 37, 2559. S. Ambe, J . Inorg. Nuclear Chem., 1975, 37, 2023. D. G . Parsons, M . R. Truter, and J . N. Wingfield, Inorg. Chim. Actn, 1975, 14, 45. J. Kress and A. Novak, J . Organometallic Chem., 1975, 99, 23. J. Kress and A. Novak, J . Organometallic Chcm., 1975, 99, 199. D. G . Gowenlock, W. E. Lindsell, and B. Singh, J . Organometallic Chem., 1975, 101, C37. B. Viard and C. Devin, Bull. SOC.cfiim. France, 1975, 1938.

Vibratiorral Spectra of Some Co-ordinatcd Lignnds

3 79 The extraction of Zr or Hf hydroxide nitrates by cyclohexanone gives samples with v(C=O) about 65cm-l to lower wavenumbers compared to free cyclohexanone. Thus, M-O=C co-ordination has

Exchange of *C02 with [M(O,CNMe,),], where M = Zr, I I = 4; M = Nb, 5 ; or M = W(NMe,),, n = 3, has been followed by i.r. spectroscopy. Both uni- and bi-dentate ligands were detected, and the results suggested sevenor eight-co-ordination. X-Ray studies revealed eight-co-ordination, and gave insight into the facile CO, exchange.43o Compound (1 04) gives v(C= 0) of the co-ordinated acyl group at 1530 cn-', together with four v ( C 0 ) bands as expected, when M = Mn or Re.431 Group-frequency assignments were listed for the Ni" chelates with 0-,u'dihydroxychalcones ( I 05) ; polymeric 0-bridged structures were suggested.432 2,6-Dimethyl-4-pyrone (dmp) forms several complexes with Sc : [ScX,],4dmp (X = C1 or NO3), [ScX3],6dmp (X = Br, I, SCN, or C104), and [Sc(SCN),],3dmp.433 In all cases, co-ordination occurs via the C=O group [v(C=O) is lowered by about 50 cm-l]. v(C0) shifts by 39-47 cm-l to lower wavenumber when 4-butyrolactam or 8-caprolactam co-ordinate to Sc"' in compounds such as [scLg]xs.434 v(C=O) of the caprolactam ligand in the lanthanide complexes [h(C8HI1ON)J+ (Ln = Y , Sm, Yb, or La) is 18-26 cm--l less than in the free ligand; therefore co-ordination to the keto-group has v(C-0) is at 1060 (i.r.), 1090 (R) cm-1 in the polymeric solid [(t-C,H,),Ga(OMe)]. v,,, v,(CO,) are at 1604, 1463 cm-l, respectively, in the related [(~-C,H,),G~(OAC)].~~~ Pyrocatechol violet forms a complex with gallium; this gives v(C=O) at 1520 cm-1, compared to 1590 cm-1 in the free ligand. This, together with U.V. data, suggests the formulation (106).437 Some assignments of - 0 M e modes have been given for [In(OMe),], as methanol solvates. The polymeric nature of the compound was confirmed by observation of v(C-0) at 1080 and 1050 cm-I, the former due to terminal, the latter to bridging l i g a n d ~ . ~ ~ ~

II =

420 430 4J1 432

433 434 4:'5

4y6 437

V. M . Kluchnikov, E. S. Solov'eva, and S. S. Korovin, Russ. J . Inorg. Chem., 1974,19, 1685. M. H. Chisholm and M. Extine, J . Amer. Chcm. Soc.. 1975, 97, 1623. S. S. Crawford, G. Firestein, and H . D. Kaesz, J . Organumetnffic Chem., 1975, 91, C57. N. S. Biradar, Jnorg. Clzim. Acta, 1975, 15, 33. F. Kfitek and B. DuSek, Russ. J . Inorg. Chent., 1974, 19, 1289. B. DuSek, F. Khtek, and V. Kohout, Coll. Czech. Chem. Comm., 1975, 40, 2569. Yu. G. Eremin and G . I. Bondarenko, R i m . J . Jnorg. Chem., 1974, 19, 1242. H. U. Schwering, E. Jungk, and J. Weidlein, J . Organometallic Chem., 1975, 91, C4. M. K. Akhmedi, A. E. Klygin, L. I. Ivanova, and E. A. Bahirov, Russ. J . Inorg. Chem., 1974, 19, 1100. P. Bianco and J. Halrtdjian, Bull. SOC.cltirtt. France, 1!)75, 2009.

380

Spectroscopic Properties of Inorganic and Organometaiiic Compounds 0I-I I

0-Bonded Amides and Ureas.-The i.r. spectrum of [VO(urea),CI,] gives urea bands in the regions expected for (107). Thus v(C=O) has shifted to lower and v(C-N) to higher w a v e n u m b e r ~ . ~ ~ ~ M+-O=C,

,N H,

(107)

N H,

v(C=O) and v(C-N) of formamide (F) are respectively lowered (25--67 cm-l) and raised (30-65 cm-') on forming the complexes MCI4,4F (M = Mn, Co, or Ni) and CuC1,,2F. The amide is therefore O - c o - ~ r d i n a t e d . ~ ~ ~ Group-frequency assignments were given for the i.r. and Raman spectra of MnC1,,2L, FeC1,,3L, CuCI2,2L, and M(NCS),,4L (M = Co or Ni), where L = acetamide. The acetamide always appears to co-ordinate via the 0 atom, The NCS is co-ordinated uia the N in the last group of complexes.441 Shifts in some characteristic vibrational modes suggest that in [Rh2(MeC02)4L,] (L = 2-, 3-, or 4-aminopyridine or nicotinamide) the L is co-ordinated via the ring N atom. I n the analogous complex with benzamide, however, co-ordination seems to take place via the 0.442 Group-frequency assignments were reported for CuBr2,2L, Cd12,2L, and ZnX,,nL (X = C1 or NCS, n = 2 or 4), where L = p r ~ p i o n a m i d e .The ~ ~ ~amide ligand appears to be N-bonded, while the NCS modes indicate that in Zn(NCS),,4L the NCS is N-bonded, and that in Zn(NCS),,ZL it is bridging. [Cd(C104)2],4CO(NH2)2,2H20 and [Cd(C~104)2],6CO(NH2),both have a lower v(C=O) and a higher v(C-N) wavenumber than in the free ligand. The urea is therefore O - b ~ n d e d . ~ ~ ~ 430

Z. 0. Dzhamalova, 0. F. Khozhaev, and N. A. Parpiev, Russ. J. Inorg. Chem., 1974, 19,

1658. M. S. Barvinok, L. V. Mashkov, and L. A. Obozova, Russ. J. Inorg. Chem.. 1975, 20, 237. u1 A. Yu. Tsivadze, Yu. Ya. Kharitonov, G. V. Tsintsadze, A. M. Smirnov, and M. N. Tevsadze, Russ. J . Inorg. Chern., 1974, 19, 1818. 4 4 2 T.A. Mal'kova and V. N. Shafranskii, Russ. J. Inorg. Chern., 1974, 19, 1366. 440

Q43

444

A. Yu. Tsivadze, Yu. Ya. Kharitonov, G. V. Tsintsadze, A. N. Smirnov, and M. N. Tevsadze, R i m . J . Inorg. Chcm., 1975, 20, 406. A. S. Karnaukhov, T. Ya. Ashikhrnina, and N. N. Runov, Russ. J . Innorg. Chem., 1975, 20,

446.

Vibrational Spectra of Some Co-ordinated Ligands

38 1 Some indifferent i.r. data suggest that M - 0 co-ordination is present for CdX2,2L (X = C1, Br, I, or SCN) and for CdX2,2DL (X = CI, Br, or SCN), where L = MeCONH, and DL = MeCOND,.445 The v(C=O) wavenumber of free urea (1686cm-l) is shifted to 16401647 cm-l in the adducts Ln13,5CO(NH,), and Ln13,5CO(NH,),,41,,10H,0, where Ln = La, Ce, Pr, or Nd; there is therefore M - 0 c o - ~ r d i n a t i o n . ~ ~ ~ Estimates of co-ordination numbers in lanthanide-DM F complexes in MeNO, solutions have been made from intensities of i.r. bands due to v(C=O) of the amide. Splitting of this band in some solutions suggests that more than one complex, with differing co-ordination numbers, is present. The co-ordination numbers decrease from 8 or 9 in Pr3+ or Nd3+ to 6 in Er3+complexes.447 C104-, and also a few ligand, wavenumbers were listed for [Ln(ClO,),],nTM MA, where TMMA = NNN'N'-tetramethyladipaniide, n = 4 for Ln = La, Ce, Pr, or Nd, and n = 3 for Ln = Sm, Eu-Lu, and Y.448 The amide v(C=O) bands shift to lower wavenumber by 32-77cm-l on co-ordination of a number of amides with ThIV, U I V , and U 0 , 2 + nitrates. The nitrate modes were consistent with bidentate nitrate c o - o r d i n a t i ~ n . ~ ~ ~ v(C=O) in [R(CN)NSnPh,], where R = EtC(O), PhC(O), PhCH,C(O) etc., are about 130cm-l lower than in the free NN-disubstituted amide; thus the co-ordination to the Sn is uia the carbonyl oxygen. When R = CF,, the decrease in v(C=O) is much smaller, oiz. 42

Nitrates and Nitrato-complexes.-1.r. spectra purport to show that the decomposition of hydrated M(NO,),(n = 3, M = Cr; n = 2, M = Co or Cu) to the oxides proceeds cia basic nitrates in which the nitrate ion is bidentate.451 The i.r. spectra of the complex [Mn(dppn),(NO,),] (dppn = 3,4-di-2-pyridylpyridazine) show that the two nitrato-groups are non-equivalent. This is confirmed by the X-ray structure determination, according to which both ligands are bidentate, but one is symmetric, the other being The complexes [NiL,](N03),, where L = R,PCH2CH2PR2,R = Me or Ph, [NiL(NO,),(H,O)], and [NiL(N03)(H,0)]BPh4. where L = (C6H11)2PCH,CH,P(C,Hll),, were characterized (ionic us. co-ordinated nitrate) from their i.r. spectra. Thus, the first type shows a single band at about 1375 cm-l, the second a doublet at 1485, 1280 The NO3 group modes were given for [LM(NO,),],nH,O [M = Ni or Cu, n = 0, M = Zn, n = 1, L = 2,6-diacetylpyridine b i ~ ( a n i l ) ] . ~They ~ ~ arc consistent with the presence of both unidentate and chelating NO3 groups, as determined by an X-ray diffraction study on the Ni compound. A. Yu. Tsivadze, Yu. Ya. Kharitonov, G. V. Tsintsadze, A. N. Smirnov, and M. N . Tevsadze, Russ. J . lnurg. Chcm., 1974, 19, 1430. ua L. Yu. Alikberova, M . G . Zaitseva, L. F. Yastrebova, and B. D. Stepin, R i m . J . Inorg. Ch(p/lr., 1975, 20, 144. p47 L. N. Lugina, N. K. Davidenko, L. N. Zabotina, and K . B. Yatsimirskii, Russ.J. Inurg. Chcnl., u13 440 450 451 452

463 OSp

1974, 19, 1456. G. Vicentini and R. Isuyania, J . Inorg. Nuclear Chcnt., 1975, 37, 1810. K . W. Bagnall and 0. V. Lopez, J.C.S. Dalton, 1975, 1409. E. J . Kupchik and J. A. Feicabrino, J . Organonictallic Chcm., 1975, 93, 325. 1. N . Kalinichenko, A . M . Sirina, and A. I . Purtov, Russ. J . Inorg. C h c ~ t . ,1974, 19, 843. J . E. Andrew, A. B. Blake, and L, R. Fraser, J.C.S. Dalton, 1975, 800. J. A. Connor and P. 1. Riley, Inorg. Chim. Acta, 1975, 15, 197. E. C. Alyea, G . Ferguson, and R. J. Restivo, Inorg. Chem., 1975, 14, 2491.

382

Spectroscopic Properties of Inorgunic and Organometaiiic Compounds

( 108)

Co-ordinated nitrate bands are present in (108), at 1040 (vl), 822/836 (vz), 1303/1405 (v,), and 754 cm-l ( v J . Combination bands at 1750 and 1820 cm-l are diagnostic of bidentate bonding.455 The i.r. spectra of lanthanide (Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Y) nitrate penta- and hexa-hydrates are very similar. In every case the pattern of absorptions suggests bidentate co-ordination of the NO, groups.456 The hexahydrates of lanthanide trinitrates Ln(N03),,6H20 (Ln = La, Ce, Pr, Nd, Sm, Eu, or Gd) give i.r. spectra which show that the NO, groups are coordinated and probably bidentate. The splitting of v,(E') of free NO3- is less than for the 'heavy' lanthanide trinitrates; thus the M-NO, co-ordination is weaker in the present ~ase.4~7 1.r. bands due to NO, in isonicotine hydrazide adducts of Pr(NO,), and Nd(N03), seem to show that both ionic and co-ordinated NO, are present. Whether the latter was uni- or bi-dentate was not, however, clear.458 The i.r. spectrum of (pyH),[Ce(NO,),] contains bands due to unidentate nitrato-groups. The splitting of v, (of the free ion) is 14Ocni-*, indicative of strong bonding.450 U'" and ThIV nitrates form complexes with Me,PO and (Me,N),PO, i.e. M(NO,),,xL. The nitrate wavenumbers show that it is always bidentate, although for U(N0,),,3Me,PO this implies 1 1-co-ordination. U(N03),,5Me,P0 also contained ionic nitrate.460 1.r. and some Raman data for tetrahydrated [U02(OH)zU02](N03)4 suggest that the NO3 ligands are bidentate. The hydroxy-groups are bridging.401 Nitrato-complexes of U 0 2 , also containing a variety of Schiff-base ligands, [UO,(NO,),(sb),], give v(N0,) bands at 1550-1480 cm-l (antisym) and about 1280 cm-l (sym). They are therefore believed to contain unidentate NO, ligand~.'~~ The separation between v,, and v, of NO, in the series [Me,Sb(NO,)],O 5 [Me,Sb(ox)(NO,)] < [Me,Sb(NO,),]( < MeNO,) suggests that the Sb-0 (of nitrate) bond in the oxinate derivative is more ionic than in [Me,Sb(NO,),], V. M. Dziomko, A. V. Ivashchenko, V. N . Avilina, and L. I. Nikol'skaya, Russ. J . Znorg. Cheni., 1974, 19, 1834. 460 G. Odent, E. Charetteur, and M.-H. Duperray, Reo. Chim. minPrale, 1975, 12, 17. 467 B. N. Ivanov-Ernin, Z. K . Odinets, B. E. Zaitsev, V. M. Akimov, M. Arias de Pasqual, and A . I. Ezhov, Russ. J . Inorg. Chem., 1974, 19, 1266. 458 N. K. Dutt, and A. K. Sen Gupta, Z . Nuturfursch., 1975, 30b, 769. 450 N. E. Mininkov, and E. F. Zhuravlev, Russ. J . h o r g . Chern., 1974, 19, 901. 4B0 J. G. H. du Preez and C. P. J. van Vuuren, J.C.S. Dalton, 1975, 1548. 401 A. Perrin and J. Prigent, Bull. Soc. chim. France, 1975, 2450. u2 R. G . Vijay and J. P. Tandon, J . Inorg. Nuclear ,]- (wavenumbers/cm-l) Ion Vibration and assignment

“i(CSd2I “i(CS&I-

v(C=S) v(C-S) u(C=S) v(C-S) v(C-S)

1015

850 960 895 510

The i.r.-active modes of [Ni(WS,),]2-, as the Ph,As+ salt, have been assigned, using data on the 68Ni/s2Niisotopic species (see Table 25).620

Table 25 Observed i.r.-active vibrational modes ftw [Ni(WS4)2]2-(wcrteriiinibersl cm-I) Wat.eriuniber Symnietry Mode (68Ni isotope) Mode description class no. Blu 1 490.0 u(W=S) B2u

B3u

2 3

4 5 6 7

8 9 10 11

172.0

449.0 320.0

167.0 ? (50)

496.0 449.0

328.0 203.0 180.0

PAW- S) u(W-S) v(Ni-S) pw(W-S)

8(SNiS’) u(W=S) u(W-S) u(Ni-S) 8(W=S) 8(SNiS’)

+ v(Ni-S)

+ 8(SWS)

Changes in the i.r. spectra of [NiL,I2-, where L = S,C,(CN),, S2C=NCN, S,C=C(CO,Et),, or S2C=N Ph, on the formation of crystalline polynuclear complexes [NiL,][(PPh,),M’], (M’ = Ag’ or Cut, n = 2 or 3) suggest that u9 620

G. Schmid and G. Ritter, Chem. Ber., 1975, 108, 3008. J.-N. Pons, J. Roger, and M. Stern, Compt. rend., 1975, 280, C, 763. A. Cormier, K. Nakamoto, E. Ahlborn, and A. Muller. J . Mul. Strucrure, 1975, 25, 43.

3 90

Spectroscopic Properties o f Inorganic and Organometailic Conipoitntls

anion-cation interaction takes place uili the niercapto-groups. I n [Ni(S,C= NPh),{(PPh,),Cu),], however, the Cu is co-ordinated via the carbiniate nitrogen."I A detailed study has been niade of the 1.r. spectra of ten 1,2-dithiolatocomplexes of Ni, of the type [Ni(S,C,R2)2]tL-(R = H, Ph, CF3, or C N ; tz = 0, 1 , or 2). The assignments were aided by the use of 58Ni and G2Niisotopic substitution i n some cases, and normal-co-ordinate analyses were carried out in all cases (UBFF). The results for the internal ligand modes are not really discussed, but they are listed, although there is appreciable discussion of the effect on v(C=C) of the change i n oxidation state, by a combination of HMO theory and Gordy's equation."?" A normal-co-ordinate analysis has been performed on trans-[Pd(SMe,),X,] (X = CI, Br, or I), using data from the normal and [2H6]-species.523 An attempt to produce thiocarbonyl complexes of Pt" gave a novel metallodithiocarboxylate [C1(Ph3P),PtCS,Pt(PPh3)J+. Characterization used i.r. data."' v(C=S) bands are at 1010 and 1090 cm-l i n the i.r. spectra of the mercaptides [MSC6H4SM], ( M = CLI or Ag), [MSCsH4], (M = Cu, Pb, Hg, or Ni), and [CUSC6H~],.625 1.r. spectra have been reported for complexes of SC(NH2)2and SC(ND,), with several metals: [Cd(thio),X,] (X = C1, Br, or I), [M(thio),Cl,] (M = Mn, F'c, or Ni), [Cu(thio),Cl], [Pb(thio),CI,], [Pd(thio),]X, (X = CI or Br), [Pt(thio),Cl,], and [Pt(thio),]CI,. Assignments were proposed from a norii7al-co-ordinalc analysis of the M-SC(NH2), fragment.52G v ( S S ) in LaSz is seen at 445, 416, 4 0 0 c i i i ~(i.r.), ~ 449, 420cnir' (Kaman). These values are not inconsistent with a site symmetry of C1,and a factor group D2h. Similar i.r. bands were seen for Ce, Sm, and G d analogues.527 In CS, or CH,CI, solutions, [(Me,NCS,),TI] shows a splitting of the i.r. band between 950 and 100 cm-l, indicating unidentate Me,NCS,- co-ordination according to criteria quoted in the literature. 'This was not observed for the solid. In agreement with the latter, a full X-ray structure determination shows the TI t o be six-co-o r di na t e .528 Some group-frequency i.r. assignments were given for the -NCS, parts of (122) and (123).529 1.r. bands were also listed for the characterization of [Sn(S,CNR,),] (R = Me or Et)."O [Me,NC(O)SMMe,] give bands due t o v(C0) at 1630 (M = Ge) or 1609 (M = Pb) c111-l. They are therefore S- rather than O-esters."l G21

652

G23 624

M. L. Calftry and D. Coucouvanis, J . Inorg. N ~ c f ~ Chetn., ur 1975, 37, 2081.

C.W. Schl3pfer and K . Nakanioto, Itlot-g. Chenr., 1975, 14, 1338.

M. Tranquille and M . T. Forel, J . A![)/. Sfrricliirc, 1975, 25, 413. J. M. Lisy, E. D. Dobrzynski, K . J. Angelici, and J. Clardy, J . Attrrr. ClrcJtir.Soc., 1975, 97,

656. G . N. Schrauzer and H. Prakash, lnorg. Chcm., 1975, 14, 1200. G28 Y u . Ya. Kharitonov. V. D. Breaa. A. V. Ablov, and N . N. Proskina, R i m . J . Inorg. Chcm., 1974, 19, 1187. m7 Y u . M . Golovin, K. I. Petrov, E. M. Loginova, A. A. Grizik, and N . M . Ponomarev, Rirss. J . Inorg. Client., 1975, 20, 155. 6 2 8 H . Abrahamson, J. R. Heiman, and L. H . Pignolet, Inorg. Chcm., 1975, 14, 2070. l a O I . Tossidis, A. Singolliton, and G. Manoussakis, Inorg. Nuclear ChC/72. Letrcrs, 1975, I I ,

626

1

283. G30

_

D. Perry and R . A. Geanangel, Inorg. Chirir. Acrc2, 1975, 13, 185. A. E. Lemire and J. C. Thompson, C'atrad. J . Cheni., 1975, 53, 3727.

Vibratiorrai Spectra of Some Co-ordiitated Ligaiicis

(122)

39 1

(123)

Fifteen complexes of the type [MBr(L-L),] ( M = As, Sb, or R i ; L-L = dialkyldithiocarbamate) have been made, and t*(C-S) and v(C-.") listed.632 [M(chel),] and [XM(chel),] [M = As, Sb, or Bi; X = C1, Br, or 1 ; and chel = (CH,),NCSe,] all give v(C-N) in the ranges 1477-1517 and 1428-1441 cm-l. v(C-Se) is between 818 and 847 ~ n 1 - l . ~ ~ ~ v(C-N) and v(C=S) bands in the complexes [Bi(SC(S)NR,),]+BF,- are at higher wavenumbers than in the tris-complexes [Bi(SC(S)NR2)3].634This was ascribed to the enhanced positive character of the Bi atom in the new species.

7 Potentially Ambident Ligands

Cyanate and Thiocyanate Complexes and Iso-analogues.-The i .r. spectra of extracts, by tributyl phosphate, of TiOCI., from solutions containing NCSshow that a Ti-NCS complex is present, formulated as [H,mH,O,TBP],[TiO(NCS),],nHNCS. Thus v(CN) is at 2040 cni--1.535 [Ti(NCS),I3- in MeCN solution gives v(CN) at 2064, 2040, and 2015 cm-l, v(CS) at 754 cni-l, and G(NCS) at 498 cni-l. All of these are consistent with Ti-N c o - ~ r d i n a t i o n . ~ ~ ~ The photochemical isomerization of [CpM(CO),(NCS)] to [CpM(CO),(SCN)] (M = Mo, n = 3; M = Fe, n = 2) has been followed by monitoring the i.r. spectrum in the v(C0) and v(CN) regions.537 A band at 740cm-l, assigned to v(CS), suggests M-SCN bonding in [CpW(SCN),]. The isomeric [CpW(NCS),] has no such band, and an abnormally great intensity for the Cp band at 840 cm-l, i.e. there is a contribution from v(CS) in this case. v,,(N3) is at 2080 cm-I in [ C P , W ( N ~ ) ~ ] . ~ ~ ~ M-N bonding was deduced from the i.r. wavenumbers of [M(NCS),],4H20,2C6HlzN4(M = Mn, Co, Ni, Zn, and, probably, Mg) and in [M(NCS),],4H20,C6H12N4 (M = Mn, Co, or Ni) (C6HI2N4:= h e ~ a m e t h y l e n e t e t r a m i n e ) . ~ ~ ~ Compound (124) gives an i.r. band due to v(N=C=O) at 2208 cm-l. This is in accord with the bridging formulation, since a terminal group should absorb cn. 30-40 cm-l higher.S40 The presence of v(NC) at 2080, 2065 cm-' and v(CS) at 762 cm-l for trans[Ru(NO)(NH,),(NCS)](NCS), is consistent with Ru-NCS co-ordination. A number of other assignments were also made, e.g. v(N0) at 1886 G313 633 6:14

635

630

G37

G38

63Q G40

641

G, E. Manoussakis, C. A . Tsipis, and C. C. Hadjikostas, Cnnod. J . Chem., 1975, 53, 1530. G. E. Manoussakis, C. A. Tsipis, and A . G. Christophides, 2.anorg. Chenr., 1975, 417, 235. G . E. Manoussakis, M . Lalia-Kantouri, and R . B. Huff, J . Inorg. Nuclear Chcm., 1975, 37, 2330. A. M. Sych and V. V. Gerbuz, Russ. J . Inorg. Chcm., 1974, 19, 1042. A. M. Sych and N. I. Bogatyr', Russ. J . Inorg. Chem., 1974, 19, 1470. D. G. Alway and K . W. Barnett, J . Orgonometallic Chenr., 1975, 99, C53. M. K . Rastogi and R. K . Multani, J . Inorg. Nuclear Chcm., 1975, 37, 1995. T. G. Ralicheva, I. V. Pologikh, and 1. V. Seliverstova, Russ. J. Znorg. Chcm., 1975, 20, 548. A. Albini and H. Kisch, J . Orgnnornetallic Chcm., 1975, 94, 7 5 . N. M. Sinitsyn, V. V. Borisov, and L. A. Pshenichnikova, Russ. J . Inorg. Chcm., 1974,19, 1667.

392

Spectroscopic Properties of litorganic and Organometallic Compoitnds Me

: N = )

MC

(C0l3 Fe

~>N=c=o

FC

(CO),

v(NCS) wavenumbers, together with v(M-py or -bipy), were listed for [CoM(NCS),],xL and [Ni(NCS),],xTHF (M = Zn or Cd; L = THF, py, bipy, phen, en, or trien).54z A detailed and careful study has been made of the XCN bonding in [Co(CN),(XCN)I3- salts. The following conclusions were drawn : (i) in protic solvents such as ethylene glycol, X-bonding prevails, being stabilized by H-bonding, (ii) in CH,CI,, Me,CO, or PhNO,, isomerization to N-bonding occurs, (iii) in DMF an equilibrium is set up between an N-bonded isomer and a species resulting from the dissociation of the XCN- group. The dissociation is essentially complete in DMSO and MeCN, (iv) the cation also affects the bonding mode in the solid state; S-bonding prevails in the K+, Cs+, and MeNH,+ salts; a mixture (25% N-bonding) is obtained for the Me,NH2+ salt, while Me,N+ and Bun4N+only give the N-bonded isomers. A detailed discussion of the mechanism of isomerization was given, and the importance of the solvent and the counter-ion stressed.643 Group-frequency assignments have been made for the ligand modes in [CoL,CI,] (L = 1-vinyl-2-methylimidazole). A number of complexes of this type, but containing NCS ligands, were prepared and characterized from their v(CN) and v(CS) wavenumbers. Evidence was found for the existence of M-N bonding and NCS bridging.644 The following isomer assignments have been made from consideration of the values of the integrated v(CN) absorption band intensities in solution: [Co(dmgH),(SCN),]-, both SCN; [Co(dmgH),(NCS),]-, both NCS; [Co(dmgH),(CN)(SCN)]-, SCN ; and [Co(dmgH)(dmgH,)(CN)(SCN)], SCN (dmgH, = dimethylgly~xime).~~~ The isomerizations of some 20 complexes of the type [Co(dnigH,),L(SCN)] (L = various pyridines) was followed by monitoring the integrated intensity of the v(CN) band (en. 3 x lo4 1 mol-l cm-, for S-bonded; ca. 10 for N - b ~ n d e d ) . ~ ~ ~ Shifts in the i.r. band at 2075 cm-1 for NCS-, observed in aqueous solutions in the presence of NP+, Pr3+,or Ho3+ have been used to characterize the complex formation. Intensities were measured and used to estimate stability constants for the complexes.647 The observed values for v(CN), v(CS) in [M(nas)(NCS),] [M = Ni, Pd, or Pt; nas = 1,8-naphthaIene-bis(dimethylarsenide)] are all very similar. Nevertheless, it was suggested that the Ni complex was N - , the others S - b ~ n d e d . ~ ~ ~ SQ3

L44 b45

P. P. Singh, U . P. Shukla, R. Makhija, and R. Rivest, J . Znorg. Nuclear Chem., 1975, 37,679. J. H . Melpolder and J. L. Burrneister, Znorg. Chim. Acfa, 1975, 15, 91. K . C. Dash and P. Pujari, J . Inorg. Nuclear Cliem., 1975, 37, 2061.

A. L. Crumbliss and P. L. Gans, Inorg. Chem., 1975, 14, 2745.

Lao A. H . Norbury, P. E. Shaw, and A . I. P. Sinha, J.C.S. Dulton, 1975, 742. b47

64n

V. S. Netsvetaeva and I. M . Batyaev, Russ. J . Inorg. Chem., 1974, 19, 684. M. Benettin, L. Sindellari, M . Vidali, and R. Ros, J. Inorg. Nuclear Chem., 1975, 37,2067.

Vibrational Spectra of Some Co-ordinated Ligands

393 Bands due to the NCS or NCO fragments in [ML(C,Cl,)(PPh,),] (M = Ni or Pd; L = NCO or NCS) are all indicative of N-bonding (see Table 26).549 A

Table 26 Pseudohalide group wauenumberslcm-l in [M L(C,CI,)(PPh,),]

M

Ni Pd Ni Pd

L NCS NCS NCO NCO

b(V,)

8 50 830 1345 -

V2@)

V3(Vah

605 598

2075 2050 2220 221 5

-_ --

similar conclusion was drawn for [NiL(c,Cl,)(dpe)] [dpe = 1,2-bis(diphenylpho~phino)ethane].~~~ Ionic C10,- but co-ordinated NCS- were detected in the i.r. spectra of “i2(L)n(NCS)aI (n = 1 or 31, [Niz(L)~(Hzo)l(cl04)4,“i,(L),1(clo4)5(Bph4), and [Ni2(L)3(H20)](C104)(BPh4)3, where L = P ~ A s ( C H , C H ~ C H , A S M ~ ~ ) , . ~ ~ ~ v(CN) values and some integrated intensity measurements were used to determine S- or N-co-ordination in some new NCS- complexes of Pd (Table 27).652

Table 27 v(CN) waoenumberslcm-l and integrated intensities/ for some new NCS complexes of Pd Compound tPd(VPP)(SCN),I [Pd(vaa)(SCN),I [Pd(vasP)(SCN),I [Pd(dpph)(NCS)(SCN)]

Nujol niull 2105 21 10 21 10 2120, 2085

CH2CI, solution 21 10 2115 (+2080 w) 2115 (+2080 w) 21 15, 2080

I cm-2 mol-1 Integrated intensity

1.9 2.1 2.3 I

The thiocyanate complex [Pd2(NCS).L(C,F5),(PPh3)z] gives a single v(CN) band at 2148 cm-’. This is consistent with the symmetrical arrangement of bridging NCS groups (125).,,,

(125)

The complexes [M(L)(NCS),(ClO,),-,] (M = Zn, Cd, or Hg; L = a number of polyamine ligands; x = 1 or 2) are shown by i.r. to be M-N bonded when M = Zn or Cd but M-S when M = Hg.554 A number of NCS- complexes of Sc, Gay and In have been shown555-558to be M-N bonded in every case. m0 66a

66s 1b4

6bo

667 s6R

J. M. Coronas and J. Sales, J . Organometallic Chem., 1975, 94, 107. J. M. Coronas, 0. Rossell, and J. Sales, J . Organometallic Chem., 1975, 97, 473. W. Levason, C. A. McAuliffe, and D. G. Watson, J . Coordination Chem., 1975, 4, 173. K. K. Chow, W. Levason, and C. A . McAuliffe, Inorg. Chim. Acta, 1975, 15, 79. R. Uson, P. Royo, J. Fornies, and F. Martinez, J . Organometallic Chem., 1975, 90, 367. A. Diaz, M. Massacesi, G. Ponticelli, and G . Pachina, .I. Inorg. Nuclear Chem., 1975, 37, 2469.

V. S. Mal’tseva and Yu. G. Eremin, Russ. J. Inorg. Chem., 1975, 20, 180. L. M. Mikheeva, A. I. Grigor’ev, and A. I. Tarasova, Russ. J . Inorg. Chem., 1974, 19, 1277. L. M. Mikheeva and A . I. Tarasova, Russ. J . Inorg. Chem., 1975, 20, 202. V. S. Mal’tseva and Yu. G. Eremin, Russ. J . Inorg. Chem., 1974, 19, 1268.

394

Spectroscopic Properties of Inorganic and Organometallic Cotnporrnh

Integrated intensities in Me2C0 solution of the v(CN) bands i n [Me,TI(NCS)], [Ph,TI(NCS)], Ph,As[Me,TI(NCS),], and [PhTl(NCS),] suggest that the first three are N-bonded, with some ionic character, while the last is S - b ~ n d e d . ~ ~ ~ v , and v,, of the pseudohalide ligand are in the regions expected for Si-N bonding in [CpFe(CO),SiX,] (X = NCO or NCS).660 v(CN) and v(NCX) were assigned for R,SiNCX (R = Me, Et, or Pr'; X = 0, S, or Se).661

Ligands containing N and 0 Donor Atoms.---The azomethine stretching mode is shifted by 10-30 cm-' to lower wavenumber (from its value of 1615 cm-l in the free ligand) in a wide variety of complexes of the dianion of the Schiff base (126).562 Some group-frequency assignments have been made for a number of Be-edta (edta = Y) complexes [H,BeY],2H20, [D2BeY],2D,0, [KHBeY], [KDBeY], etc. There was evidence for existence in solution of the equilibrium:663 [BeHYI-

+ H,O

[Be(OH)H,Y]-

Shifts in .(PO,) and v(CH) wavenumbers in a number of alkaline-earth metal nitrilotrimethylphosphonates [ML]"- { M = Mg, Ca, Sr, or Ba; Ls- = [N(CH,P0,),l6-} are consistent with M-N rather than M - 0 ~ o - o r d i n a t i o n . ~ ~ ~

The i.r. spectra of [M(DMF),(NO,),I, [M(bipy)(NO,),], [M(phen)(NO,),], ~ ) ~ all ] consistent with M-N02 (M = Zr or Hf), and ( B U , N ) ~ [ Z ~ ( N Oare co-ordination, i.e. they are n i t r o - c ~ m p l e x e s . ~ ~ ~ Nitrito- and nitro-isomers [CpMoO(L)] (L = O N 0 or NO,) are distinguished by their characteristic i.r. bands. Thus L == O N 0 gives features at 1470 and 1060cm-', and L = NO2 has bands at 1440 and 1310cm-l. If L = ONO,, the usual bands of unidentate nitrate are seen.s6s The reaction between [ MoOCl,(MeCN),] and oxH under anaerobic conditions affords [MoOCl,(oxH),]. The co-ordination of neutral oxH ( = quinolin-8-01) is shown by the i.r. bands at 3325 and 3220 cm-1.567 Thiocyanato-complexes of Mn, Co, Ni, and Cd with ortho-, nteta- or paraisomers of methoxybenzoylhydrazine give very complex i.r. spectra. The g6B 680

661

682

6(i4

6a5

687

N. Bertazzi, G. C. Stocco, L. Pellerito, and A. Silvestri, Atti Accad. Sci.,Lett. Palernto, Parte I, 1973, 33, 181. M. Hiifler, J. Scheuren, and D. Spilker, J. Organometallic Chem., 1975, 102, 205. J. A. Seckar and J. S. Thayer, Inorg. Clietn., 1975, 14, 573. H. A. Tayim, M. Absi, A. Darwish, and S. K. Thabet, Inorg. Nuclear Chent. Letters, 1975, 11, 395. N. I. Voronezheva, A. I. Grigor'ev, and N. M. Dyatlova, Russ. J. Inorg. Chetn., 1974, 19, 1770. A. I. Grigor'ev, L. V. Nikitina, and N. M. Dyatlova, Russ,J. Inorg. Chetn., 1974, 19, 1079. A. M. Golub and T. P. Lishko, Russ. J. Inorg. Chem., 1974, 19, 1292. M. S. Bhalla and R. K. Multani, J. Organonietallic Chem., 1975, 101, 93. C. A. McAuliffe and B. J. Sayle, Inorg. Chirii. Acta, 1975, 14, L43.

Vibrational Spectra of Some Cb-ordinated Ligatids 395 following conclusions were drawn from slender evidence:5s8(i) all of the hydrazine derivatives act as N/O chelates (127); (ii) NCS is co-ordinated via N in all cases. A cyclic structure H2hCH2C(OH)=O- hCI2is proposed from the i.r. spectra in the v(C0) region of 1 : 1 complexes of MCI, ( M = Zn, Cu, Ni, Co, Fe, or Mn) and g l y ~ i n e . ~ ~ ~ Ethylenediaminediacetato-compounds of Ru"', Cs2[Ru(Hq)C1,],3H,O, K[Ru(q)C1,],2H20, and [Ru(q)CI(H,O)],H,O, where q2- = -02CCH2NH(CH,),NHCH,CO,-, have been characterized by their i.r. spectra. I t appears that Hq acts as a bidentate and q as a quadridentate ligand.570 The absence of v(C0) of C0,H (ca. 1700cm-') in the i.r. spectra of [M1"(NH2CH2C02H)(NH,CH,C02)CI] (M = Rii, Rh, or Ir) shows that the glycine molecules are co-ordinated in the betaine form H3N+CH,C02-.571 The observation of va,(CO2), v 8 ( C 0 2 at ) more than 1600, and approx. 1360 crn-l, respectively, in [(nbd)Ru(gly),], [(cod)Ru(gly),], [(cod)Rh(gly)], [(cod)Rh(pro)], [(cod)Ir(gly)], and [(cod)Ir(pro)] (nbd = norbornadiene, cod = cycloocta-1,5-diene, gly = glycine, and pro = proline) shows that the amino-acid carboxylate is unidentate, and so N/O chelation has The v(C0) and v(NH) positions indicate that (respectively) the ketonic and amino-groups are not co-ordinated in [Ma2],4H,O, [M(hip)J,6H2O, [ M(a),],pz, and [Ni(hip),],pz (M = Co or Ni; pz = piperazine; hipH = hippuric acid; aH = aceturic The separation between v, and va, of the C 0 2 group, however, shows that the carboxylato-group is bidentate in all cases except [Co(a),],pz, where it is unidentate. Evidence has been presented for the detection of the low-temperature transient (128), during the 365 nm photolysis at 77 K of [Co(NH,),(NO,)]CI, as an i.r. study in the 1200-500 cm-1 region.574

The occurrence of v(C=O) at 1554 (Ni), 1555 (Co) cm-l in (129) suggests that there is an interaction between the C=O bond and the adjacent ~ e t a 1 . ~ 7 ~ The i.r. spectrum of the 2,2',2"-nitrilotriethanol complex of CoI'', [Co(OC,H,),NC2H40H(OC2H,)N(C2H40H)2],6H20, contains a very broad feature at 3200-

b70

672 67R

674 67b

Yu. Ya. Kharitonov, R. I. Machkhoshvili, N . 13. Generalova, and R. N. Shchelokov, Russ. J . Inorg. Chem., 1975, 20, 387. I. A. Sheka and K. I. Arsenin, Ukrain. khint. Zhur., 1975, 41, 563. N. A. Ezerskaya, T. P. Solovykh, 0. N. Evstaf'eva, L. J. Shubochkin, and N. K. Bel'ski, Russ. J . Inorg. Chem., 1975, 20, 581. V. 1. Nefedov, I. V. Prokof'eva, A. E. Bukanova, I. K . Shubochkin, Ya. V. Salyn', and V. L. Pershin, Russ. J. Inorg. Chem., 1974, 19, 859. C. Potvin, L. Davignon, and G. Pannetier, Bull. Soc. chin?.France, 1975, 507. G . Marcotrigiano and G . C. Pellacani, Inorg. Nuclear Chem. Letters, 1975, 11, 643. D. A. Johnson and K . A. Pashman, Inorg. Nuclear Chem. Letters, 1975, 11, 23. G. C. Percy, J . Inorg. Nuclcar Chem., 1975, 37, 2071.

396

Spectroscopic Properties of Inorganic and Organometallic Compounds

3600cm-l. This is probably due to the formation of hydrogen bonds between ligand OH groups and the water of c r y s t a l l i ~ a t i o n . ~ ~ ~ An alternative interpretation to that previously put forward has been proposed for the 1170 cm-l band (hitherto assigned exclusively to an O N 0 vibration) in the i.r. spectra of cis-[Co(tn),(NO,),]+ (tn == 1,3-diarninopropane). This was based on deuteriation experiments, but no completely unambiguous interpretation emerged.677 An i.r. band at 1700 cm-l, due to the v(C=O) of a free C0,H group, is found for [Rh(NH,CH,C0,H)(NH2CH2C02),Cl], showing the presence of one unidentate glycine ligand.57s A hydridic Ir complex, containing cod and dipyridyl ketone (dpk), has no v(C=O) band, and a pyridine ring mode at 1600cm-l. These observations suggest that the dpk is co-ordinated as in ( I 30).679 The adduct 3CsN02,Ni(N0,), gives bands due to co-ordinated nitro-ligands at 1345, 1320 cm- (N-0 stretching), 865 cm-1 (deformation) that are believed to be characteristic of a symmetrically bonded group. Bands due to free NO2were also present [v(NO) at 1270 and 1380 ~ n i - - ~ ] . ~ ~ O t

(130)

Shifts in v(NH), 8(NH,), and v(C=O) on coniplexation of the hydrazides of p-Me-, p-MeO-, or p-CI-benzoic acids ( = HL) to give NiS04,3HL,2H,0 or Ni(N03)2,3HLshow that the NH, group and the C=O group are taking part in binding to the v(NH) and v(C=O) were listed for the 13-isonitroso-imine complexes (131 ; X = OMe, Ph, or NHPh).582 1.r. bands (1550 --1660 cn-I) characteristic of aromatic and imine modes have been listed for 24 Ni” complexes with N,O-donor ligands of the type [Ni(chel)X,] [X = CI, Br, 1, or NCS; chel = (132); n = 2 or 3 ; R = 0-C6H4,(CH,),, (CH,)3, or CH2CHMe].5s3 678

V. V. Udovenko, 0. N. Stepanenko, and B. G . Eroshok, Russ. J . Inorg. Chem., 1974, 19, 1341.

677

M . B. Celap, M . J. Malinar, and P. N. Radirojsa, Inorg. Chem., 1975, 14, 2965. A. E. Bukhanova, 1. V. Prokof’eva, and T. P. Sidorova, Russ. J . Inorg. Chem., 1974, 19, 1825.

67@

GBo 681

689

683

G . Zassinovich, Ci. Mestroni, and A. Camus, J . Organoiiietallic Chem., 1975, 91, 379. T. A. Andreeva and S. S. Pozharskaya, R i m . J . Inorg. Cfiem., 1975, 20, 431. P. 1. Shman’ko and S. S, Butsko, Russ. J . Imorg. C’hem., 1975, 20, 241. R. R. Iyengar, K . S. Bose, and C. C. Patel, J . Inorg. Nuclear Chem., 1975, 37, 75. L. G. Armstrong and L. R. Lindoy, Inorg. Chem., 1975, 14, 1322.

Vibrational Spectra of Some Co-ordinated Ligands

397

v(G,1-0) bands are at about 1540 cm-l in (133) and (134), i.e. some 1520 cm-l higher than in similar mononuclear a d d u ~ t s . ~ ~ * The arginine complexes [Ni(arg)X],nH,O (X := C1, Br, NO3, or Clop) and [Ni(argH),X2],nH20 (X = C1, NO3, Clod, or OH) have been partially characterized by i.r. Only for [Ni(argH)2(N03)2],H,0and [Ni(argH)(OH),],H,O are the X ligands co-ordinated. Perhaps the most interesting observation is that the complexes containing ionic Clod- rearrange under the pressure of KBr disc formation, to give bidentate, co-ordinated R3

R3 [PtMe,Br(ONO)(lut),], with v(N=O) at 1511, v(N-0) at 960 cm-l, isomerizes to the nitro-form on heating [v,,(NO,) 1420, v,(NO,) 1332/1322cm-l] (lut = lutidine).68s The new compounds K,[Pt(ONO),(NO,),] and K2[(0,N),Pt(ONOa)aPt(ONO),] were characterized by i.r.587 v(N0,) occurs as a single i.r. band at 845 cm-l in K[Pt(gl)(NO,),(H,O)] The i.r. spectra of (81 = glycinato); thus the two NO2 groups are Pt(o- or p-MeOCsH4CONHNHa)2contain bands due to v(C-N) and v(C=O) m5

R. J. Butcher and E. Sinn, J.C.S. Chem. Comm., 1975, 832. S. T. Chow and C. A. McAuliffe, J . Inorg. Nuclear Chem., 1975, 37, 1059. J. R. Hall and G. A. Swile, J . Organometallic Chem., 1975, 96, C61. L. K. Shubochkin, E. F. Shubochkina, and V. I. Nefedov, Russ. J . Inorg. Chem., 1974, 19, 1356. G. S. Muraveiskaya, T. N. Leonova, and V. F. Berezina, Russ. J . Inorg. Chem., 1974, 19, 1822.

398

Spectroscopic Properties of liiorganic and Organometnllic Compoimds

in the same regions as in the analogous benzoylhydrazine and nitrobenzoylhydrazine complexes.58B [Pt(salnr)Me,X], where salnr = an N-substituted salicylaldiminate anion and X = 3,5-lutidine or PPh3, all give v(C-0) due to a bidentate salicylaldimine ligand between 1300 and 1400 cm-l. When X = PPh,, two 6(Me) modes are seen, at 1213 and 1235 cm-l. The lower of these can be assigned to the Me trans to the PPh, group. In the dinuclear [PtMe,(salnr)], v(C-0) is at 1278 cm--', due to bridging salnr (135).590 In the i.r. spectra of Cu" complexes of N-benzoylglycine, (i) there is a considerable shift of v(NH) to lower wavenumber on co-ordination ( 5 0 - 1 50 cm-I), (ii) there are v(C0,-) bands indicative of unidentate or bridging N-benzoylglycine. The complexes concerned were [CuL,],nH,O (n = 1 or 4)and [CuL,],L', (n = 2; L' = piperazine, en, py, or ~ h e n ) . ~ ~ ' Large changes were observed in the i.r. spectra (1200-1800 cm-') of Cu" and Zn" complexes of glycylglycine in D 2 0 on going from acidic to neutral solution. These were interpreted in terms of equilibria among free and complexed forms. In particular, for Cu", at 3 < pD < 5, M-L bonding is via amino-nitrogen and peptide oxygen, but at higher pD this changes to bonding via amino-N, peptide-N (deprotonated), and C=0.5n2 v(0H) of (136) is at 3230 cm-l. Thus OH is present, and H-bonded, but not so strongly as in the free ligand.5g3 1.r. spectroscopy has been used in a study of amine complexes of metal salts of PhCONHCH,CO,H (hippuric acid, chelH), i.e. [M(chel),L,] [M = Zn, Cd, or Hg; L, = py, phen, (en),, en, morpholine, piperazine, etc.]. The v(C02)data show that for M = Zn, chel is unidentate, while for M = Cd or Hg, symmetrical or unsymmetrical bidentate co-ordination via the CO, group is indicated, i.e. the co-ordination is p s e u d o - o ~ t a h e d r a l . ~ ~ ~ Assignments were proposed for v(NH), v(CO), and v(C0,) (s and as) for the Zn, Cd, and Hg complexes of N-acetylglycine (aceturic acid, acetuH) and their adducts with a number of amines (these were all attached via the N). vaS(CO,)ve(C02),which has been proposed as a measure of the M - 0 bond strength, lay in the order Zn > Cd > Hg.595 v(C00) and 6(CH) modes of the edta4- ligand are seen at 1415, 1330cm-l, respectively, in [Cd(edta)BrI3-. Acidification of the solution leads to the formation of [Cd(Hedta)Br,],-, characterized by 6(NH) at 1345 cm-1.6n6 [MeCH(OH)CH,Hg(ONO)] gives v(N=O) at 1390 cm-l, v(N-0) at 1046 ~ r n - l . ~ ~ ' 688

6oo

b04 bQ6

b06

697

Yu. Ya. Kharitonov, R. 1. Machkhoshvili, A. N. Kravchenko, and R. N. Shchelokov, Rum. J . Inorg. Chem., 1975, 20, 151. J. R . Hall and G. A. Swile, Austrul. J. Chct?i., 1975, 28, 1507. G. Marcotrigiano and G . C. Pellacani, Z . anorg. Chcnt., 1975, 413, 171.

M. Tasumi, S. Takahashi, T. Nakata, and T . Miyazawa, Bull. Chem. Soc. Japan, 1975, 48, 1595. H . Endres, H. J. Kellcr, M . Megnamisi-Belombe, and D. Nothe, Z. Nafurfursch., 1975, 30b, 535. G. Marcotrigiano and G . C. Pellacani, Z.anorg. Chem., 1975, 415, 268. G. Marcotrigiano, L. Menabue, and G. C. Pellacani, J . Inorg. Nuclear Chem., 1975,37, 2344. Zh. G. Abraniyan, N. M. Dyatlova, A. Ya. Fridman, and Kh. R. Rakhmov, Russ. J. Inorg. Chcnt., 1974, 19, 793. S. Shinoda and Y. Saito, J . Orgartor~zetallicChcnr., 1975, 90, I.

Vibrational Spectra of'Sonie Co-ordinatcd Ligaiids

399

0-H-0

/

Me

v(C0,) of unco-ordinated C 0 2 H groups are at 1690-1770 cm-l, and of co-ordinated C0,- are at 1610-1660 cni-I in the i.r. spectra of eleven hydrated lanthanide dipicolinate and quinolinate complexes of the types [Ln(dipi)(di~iH)(H,O)~l,[Ln(dipiH),(H,O)], and [Ln(q~in)(quinH)(H,O)~](dipiH, = pyridine-2,6-dicarboxyiic acid ; quinH, = pyridine-2,3-dicarboxylicacid).6Q8 Some ligand modes, v(C=N), v(C- 0) ctc., were assigned for lanthanide Schiff-base complexes [M,(sb),] and [M(OPri)(sb)], where M = La, Pry or Nd; sb = (137).6uu The i.r. spectrum of [(oxineH),(U0,),(C,04)3],(oxine),(H,0), contains bands at 1094 and 1109 an-', due to v(C-OH) of the unco-ordinated quinolinol, and v ( C - 0 ) of co-ordinated quinolinate, respectively.s00 Characteristic i.r. bands have been listed for U022+, NO3-, and L in the complexes [UO,(L)(NO,),], where L = (13Sa) or ( 1 3 8 b ) F

(

I Ma)

(138b)

The mode of co-ordination of a number of a-amino-acids, e.g. glycine, a-alanine, norvaline, etc,, to MCI, (M = Ga or In) has been studied by i.r. The co-ordination is said to occur through the N H , and the carboxylic 0 of the non-ionized C 0 2 H group.6o2 The relative intensities of C=O bands from the keto-group and the N-C=O co-ordinated to GaCl, suggest group of 6-piperidino-N-niethylanthrapyridone 60H Oo0

A. Anagnostopoulos, J . Coordination Chern., 1975, 4, 23 1 . S. K. Agarwal and J. P. Tandon, 2. Naturjursch., 1975,30b, 50. E. N. In'kova and V. P. Arsent'eva, Russ. J . Inorg. Chetn., 1974, 19, 742. B. Kim, C. Miyake, and S. Imoto, J. Inorg. Nuckar Chem., 1975, 37, 963. I . A. Sheka and K. I. Arsenin, Ukmin. khim. Zhur., 197.5, 41, 451.

400

Spectroscopic Properties of Illorganic and Organometallic Compounds 0

( I 39)

that the former is involved in the bonding, i.e. the complex contains the unit (1 3 9 ) . 6 0 3 [In(NO,),],MeOH gives bands due to NO, at 835 (a), 1276 ( v B ) , and 1390 (vaJ cm-l, so that In-NO, co-ordination is present. Similar results were found for the 2-aniinoet hanol derivative [In(N02)3(0C2H4NH,)].604 Some complexes of In' with bidentate monoprotic ligands, e.g. quinolin-8-olate (qno), have been prepared. The i.r. spectrum shows that the qno is chelated, and the wavenumbers of the characteristic bands near 11 10 and I580 cm-l are very close to those for the In"' derivative.,05 The i.r. spectra of R1,Sn(OCYR2) and R*,Sn(OCYR2), [Y = NCN or C(CN),; R2 = Me o r Ph] are consistent with the anionic ligands being bridging, via O/N or N/N co-ordination, to the metal. The Sn is respectively five- and sixco-ordinate in the two series.6o6

Ligands containing N and S Donor Atoms.-A review of transition-metal complexes of t hiosemicarbazones H2NCSNHN=CR1R2 and thiosemicarbazide H,NCSNHNH, includes a useful survey of the i.r. spectra of the co-ordinated ligands.,07 The Agi salt of AsF,- and [Re(CO),Br] react in the presence of NSF, to form [Re(CO),NSF,]+[AsF,]-. v(SN) and v(SF) shift to higher wavenumber compared to free NSF,, showing that the NSF3 is bound via the N. The v(C0) modes were consistent with C,, local symmetry for the Re(CO),.608 Some group-frequency assignments were made for Fe", Co", Ru'", Ru", Rh"', Pd'", Ir"', and PtIV complexes containing (140). Co-ordination always seems to occur via the S(H) atom, after loss of H, and via a N atom, sometimes of N=C-S, more usually of an imino-group derived from the N H 2 of the free ligand,,O9 1.r. data have been given as evidence for the proposal that thioisonicotinamide (141) co-ordinates to Ru" and Ru"' via the ring N atom, and not by the S or N H 2 groups.61o (Ios

Oo6 (Io6

Oo7 Oo8 609

010

B. E. Zaitsev, N. P. Vasil'eva, B. N. Ivanov-Emin, and M. V. Kazankov, Russ. J , Inorg. Chem., 1974, 19, 1584. A . M . Golub, R. Akmyradov, and S. L. Uskova, Russ. J. Inorg. Chem., 1974, 19, 958. J . J. Habeeb and D. G. Tuck, J.C.S. Dalton, 1975, 1815. H . Kohler, L. Neef, L. Korecz, and K. Burger, J . Organometallic Chem., 1975, 90, 159. M. J. M . Campbell, Coordination Chem. Rev., 1975, 15, 279. R. Mews and 0. Glemser, Angew. Chem. Internat. Edn., 1975, 14, 186. M. R. Gajendragad and U. Agarwala, J . Inorg. Nuclear Chem., 1975, 37, 2429. R. W. Craft and R . G. Gaunder, Inorg. Chem., 1975, 14, 1283.

Vibrational Spectra of Some Co-ordiiinted Lignnds

40 1

Co"' complexes of the thiocarbazoic acids NHR1NR2COSH (R' == R2 = H ; R' = H, R2 = Me; R1 = Me, R2 = H) all exhibit N/S chelation. Thc i.r. spectra show decreases in v ( N H ) and 8 ( N H , ) , and an increase in v ( C - O ) , as required by this."l

1.r. data have been used to determine the bonding type of some complexes of derivatives of the cysteinato ligand CyS, H,NCH(C02-)CH2S. Thus [Co(en),(CySO)]+ has v(S=O) at 953 cm-l, as for an S-bonded sulphenato-ligand, while [Co(en),(CySO,)]+ shows v n s ( S 0 2 )at 1 1 50 cm-l, again typical of an S-bonded I igand .612 Complexes of 2-mercaptopyrimidin-4-01 ( 1 42) with Rhlil, Pd", I'diV, Pt", and Pt'" give i.r. bands as expected for a bidentate chelating ligand, except for ptll 613

The disappearance of ligand modes due to v(NH) ( 3 3 0 0 ~ n - ~and ) v(SH) (2530 cni-l) on the formation of the complex [(a-mpg)Ni]-, where the ligand is a-mercaptopropionylglycine, is evidence for the participation of the S and the peptide N on co-ordination. The complex is therefore (143).014

( 143)

The ligand pms (144) forms complexes [Ni(pms)X]+, where X = C1 or Br, in which the S S stretch occurs as a Ranian band at 501 cm-l, compared to 506-512cm-1 in the free ligand. This slight shift was attributed to S-coordination, as in (145). This was confirmed by a single-crystal X-ray 1,3,5-Triazine-2,4,6-trithioI (146) forms complexes with Cu" and Pd" whose i.r. spectra suggest that they are polymeric, with ligands bridging via N and S atoms.61s 'Iu (119

ala

A. Monacci, F. Tarli, and S. Viticoli, J . Inorg. Nuclear Chem., 1975, 37, 2 5 5 8 . C. P. Sloan and J. H . Krueger, Znorg. Chetn., 1975, 14, 1481. I . P. Khullar and U. Agarwala, Ausrral. J . Chem., 1975, 28, 1529. Y . Sugiura, Y . Hirayama, H . Tanaka, and H. Sakurai, J . Inorg. Nuclear Cheni., 1975, 37, 2367. L. G . Warner, M. M. Kadooka, and K . Seff, Inorg. Clietn., 1975, 14, 1773. J. C. Chudy and J. A. W. Dalziel, J . Znorg. N d m r Chetii., 1975, 37, 2459.

402

Specttmrwpic Properties o j Itrorgurric arid Orgammetallic Conipoutlds

(145)

(146)

The copper-pyridine-2-thioloato-complex [Cu(pyS)] gives an i.r. band with some v(C-S) character at 1 1 31 cm-l. There is a similar feature at 1137 cni-l in [co(pys),].o" lminol forms of acid amides are unknown except in very rare co-ordination situations. An example is [Cu"(ptgH)X,] (147), where ptgH = N-(2-pyridylniethyl)-2-(ethylthio)acetamide. The amide 1, 11, and I11 bands are at very different positions from usual, i.e. in the X = C1 coniplex they are at 1660, 1367/1376, and 1228 cm-l, respectively. A number of other assignments were made, not ail on very strong evidence.G18

( 147)

(148)

It has been suggested that shifts in ligand ring modes in complexes of Zn, Cd, and Hg of the ligands (148; R = Ph, o-tolyl, p-tolyl, benzyl, or Me) show that the Zn and H g complexes involve co-ordination of the pyridine N atom. That of Cd is thought not to, however.G19 Bands characteristic of all the ligands were assigned in [ML,A,] (M = Zn or Cd; A = NCS, acetate, or BF4; rind L = OCNHC2H4SCH2or SCNHC2H4S).';20 The BF4- group is unidentate, as indicated by splitting of (tlu) v 3 and v4.

Ligands containing 0 and S Donor Atoms.---v(S0) in [VO(ReOr)J,5DMS0 is at 940 cin-l. The DMSO is therefore U-bonded, since S-co-ordination gives a band at 11 10---1115cni-1.621 trans-[Cr(en),( Me,SO)(HCON Me,)](ClO,), gives i.r. bands at 982 cm-l, assigned to v(SO), and at 1660cm-', assigned to v ( C 0 ) ; both the DMSO and D M F ligands are therefore The reaction of [M(CO),Br] with AgAsF, in the presence of SO, yields [M(CO),SO,]AsF, (M = Mn or Re). When M = Mn, the v ( S 0 ) waveN. Lenhart and H. Singer, Z.Nururforsth., 1975, 30b, 284. M. Nonoyania, Itrorg. Chin?.Acta, 1975, 13, 5. C. S. ti. Prasad and S. K. Banerji, J. Inorg. Nuclear Chem., 1975, 37, 1989. 6 2 0 G. Colombini and C. Preti, J . Inorg. Nuclear Chrnr., 1975, 37, 1159. Yu. A. Buslaev. A. A . Kuznetsova, V. V. Kovalev, and V. T. Kalinnikov, Riis.s. J. Inorg. Chetn., 1974, 19, 1863. u 2 W. G. Jackson and W. W. Fee, JtrorR. Chem., 1975, 14, 1174.

I4hrntioital Spectra Qf' Sonte Co-ordiiiated Lignrid.5 403 numbers are 1311/1305, 1119cn-l, and when M = Re they are 1313/1307 and 1 1 14 C ~ I - ' . ~ ~ ~ v(S=O) and C10,- wavenumbers were listed for [M(L),(CIO,),] (M = M n , Co, Ni, Cu, or Zn, all with n = 2 ; or M = Fe, Co, Ni, or Zn, all with IZ = 3 ; L = 2,2'- s~ l p h i n y l d i e th a n o I). ~ ~ ~ 1.r. evidence [,(PO) and u(PS)] suggests that the petp, pbtp, and ptp ligands, all of which are pyrothiophosphates, are characterized by P-S-P, rather than P-0-P linkages in the metal complexes: [M,L(OH,),] ( M = Li-Cs; L = petp or pbtp), [M,(ptp)(OH,),] (M = Mn, Co, Ni, or Zn), [M(petp)(OH,)] ( M = Mn, Co, or Zn), and [A12(pbtp)3],3H20.625 The ligand petp = (EtO),P204S2-;pbtp = (Bu"O),P2O4S2-;ptp = P20,S"-. The complex (149), containing bridging dithionite groups, has v(C0) at 2070, 2059, and 2024 cm-l, with v ( S 0 ) at 1223 and 1040 cm-l. Both sets are at higher wavenumber than in the related species containing an Fe-SO,-Fe bridge.626 Previous indications that [Ru( Me,SO),CI,] contained both S- and 0-bonded ligands were confirmed by a single-crystal X-ray

0--S,

/ ' 0

-,,

Similarly, the two types of DMSO ligands are thought to be present in [Ru(DMSO)~C~]CI, and [Ru(DMSO),]CI,, since v ( S 0 ) is found at both ca. 900-950 cm-l and at 1100 cm-1.G28 v ( S 0 , ) and v(SN) were listed for [Ru(CO),(PPh,),L] (L = RS02NC0 or RS02NCONS02R),and for [Pd(L-L)(NHSO,R),] (L-L = bipy or hen).^,^ 1.r. spectra of Co", Nil', and Cu" complexes of methylenebisthiopropionic acid CH2(SCH,CH,CO2H), are said to show that the ligand is quadridentate, being bonded by both S atoms and both carboxylate C=O groups.63o The sulphinato-0,s-complexes of Pd" [{R(O)OS},Pd] (R = Ph or p-tolyl) show two strong i.r. doublets, one due to v ( S 0 ) at 1210/1200cm-1 and one due to u(S0Pd) at 990/975 cm-l. The large wavenumber difference between these was seen as evidence for the presence of simultaneous M - 0 and M-S bonding, probably in a polymeric structure (1 50).631 62:'

@z4

83'

6Zy 02" 0:IU

K. Mews,

Angew. Cliem. Internat. Ecln., 1975, 14, 640. E. Giesbrecht and V. K . L. Osorio, J . Inorg. Nuclear C'hern., 1975, 37, 1409. C. M . Mikulski, L. L. Pytlewski, and N . M. Karayannis, Inorg. Chem., 1975, 14, 1559. N. H . Tennent, S. R. Su., C. A. Poffenburger, and A. J. Wojcicki, J . Organotnerallic Chctn., 1975, 102, C46. A. Mercer and J. Trotter, J.C.S. Dalton, 1975, 2480. T . Bora and M . M. Singh, R i m . J . Inorg. Chetn., 1975, 20, 231. S. Cenini, M. Pizzotti, F. Porta, and G . La Monica, J . Organonlrtallic C h ~ n i . 1975, , 88, 237. A. Kumar, S. Jain, and S. K. Tiwar, J . Inorg. Aridcur Cliem., 1975, 37, 2439. I . 1'. Lorenz, E. Lindner, and W. Reuther, A r g e w . Chem. Internat. Erln., 1975, 14, 256.

14

404

Spectroscopic Properties of Iiiorgartic and OrganometalIic Compounds

A comparison of the v ( S 0 ) wavenumbers in the series [Pd(R,SO)X,], and [Pd(R,SO)(CO)X,] shows that it is much lo\ier i n the latter series (R = Me or Et; X = CI or Br). The former are S-, the latter 0-bonded.G32 The values of v a s ( S 0 2 ) , vP(SO2), S(SO,), and p ( S 0 2 ) in the sulphinatocomplexes [PdCl(O,SR1)(OH,)]-, [(R1S0,),PdL,2], [Pd(O,SR1),]-, [(R1S02),Pd,C1,I2-, and [(R'S02)4Pd2C1212are all consistent with S-~o-ordination."~ trans-[PtCl(SO2R)(PPh,),I gives i.r. bands due to v,,, v h ( S 0 2 ) at 1210, 1057 cm-l, respectively, when R = Ph, and at 1218, 1071 cm-l when R = Me.G3' have been isolated. Pairs of isomeric complexes ~is-/tuans-[Pt'~CI,(R,SO)L] The sulphoxide ligand has v ( S 0 ) at 1 150 -1 185 cm-', and so is S-bonded (R = Me or Et; L = py, NH,, or piperidine). I n addition, the v ( S 0 ) wavenumbers are cis < trans in every case.635 The complexes [L,Zn(bipy),] (n = 1, 2, or 3) are 0,s-bonded when iz = 2 but 0,O-bonded when n < 2.636 1.r. data are indicative of 0 - rather than S-bonding in the sulphinatocomplexes [L,Cd(O,SPh),], where L, = (en), or (en)3; when L, = by),, bipy, or phen, the sulphinato-ligands are probably 0.0'-bonded, bridging or ~helated.~,' Characteristic i.r. shifts in v ( S 0 ) and v ( C - S ) of DMSO on formation ol' [Ln(DMSO),](PF,), (Ln = La--Lu except Pin, or Y ; n = 7 or approx. 7) show that Ln-0 co-ordination has occurrcd in all cases."* v(S=O) is shifted to lower wavenumbers in complexes of all the lanthanides (except Pin) or Y with trans-1,4-dithian 1,4-dioxide. Co-ordination has taken place via the 0 Raman spectra of AIEt,Cl-DMSO mixtures reveal the presence of only AIEt2CI,DM SO, AIEt3,D M SO, and [AICl,( 1) M SO),]. With A1E tC1,-D M SO, many different species are present, including AIEtCI,,DMSO and AIC13,DMS0.H40 The very small difference in wavenumber between v, and v,, of the SO2 in [Ph,-,Sn(CH=CH,)(SO,Ph),], where n = 1 or 2, shows that the sulphinate is symmetrically 0,O'-bonded, as in (1 51).611 03d 03s OYp

83L

03'

Oso (Is9

840

a41

E. A . Andronov, k'u. N. Kukushkin, V. G. Churakov, and Yu. V. Murashkin, Russ. J . Inorg. Chem., 1975, 20, 634. I. P. Loreni, E. Lindner, and W. Reuther, Z . anorg. Chem., 1975, 414, 30. S. P. Dent, C. Eaborn, and A. Pidcock, J . Organometallic Chem., 1975, 97, 307. Yu. N. Kukushkin, E. D. Ageeva, V. N. Spevak, and Yu. N. Fadeev, Russ. J . Itiorg. Chenz., 1974, 19, 1024.

E. Lindner, D. W. R . Frembs, and D. Krug, Chem. Ber., 1975, 108, 291. M . J. Mays and P. A. Vergagno, Inorg. Nuclear Chem. Letters, 1975, 11, 381. M. K . Kuya, 0. A. Serra, and V. K . L. Osorio, J . Inorg. Nuclear Chem., 1975, 37, 1998. G . Vicentini, L. B . Zinner, and L. R. F. de Carvalho,J. Inorg. Nuclear Chem., 1975,37,2021. J. Meunier and M . T. Forel, Bull. Soc. chrnt. Frunce, 1975, 2465. U. Kunze and J. D. Koola, Z . Naturfiwsch., 1975, 30b, 91.

8

Mossbauer Spectroscopy ~

~~

BY R. GREATREX

1 Introduction It is clear that the literature on Mossbauer spectroscopy is continuing to expand at a formidable rate, the number of papers reported in this chapter exceeding last year’s total by about 40%. This estimate includes all the papers that were published in full in the Proceedings of the important International Conference at Bendor,l but the 250 or so contributed papers that were published as abstracts in Volume 1 of the Proceedings of the equally notable Conference at Cracow are excluded from the figure, only the invited lectures contained in Volume 2 3 being taken into consideration. The reason for this sustained high level of interest lies in the ability of Mossbauer spectroscopy to yield fundamental information over an extremely wide range of interacting disciplines, a point made frequently but seldom as succinctly and cogently as in Gonser’s concluding le~ture.~ He singled out two developments of particular significance for the future: the y-ray laser 6-7 and advances in biological applications.E Two new resonances, neither of which is destined for extensive chemical application, have been reported during the year; they are the 159 keV resonance in l17Sng and the 61 keV resonance in la5Prn.lo In addition, the following 37 resonances have received attention: 67Fe(14.412 keV), 61Ni(67.40 keV), 67Zn (93.26 keV), 73Ge(13.3 keV), s3Kr (9.3 keV), g 9 R(90 ~ keV), ll*Sn (23.875 keV), lZISb(37.15 keV), 125Te(35.48 keV), 1271(57.60 keV), le91(27.72 keV), lzeXe (39.58 keV), 133Cs(81.00 keV), lalPr (145.43 keV), la5Nd(72.5 keV), lj9Sm (22.5 keV), 161Eu(21.6 keV), 1 6 3 E(103.2 ~ keV), 154Gd(123.07 keV), 156Gd (86.54 and 105.32 keV), Is6Gd (88.97 keV), 157Gd(64.0 keV), leoDy(86.79 keV), lalDy (25.65 keV), lasEr(80.56 keV), lsgTm (8.40 keV), 170Yb(84.26 keV), 174Yb (76.5 keV), 177Hf(112.97 keV), lsoW(104 keV), lelTa (6.25 keV), le2W (100.10 keV), lg31r(73.0 keV), la6Pt(98.8 keV), ls7Au(77.34 keV), and 237Np (59.54 keV).

lo

‘Proceedings of the International Conference on the Applications o f the Mossbauer Effect, Bendor (France), 1974’, J . Phys. (Paris), Colloq. No. 6, Supplement to No. 12, Vol. 35, 1974. ‘Proceedings of the International Conference on Mossbauer Spectroscopy, Cracow, 1975’, Vol. 1 , Contributed Papers, ed. A . 2. Hrynkiewicz and J. A . Sawicki, A . G.-H., Cracow, 1975. ‘Proceedings o f the International Conference on Mossbauer Spectroscopy, Cracow, 1975’, Vol. 2, Invited Lectures, ed. A. 2. Hrynkiewicz and J. A . Sawicki, A. G.-H., Cracow, 1975. U. Gonser, ref. 3, p. 475. V. I. Goldanskii and V. A. Namiot, ref. 3, p. 429. Yu. M. Kagan, ref. 3, p. 17. G . C. Baldwin, J. W. Pettit, and H. R. Schwenn, ref. 3, p. 413. H . Frauenfelder, ref. 3, p. 305. W. Miiller, H. Winkler, and E. Gerdau, ref. 1, p. 375. 11. Bokemeyer, K. Wohlfahrt, E. Kankeleit, and D. Eckardt, Z . Phys. ( A ) , 1975, 274, 305.

405

406

Spec t mscop ic Propert ies of’ Ir torgn I I ic

a r i d 0rgano nic t a llic C’o riipo 11 r idr.

The plan of this chapter reinains unaltcred from that adopted last year. After this short introduction, Sections 2 and 3 deal briefly \ k i t h theoretical cievelopnients and advances in methodology, and these are followed by more extensive sections (4-6), covering in turn iron-57, tin-1 19, and the other isotopes listed above, the latter being subgrouped into main-group elements, transition elements, and lanthanide and actinide elements. The final section is a bibliography, which lists papers on iron- and tin-containing alloys, together with a number of other papers not discussed in the main text.

Books, Conference Proceedings, and Reviews.--Three volumes of the Miissbauer Effect Data Index (MEDI) have been published during the One of these issues covers the years 1966--68, not previously indexed, and as a result Mossbauer spectroscopists now have at their disposal a complete bibliography, from the discovery of the effect up to 1974. U. Gonser has edited a book entitled ‘Mossbauer Spectroscopy’ that is Volume 5 in the series ‘Topics in Applied Physics’.’* His introductory chapter covers the basic principles of the technique,l6 and in the following five chapters leading scientists review applications in chemistry,ls magnetism,17 biology,l* lunar geology and mineralogy,l9 and physical metallurgy.20 In another book, written in German but containing a summary in English, the role of Mossbauer spectroscopy as a research method in applied organic chemistry is discussed.21 As mentioned earlier, the Proceedings of the International Conference on Applications of the Mossbauer Effect, Bendor (France), 1974 have been pub1ished.l This Conference attracted 218 participants from 29 countries and produced 131 contributed papers in addition to 17 invited papers. For the purposes of this Report, all the papers have been regarded as primary publications and are mentioned individually in the appropriate sections. Topics covered by substantial review articles included: theoretical determination of charge and spin densities 22 (see also ref. 39), relaxation of 3d and 4f electrons in metals and alloys,23 interconfiguration fluctuations in metallic rare-earth l1 la l3

l6

l7 ln l9 2o 21

??

23 24

J. G. Stevens and V. E. Stevens, ‘Mijssbauer Effect Data Index covering the 1966-1968 Literature’, lFi/Plenum, New York, 1975. J . G. Stevens and V. E. Stevens, ‘Mossbauer Effect Data Index covering the 1973 Literature’, IFI/Plenum, New York, 1975. J. G. Stevens and V. E. Stevens, ‘Mijssbauer Effect Data Index, covering the 1974 Literature’, lFl/Plenum, New York, 1975. ‘Topics in Applied Physics, Vol. 5 , Mossbauer Spectroscopy’, ed. U. Gonser, SpringerVerlag, Berlin, Heidelberg, New York, 1975. U. Gonser, ‘From a Strange Effect to Mossbauer Spectroscopy’, ref. 14, p. 1. P. Giitlich, ‘Mossbauer Spectroscopy in Chemistry’ , ref. 14, p. 53. R. W. Grant, ‘Mossbauer Spectroscopy in Magnetism: Characterization of Magneticallyordered Compounds’, ref. 14, p. 97. C. E. Johnson, ‘Mossbauer Spectroscopy in Biology’, ref. 14, p. 139. S . S. Hafner, ‘Mossbauer Spectroscopy in Lunar Geology and Mineralogy’, ref. 14, p. 167. F. E. Fujita, ‘Mossbauer Spectroscopy in Physical Metallurgy’, ref. 14, p. 201. D. Christov, Z. Bontschev, and Z. Busova, ‘Mossbauer Spectroscopy as a Research Method in Applied Organic Chemistry-Present State and Prospects’, Bulgarian Academy of Science, Sofia, 1974. A. J. Freenian and D. E. Ellis, ref. 1, p. 3. L. L. Hirst, ref. 1, p. 21. E. R. Bauminger, I. Felner, D. Froindlich, D. Levron, I. Nowik, S . Ofer, and R. Yanovsky, ref. 1, p. 61.

407

Mossbauer Spectroscopy

covalency effects in hyperfine interaction^,?^ volume dependence of hyperfine interactions (in 57Fe,llgSn, 151Eu, 153E~, lSITa, and 1g7A~),2s Jahn-Teller effecfs,27 electronic structure of biomolecules 28 and synthetic analogues of active sites of the iron-sulphur texture high-field Mossbauer spectrosc~py,~ amorphous l solids,32 radiation damage and lattice defects,33 studies of fine and the complementary nature of Ranian and Mossbauer spectroscopy in the study of lattice dynamics of molecular solids.35 The Proceedings of the International Conference on Mossbauer Spectroscopy, Cracow (Poland), 1975 have also appeared. Volume 1 contains abstracts of the contributed papers on topics ranging from progress in theory and methodology to applications in many areas of chemistry, physics, and biology. The final section, on special applications and unconventional experiments, contains interesting papers on the study of magnetic recording tapes and the analysis of samples returned by the American Apollo and Russian Luna missions, and applications involving polarized gamma-rays also feature prominently. However, the contribution which most accurately reflects the section heading is the one which deals with an investigation into the seasonal variation of the concentration of iron in the atmosphere! No doubt the full papers based on these abstracts will be published in the primary journals, and for this reason these contributions are not discussed individually in this Report. Volume Z 3 of the Proceedings records, in full, the 30 invited review-type lectures which cover such topics as: coherent phenomena associated with the interaction of Mossbauer radiation with crystals,6 y-ray crystallography using the Rayleigh scattering of y-rays 36 (see also refs. 62, 122, 130, and 131), amplitude and phase modulation of Mossbauer y - q ~ a n t a ,polarization ~~ studies,3s theoretical determination of charge and spin densities 39 (see also ref. 22), magnetic structure and transferred hyperfine interaction^,^^ calibration of the isomer shift,41 emission relaxation 4 4 biological s t i ~ d i e s , ~46 ~ clay minerals,47 451

25 2fl

37 JB

zo 30

3L

31 3:j

53

36

38 37 :jH

8v ("

42

43 44

dB

47

Ci. A. Sawatzky and F. Van der Woude, ref. 1 , p. 47. ti. M. Kalvius, U. F. Klein, and G . Wortmann, ref. 1 , p. 139. F. S. Ham, ref. 1, p. 121. E. Munck and P. M. Champion, ref. 1 , p. 33. R. B. Frankel, B. A. Averill, and R . H. Holm, ref. 1 , p. 107. U. Gonser and H.-D. Pfannes, ref. 1 , p. 1 1 3. J. Chappert, ref. 1, p. 71. J. M. D. Coey, ref. 1, p. 89. G. Vogl, ref. 1, p. 165. H. Keisch, ref. 1 , p. 151 (see also R. Keisch, A h . Cliem. Ser., 1974, 138, 186). Y. Hazony and R. 11. Herber, ref. 1, p. 131. D. A. O'Connor, ref. 3, p. 369. W. K. Wojtowiecki and S. B. Sazonov, ref. 3, p. 399. D. Barb, ref. 3, p. 379. A. J. Freeman, ref. 3, p. 435. 1. Nowik, ref. 3, p. 83. W . Kiindig, ref. 3, p. 355. E. F. Makarov and R. A. Stukan, ref. 3, p. 133. H . H. F. Wegener, ref. 3, p. 257.

G . K. Shenoy and B. D. Dunlap, ref. 3, p. 275. I;. Parak, ref. 3, p. 285. E. N. Frolov, G. I. Lichtenstein, and V. I. Goldanskii, ref. 3, p. 319. J. M. D. Coey, ref. 3, p. 333. U. Gonser, ref. 3, p. 113.

408

Spectroscopic Properties of’Inorganic and Organometallic Compounds

catalysis,48non-crystalline materials and liquid crystals,60phase transitions,61and critical magnetic phenomena.s2 Several other international conferences 63-56 have featured papers on Mossbauer spectroscopy but only those from the 24th American Institute of Physics Conference on Magnetism and Magnetic Materials 66 are discussed individually in this Report. Several introductory and general reviews on Mossbauer spectroscopy have a p p e a ~ e d , ~ ~and - ~ l more specific reviews have covered the diffraction of Mossbauer y-radiation 6 2 (see also refs. 6, 37, 122, 130, and 131), decay aftereffects and associated p h e n ~ r n e n aand , ~ ~ Mossbauer studies at high pressures 64 and very low temperatures.66 Applications of Mossbauer spectroscopy in solid-state sciences have been reviewed,66and several topics in solid-state chemistry have received attention ; these include : phase transformations in iron oxides during oxidation and r e d ~ c t i o n ferrites , ~ ~ in general,68silicate and phosphate glasses,6s corrosion and related 71 and impurities in gems.72The study of electrondensity distributions in solids where intervalence fluctuations are possible (e.g. Fe,O, and Eu3S,) has also been Other areas of chemistry which have been reviewed are co-ordination chemistry,74metal sandwich and ‘O

bo 61

6s

V. I. Goldanskii, Yu. V. Maksimov, and I. P. Suzdalev, ref. 3, p.

163.

F. J. Litterst and G. M. Kalvius, ref. 3, p. 189. I. Dtzsi, ref. 3, p. 221. C. Hohenemser, ref. 3, p. 239. ‘Proceedings of the 18th Congress on Magnetic Resonance and Related Phenomena, Ampere, 1974, ed. P. S. Allen, E. R. Andrew, and C. A. Bates, North-Holland, Amsterdam, 1975.

64

‘5

‘Proceedings of the 17th Nuclear Physics and Solid State Physics Symposium, 1972’ (publ. 1973), Volume C. ‘International Conference on Hyperfine Interactions Studied in Nuclear Reactions and Decay: Contributed Papers’, ed. E. Karlsson and R. Wappling, Almqvist and Wiksell, Stockholm, 1974.

b7 b9

8o

a3

a4

a6

6B 70

71 72

7s

Amer. Inst. Phys. Conf. Proc. No. 24, ‘Magnetism and Magnetic Materials’, 1974, ed. C. D. Graham, G. H. Lander, and J. J. Rhyne, A.I.P., New York, 1975. T. Tominaga, Gendui Kagaku, 1975, 46,32. B. W. Dale, Contemporary Phys., 1975, 16, 127. E. Fluck, ‘Mossbauer Spectroscopy’, in ‘Method. Chim. Part A’, ed. F. Korte, Academic Press, New York, 1974, p. 471. J. G. Stevens, M a p . Resonance Rev., 1974, 3, 63. T. Tolgyessy, Jad. Energ., 1974, 20, 349. V. A. Belyakov, Uspckhi Fiz. Nauk, 1975, 115, 553. P. Glentworth and A. Nath, in ‘Radiochemistry’ (Specialist Periodical Reports), ed. G. W. A. Newton, The Chemical Society, London, 1975, Vol. 2, p. 74. W. B. Holzapfel, C.R.C. Crit. Rev. Solid State Sci., 1975, 5 , 89. J. M. Williams, Cryogenics, 1975, 15, 307. G. M. Kalvius, Atomic Energy Rev., 1974, 12, 637. B. N. Maimur and V. F. Moroz, Nov. Metody Issled. Protsessov Vosstanov. Chern. Met., Doklady Simp., 1971 (publ. 1974), 56. C. I. Nostor, Studii Cercetari Fiz., 1974, 26, 623. G. Tomandl, Fuchausschussber. Dtsch. Glastech. Ges., 1974, 70, 252. H. M. Gager and M. C. Hobson, Cutal. Rev.-Sci. Eng., 1975, 11, 117. H. Ebiko, Hyomen, 1974, 12,668. C.M. Scala, Austral. Gemmol., 1974, 12, 119. S. P. Ionov, G. V. Ionova, V. S. Lubimov, and 1:. F. Makarov, Phys. Status Solidi ( B ) , 1975, 71, 11.

74

76

E. F. Makarov and R. A. Stukan, Fiz. Mat. hcietody Koord. Khim., Tezisy Doklady, Vses. Soveshch., 5th, 1974 (publ. 1974), 8. M. L. Good, J. Buttone, and D. Foyt, Ann. New York Acad. Sci., 1974, 239, 193.

Mossbauer Spectroscopy 409 europium-edta c h e l a t e ~ .Haem ~ ~ proteins 77-7a and other biological systems 79, 8o have also been covered (see also refs. 8, 18, 28, 29, 45, and 46). 2 Theoretical

This section covers only papers of a general theoretical nature. Theoretical developments related to particular isotopes are discussed later in the appropriate section, and several reviews on theoretical aspects have already been referred to in Section 1 . The exciting possibility has been discussed of using radiation from highenergy synchrotron storage rings as a source for Mossbauer measurements. The main problem is that, although the spectral density of the required radiation is estimated to be several orders of magnitude greater than that emitted by conventional radioactive sources, the non-resonant background is likely to be a few billion times more intense. However, it is suggested that this might be overcome by means of time-filtering techniques.81 Operating conditions have been discussed for a gently pumped y-ray laser using isomer separation and the Mossbauer effect, and a vigorously pumped type using fast neutron excitation of compressed matter.82 More recent papers on y-ray lasers have already been m e n t i ~ n e d . ~ - ~ There has been much interest in applications of the Mossbauer effect to the study of unusual metastable atomic or chemical configurations occurring at the source atom, for example, those produced by B-decay and its associated shake-off reactions which precede the decay of the Mossbauer state. In general, a metastable or ground-state configuration is reached in a time which is short compared with the lifetime of the Mossbauer level, and the corresponding emission spectrum consists of a superposition of spectra belonging to different short-lived configurations. However, the question arises as to what form the Mossbauer spectrum will take when the lifetimes of the atomic states are comparable with that of the Mossbauer level, and calculations have now been performed both for conventional Mossbauer experiments and for experiments involving time filtering. The simulated spectra show that the time-differential experiment is capable of differentiating between time-dependent effects in the atomic environment and a superposition of spectra belonging to different static configurations, whereas the conventional emission experiment may not be.83 It has been shown that the hyperfine components in the emission spectrum of a Mossbauer source interfere, and that the interference can be observed by the y-y-coincidence method. The effect should appear in the presence of both niagnetic splitting and electric quadrupole splitting of the nuclear levels.84 78

77

7n 7p

Hn

H1 n3

n3

1. Dtzsi and T. Lohner. Zzotoptechnika, 1974, 17, 458. E. Munck and P. M. Champion, Ann. New York Acud. Sci., 1975, 244, 142. A. Trautwein, Structure and Bonding, 1974, 20, 101. c. E. Johnson, in 'Amino-acids, Peptides, and Proteins' (Specialist Periodical Reports), cd. R. C. Sheppard, The Chemical Society, London. 1975, Vol. 6, p. 256. W. T. Oosterhuis, Structure and Bonding, 1974, 20, 59. S. L. Ruby, ref. 1, p. 209. L. Wood and G. Chapline. Nature. 1974. 252, 447. E. Kankeleit, 2. Phys. ( A ) , 1975, 275, 119. A, S. Ivanov, A. V. Kolpakov, and R. N. Kuz'min, Soviet Phys. J.E.T.P., 1975, 40, 328 (Russian original Zhur. eksp. teor. Fiz,,1974, 67, 661).

410

Spectroscopic Properties of Inorganic and Organometallic Compounds The form of the Mossbauer spectrum for y-rays emitted from atoms bound to the free surface of a fluid or liquid crystal has been discussed. The spectrum is expected to show a low-frequency anomaly associated with the two-dimensional character of the capillary waves, and this was discussed for liquid metals, for viscous fluids, and for thin films of a liquid above a solid surface. If the anomaly turns out to be visible it could give information on dissipative effects in monomolecular layers at frequencies of the order of los-lo0 H z . ~ ~ Analytical expressions have been derived for determining hyperfine parameters from Mossbauer spectra involving 9 + $ nuclear transitions.Rsr87 It was pointed out that computer programs which adjust the energy-level separations in a leastsquares fit to the 57Fe Mossbauer spectrum can lead to unphysical results; instead it is better to adjust the actual parameters in the nuclear H a m i l t ~ n i a n . ~ ~ A non-iterative method for fitting Lorentzian functions to Mossbauer spectra has been described.88 Fourier analysis of Mossbauer spectra has been The width, intensity, and area of a Mossbauer line have been computed by numerical integration as a function of absorber thickness, and analytical expressions valid for thin absorbers were presented.OO Special attention was paid to asymmetric, quadrupole-split 57Fe spectra, which are easily misinterpreted unless very thin absorbers are ~ s e d . ~AO new ~ ~ method ~ of estimating recoilfree fractions from thickness-dependence measurements in both unpolarized and polarized spectra was ~ u t l i n e d .The ~ ~ calculation of optimum absorber thickness has received further consideration.02~ 93 It has been pointed out that effects which give rise to unequal line intensities in quadrupole-doublet Mossbauer spectra, namely preferential crystal alignment and the Goldanskii-Karyagin effect, will also produce unequal linewidths, the more intense line also being the It should be mentioned that this phenomenon, which is a direct consequence of the form of the resonance integral, is quite well known, and it is therefore unfortunate that no reference was made to earlier papers o n the subject [e.g. T. C . Gibb, R. Greatrex, and N. N. Greenwood, J . Chern. SOC.( A ) , 1968, 8 901. It has been shown that in the case of a dipole transition (e.g. 57Fe,llOSn,61Ni) the angular dependence of the intensity of an absorption line for a non-polarized y-beam can be described by an intensity The method has been applied to spectra of a single crystal of FeC1,,4H20, but it is also applicable to cases where there are more than one absorbing nucleus per unit celLos The relative line intensities for 57Fenuclei in uniaxial, ferromagnetic single crystals have been calculated as a function of the magnitude and direction of an applied magnetic 86

Ra R7

82

O4

O6

P. G. DeGennes, J. Phys. (Paris), 1975, 36, 603. L. Hiiggstrom, ref. 55, p. 274. S. K. Arif, D. St. P. Bunbury, G . J. Bowden, and R. K. Day, J . Phys. ( F ) , 1975, 5, 1037. T. Mukoyama, Nuclear Instr. and Methods, 1975, 126, 153. K. Kuebenbauer, Acta Phys. Polon. ( A ) , 1975, 47, 11. S. Morup and E. Both, Nuclear Instr. and Methods, 1975, 124, 445. J . M. Williams and J. S. Brooks, Nuclear Instr. and Methods, 1975, 128, 363. S. Nagy, B. Levay, and A. Vertes, Magyar KPnt. Folydirat, 1975, 81, 4. S. Nagy, B. Levay, and A. VCrtes, Acta Chim. Acad. Sci. Hung., 1975, 85, 273. R . P. Vardapetyan, Soriel Phys. SolidStatri, 1975, 17, 1215 (Russian original Fir. Tverd. Tela, 1975, 17, 1850). R. Zimmerman, Chem. Phys. Letters, 1975, 34, 416. K. Zimmerman. Nuclear Instr. and Methods, 1975, 128, 537.

Mossbauer Spectroscopy

41 1

field.Q7The effect of varying the temperature in the region of the Curie point on the Mossbauer spectrum of a ferromagnet has also been The problem of calculating the line intensities in Mossbauer spectra obtained using polarized y-rays and polarized absorbers has been discussed, with particular reference to 67Fe,9Q and a general FORTRAN program for generating polarization patterns has been written.loO Theoretical equations have been given for the polarization dependence of the absorption cross-section in an absorber of finite thickness;lol their use in the interpretation of data on FeC1,,4H20,Fe(NH,),(S0,),, 6H20, and Na,[Fe(CN),(N0)],2H20 is mentioned later (see pp. 424,427, and 442). The possibility of observing the classical Faraday effect with linearly polarized Mossbauer radiation has been discussed,102and a new method of detecting double y-ray-nuclear magnetic or -acoustic resonances with polarized y-rays 1 has been proposed.lo3 It has been shown that the Am = 0 and Am = components of a Mossbauer spectrum which is influenced by electronic relaxation can be distinguished by the application of a polarized source.1o4 Some three years ago Straub and co-workers obtained Mossbauer spectra, on some haemin derivatives of porphines which occur in haemoglobin, that could not be explained on the basis of Blume's original relaxation model. The observed effect was a reversal in the asymmetry of the relaxation-broadened quadrupole doublet at low temperatures. However, it has been shown that the results can be explained satisfactorily if the effects of off-diagonal hyperfine interactions are taken into account. These terms become particularly important at low temperatures.106 Redfield's relaxation theory, which essentially includes all treatments published so far, has been given in a form which is sufficiently general to deal with all types of experiment sensitive to the dynamical behaviour of a small subsystem coupled to its environment. Special attention was paid to the treatment of a spin system of cylindrical synitnetry relaxing via magnetic dipole interactions with the surroundings.106 The conditions under which Hirst's relaxation theory can be applied to phonon relaxation processes have been investigated, and the theory has been applied to a study of the Mossbauer lineshape in the presence of relaxation between two electronic Kramers' d o ~ b 1 e t s . l ~ ~ A consistent description of relaxation phenomena has been given within the framework of the Liouville formalism.1o8 The generalized stochastic theory of Mossbauer lineshape has been applied to paramagnetic systems in external magnetic fields and to magnetically ordered systems. A computer program for the simulation of Mossbauer relaxation spectra in the case of effective spin S = 9 and I 8 ) --f 14 ) Mossbauer transitions was described.'O@ A model for L. G . Onoprienko, Fiz. Met. Metallovrd., 1975, 39, 751. V. N. Kashcheev, Soviet Phys. Solid State, 1975, 17, 2194 (Russian original Fir. Tverd. Tela, 1975, 17, 3352). 88 J. M. Daniels, Nuclear Znsrr. and Methods, 1975, 128, 483. Inn D. Barb, D. Tarina, and D . P. Lazar, Rev. Rouniainr Phys., 1975, 20, 673. 1'11 T. C. Gibb, J . Phys. (C), 1975, 8. 229. I o 2 D. Barb and M. Ragalski, J . Chim. phys., 1975, 72, 470. ln3 A. V. Mitin and G. P. Chugunova, Phys. Srarus Solidi ( A ) , 1975, 28, 39. loo S. Morup, ref. 1, p. 683. S. Dattagupta, Phys. Rev. ( B ) , 1975, 12, 3584. Io8 J. Bosse, H. Gabriel, and W. Vollrnann, Phys. Sfatus M i d i ( B ) , 1975, 68, 81. lo' C. Chopin, F. Hartniann-Boutron, and D. Spanjaard, rcf. 1, p. 433. l o 8 F. Hartmann-Boutron and D. Spanjaard, J . Phys. (Paris), 1975, 36, 307. I f l o D. Barb and L. Diamandescu, Rev. Roumaine Phys., 1975, 20, 259. O7

41 2

Spectroscopic Properties of Inorganic and Organometa flic Cornpoiinch

calculating Mossbauer spectra in the presence of a fluctuating electric field gradient has been mentioned; spectra with one doublet or with two doublets may be obtained, depending on the rate of fluctuation.l1° The effect of nuclear motion on Mossbauer spectra has been considered theoretically. Relaxation effects occur because the nucleus interacts differently with its surroundings at different sites. At the same time, an additional broadening is observed because of the nuclear motion. The Blume result for pure relaxation and the Singwi-Sjolander difiusion broadening are obtained as two limiting cases of the theory. Applications of the theory to experimental cases were suggested. Iron-57 dissolved in a phosphoric acid and water mixture is one possibility; the nucleus jumps from one position to another as the temperature of the system is raised through its glass transition, and thereby finds itself in a succession of different electric field gradients, which leads to the relaxation. Other possibilities include diffusive jumping of "7Fc nuclei between different sites in antiferromagnets (e.g. MnNi) or ferromagnets (e . g . FeCo) with high ordering temperatures."l It has been suggested that the line broadening measured directly from high-temperature Mossbauer spectra is not directly proportional to the diffusivity. Instead it should be corrected to take account of the decrease in linewidth with temperature. The effect of including the correction is to lower the temperature at which diffusive line broadening can be detected.112 The effect of anisotropic atomic motion (e.g. vibration, diffusion, or eddy currents) on the Mossbauer lineshape has been discussed. Anisotropic continuous diffusion in polycrystalline materials can result in different broadenings of the u and rr components of a quadrupole doublet, whereas jump diffusion leads to almost equivalent broadening of these lines.113 The effect of the dimensionality of jump diffusion on the line broadening has been discussed (see also last year's Report, p. 418, ref. 55). The role which the Mossbauer effect can play as a probe of the detailed behaviour of a particle undergoing Brownian motion has been discussed,'15 and the effects of anisotropy of both the rotational and the translational diffusion of ellipsoidal Brownian particles on the shape and asymmetry of the Mossbauer spectrum have been considered theoret ically.116 The Mossbauer scattering lineshape has been calculated for iron-57, taking into account not only nuclear resonant scattering but also Rayleigh scattering, incoherent thickness effects, and angular distribution factors. The calculations showed that in scattering experiments the effects of saturation in the line intensity are quite different from those in transmission spectroscopy, and that the scattering spectrum is quite sensitive to the value of the recoil-less fraction."? Formulae have been given for the scattering resonance cross-section in the case of a nonisotropic Debye-Waller factor and a non-axially symmetric hyperfine interA. Gerard and F. Grandjean, ref. 1, p. 452. S. Dattagupta, Phys. Rev. ( B ) , 1975, 12, 47. M. Ron and F. Hornstein, ref. 1 , p. 505. 113 V. I. Goldanskii and S. V. Karyagin, Phys. Status SoIidi ( B ) , 1975, 68, 693. n4 S. V. Karyagin, Societ Phys. Solid Stntc, 1975, 17, 1220 (Russian original Fiz. Tcerd. Tela, 1975, 17, 1856). 115 L. Gunther and J. Zitkova-Wilcox, ref. 1, p. 519. A. Ya. Dzyublik, Sooiet. Phys. J.E.T.P., 1975, 40, 763 (Russian original Zhur. eksp. reor. Fiz., 1975, 67, 1534). 117 B. Balko and G. R. Hoy, Phys. Reu. ( B ) , 1974, 10, 4523.

111

Mossbauer Spectroscopy 413 action.118 The quantitative interpretation of Mossbauer backscat ter spectra, with particular reference to internal-conversion electrons, has been treated by assuming that electron attenuation in a surface film can be satisfactorily described by a simple exponential law. The theory of Krakowski and Miller (1972) was extended to include multilayered samples, and a relationship between the spectrum area and layer thickness derived. As an example, numerical results were described for an oxide film grown on pure iron.Ilg A general expression has been derived for the resonant scattering cross-section, which includes the effects of electron spin relaxation.120 The polarization characteristics of Mossbauer coherent scattering from magnetically ordered crystals have been considered theoretically,121and the use of coherently scattered Mossbauer radiation in the study of structural phase transitions has been demonstrated for a BaTiO, single The time distribution of radiation re-emitted from a Mossbauer absorber has been The influence of an electric field on the Mossbauer spectra of ferroelectric materials has been discussed, and it is suggested that Mossbauer spectroscopy should prove useful for the study of the domain structure of polycrystalline ferroelectri~s.~~~ The general expression for the Mossbauer lineshape in the presence of r.f. perturbation, derived earlier, has now been extended to include the calculation of the off-diagonal matrix elements of the correlation function.126 As discussed in last year’s Report (see p. 418, ref. 53), a method for narrowing Mossbauer lines by using a properly chosen r.f. field to remove the effect of a non-uniform isomer shift has been proposed . l Z 6 Double-time Green’s function techniques have been used to calculate Mossbauer parameters at the high-temperature limit for a lattice containing a vacancy and an interstitial atom.127The limitations of the Debye model in the calculation of 120 Mossbauer recoil-less fractions have been 131 The theory of Mossbauer diffraction has received further consideration (see also refs. 6, 36, and 37). 1309

3 Instrumentation and Methodology Some technical developments in Mossbauer spectroscopy have been reviewed ; these include the use of current integration to improve the efficiency of data collection, and factors limiting the achievable feedback stability of drive H. Bokemeyer, D. Eckardt, and K. Wohlfahrt, ref. 1 , p. 389. J . Bainbridge, Nuclear Instr. and Methods, 1975. 128, 531. l Z 0 A . M. Afanas’ev and V. D. Gorobchenko, Soviet. Phys. J.E.T.P., 1975, 40, 1114 (Russian original Zhur. eksp. teor. Fiz., 1975, 67, 2246). V. A . Belyakov and E. V. Smirnov, Soviet. Phys. J.E.T.P., 1975, 41, 301 (Russian original Zhur. eksp. teor. Fiz., 1975, 68, 608). lza E. V. Zolotoyabko and E. Iolins, Lutv. P.S.R. Zinat. Akad. Vestis, Fir. Teh. Zinat. Ser., 1975, 46. la’ H. Drost, K. Palow, and G . Weyer, ref. 1, p. 679. A. S. Ivanov, A. V. Kolpakov, and R. N. Kuz’min, Soviet. Phys. J.E.T.P., 1974, 39, 336 (Russian original Zhur. eksp. tcor. Fiz., 1974, 66, 697). I z 6 B. Krishnamurthy and K. P. Sinha, J . Magn. Resonance, 1975, 17, 189. Iz6 V. I. Goldanskii, S. V. Karyagin, and V. A. Namiot, ref. 1 , p. 193. S. K. Roy, M. Singh, and B. P. Srivastava, Indian J . Pure Appl. Phys., 1975, 13, 217. S. Kumar, Phys. Status Solidi ( B ) , 1975, 69, K145. K. Mahesh, Proc. Nuclear Phys. Solid State Phys. Symp., 1973 (publ. 1974), 16C, 177. la0 M. A. Andreeva and R. N. Kuz’min, Phys. Status Solidi ( B ) , 1975, 71, K201. lS1 F. N. Chukhovskii and I. P. Perstnev, ref. 1 , p. 185. lYz E. Kankeleit, ref. 3, p. 43. 118

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414

Spectroscopic Properfit~s of‘ Inorganic arid Orgariorrietcrllic Conipouncls

As predicted in last year’s Report, there has been a continuing interest in the study of surfaces by means of conversion-electron Mossbauer spectroscopy. The energy loss of these electrons is related to the depth of the emitting atoms below the surface, and by selecting the electrons in terms of their energy, with a p-spectrometer, it is possible to analyse layers of known thickness and depth. The criteria necessary for the useful application of the technique have been enumerated,l0 and systems have been described.l0* 134 The advantages of the technique for the study of single-crystal specimens,135and for the study of “Fe implanted into solids, have been d i s c u s ~ e d13’ . ~ ~I n~ particular ~ i t was pointed out that the background from iron impurities in the bulk target, often significant in transmission experiments, is negligible in electron counting because of the very small penetration range of the low-energy conversion electrons. Other advantages include the high sensitivity of the technique to small amounts of 67Fe,and the fact that very strong sources can be used without danger of overloading the detection system. The technique should prove invaluable for the study of corrosion, diffusion, radiation damage, amorphous materials, and other depthA technique for reducing the background noise level selective surface on Mossbauer scattering spectra 138 and a simple proportional counter for effective detection of low-energy electrons have been des~ribed.”~Applications of conversion-electron spectroscopy to the study of oxide systems are discussed later (see p. 449). A Mossbauer spectrometer utilizing a multiwire proportional chamber has been described. I n this system the multiwire chamber is shaped like a sector of a cylinder and surrounds the y-ray source, which is located at its centre of symmetry. The absorber is coaxial with the chamber and also surrounds the source, which moves back and forth with constant velocity vo in a fixed direction perpendicular to the axis of the cylinder. Pulses arising at each wire are caused by y-rays emitted at an angle 8 with respect to the direction of motion of the source, and are transmitted through the absorber with a Doppler shift corresponding to the relative velocity between the source and absorber of u = uocos 8. The total velocity range covered therefore depends only on ro and the angle 6’ subtended at the source by the multiwire chamber. The system has the advantage that the source does not need to be collimated, and very high count rates are therefore possible. The geometrical problems concerning the velocity smear relative to each wire and technical problems encountered in the construction of the device have been discussed in detail.140 The advantages of an on-line mini-computer system over the multichannel analyser system have been The use of tin-loaded plastic scintillators in Mossbauer spectroscopy has been discussed. The decay time of the scintillations is two orders of magnitude 133B

J . P. Schunck, J. M. Friedt, and Y. Llabador, Rev. Phys. Appl., 1975, 10, 121. 1. L. Gruzin, Yu. V. Petrikin, and R. A. Stukan, Prihory Tekhn. Eksp., 1975, 48. M. J. Tricker and A. G, Freeman, Surface Sci., 1975, 51, 549. 138 B. D. Sawicka and J. A. Sawicki, Nucleonika, 1974, 19, 811. 13’ J. Stanek, J. Sawicki, and B. Sawicka, Nuclear Instr. and Methods, 1975, 130, 613. 138 Yu. F. Babikova, M. R . Gryaznov, L. M. Isakov, N. S. Kolpakov, and M. N. Uspenskii, Pribory Tekhn. Eksp., 1975, 152. 138 Y. Isozumi and M. Takafuchi, Bull. Inst. Client. Res. Kyoto Univ., 1975, 53, 63. u0 G . C. Bonazzola, T. Bressani, E. Chinvassa, G. Dellacasa, A. Musso, and B. Minetti, ref. 1, p. 687. 141 R. Nagarajan, Proc. Nuclear Ph1.s. Solid State P / I ) > SSynp., . 1973 (publ. 1974), 16C, 329.

133

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Miisshorrer Spectroscopy

41 5

less than for convenlional Nal/Tl detectors, but thc high count-ratc advantages can only be realked if the Mossbauer transition is well separated from other contributions in the energy spectrum.14J Several resonance counters for Mossbauer spectroscopy have been d e s ~ r i b e d . l ~ ~ - ~ ~ ~ A compact linearly polarized Mossbauer source has been described. I t consists of a 6 7 C O / Cemitter ~~ covered with a polarizer of [Fe(H,0)6]SiF6 diluted with [Zn(H,O),]SiF,. The source emits a single line and has the advantage of requiring no applied magnetic field.lJ7 The use of a polarized 67Co/Fe(six-line) Mossbauer source offers a particularly powerful method of studying the orientation of the electric field-gradient tensor in single crystals, and several applications of this technique are discussed later (see pp. 424, 427, and 442). The method has the significant advantage over a conventional angular dependence study that much smaller crystals with only one well-developed face may be used.lol A simple instrument to enable velocity calibration of Mossbauer transducers has been reported. The device is based on the moire technique, and requires only a simple lamp as the light sourcc. It is claimed to give values for the ground and excited states of iron in good agreement with those of Stevens and Preston (197O).lp8 A magnesium alloy which has a high density, is corrosion resistant, and has a low absorptivity for y-rays has been recommended for use as a window material in Mossbauer cryostats.14QThe solder Ga,,ln,,, which is liquid at room temperature, has been shown to be useful for making good thermal contact between a Mossbauer source and a cold finger at very low temperatures (0.07 < T/K < l.0),150 A brief description has been given of a sample holder and heater assembly designed for accurate measurements in the temperature range 4.2-30 K. The device is attached to the cold finger of a liquid-helium cryostat and ensures a homogeneous distribution of temperature over the sample.lS1 A cell for Mossbauer absorption measurements on liquids at high pressures has been described. Results obtained with a supercooled solution of FeCI, in glycerol are described later (see p. 424).lS2 4 Iron-57 General Topics.-Ni~clear Parameters arid Isonier-shift Calibrations. The results of relativistic SCF calculations of I $(O) l2 and 3d have yielded electrondensity differences between various iron configurations that are greater by a us

J. Becker, L. Eriksson, L. C. Moberg, and Z . €1. Cho, Nuclear Instr. and Methods, 1975, 123, 199. L. Gumnerova and M. Apostolova, God. Sojii, Univ., Fiz. Fak., 1970-72 (publ. 1973), p. 383.

D. K. Kaipov, T. A. Orazbaev, E. F. Calyutina, and L. S. Sergeeva, Pribory Tekhn. Eksp., 1974, 75. 146 V. I. Gudov, V. I. Stepanenko, V. L. Fedorin, and V. S. Shkalikov, Trudy Metrol. Znst. S.S.S.R., 1974, 106. J. Fenger, Dan, A.E.C., Res. Establ. Risoe, Risoe-M, 1974, 1695. l P 7 F. Varret, P. Imbert, G . Jehanno, and R . St. James, Phys. Status Solid ( A ) , 1975, 27, K99. 148 H. P. Wit, Rev. Sci. Instr., 1975, 46, 927. 14Q S. K. Godovikov and V. G. Snigirev, Pribory Tekhn. Eksp., 1975, 243. l J 0 L. Bogner and E. R. Seidel, Cryogenics, 1975, 15, 680. lol V. Petrouleas, A. Simopoulos, and A. Kostikas, Phys. Reo. (B), 1975, 12, 4675. l G 2 D. C. Champeney, E. S. M. Higgy, and R. G. Ross, J . Phys. ( C ) , 1975, 8, 507.

la4

41 6

Spectroscopic. Properties of iiiorgcrnic and Organometullic Compounds

factor of 1.55 than those calculated with a non-relativistic Hartree-Fock method. Furthermore, use of the new densities removes a disparity between the values of the fractional increase in the "Fe nuclear radius upon excitation, A R / R , given by McNab et a / . (1971) and Duff (1974, see last year's Report, p. 423). Based on the data of McNab et al., the recalculated value is A R / R = -5.8 x In an independent study, relativistic calculations of various electronic configurations of the iron atom have been used in conjunction with Huckeltype MO and limited-configuration-interaction calculations of iron-containing clusters to determine electron densities at the iron nucleus, and these have been combined with the experimental isomer shifts to yield new values for ARIR. Three different systems were analysed: FeO,g- and FeOal'- clusters in y-irradiated, 67Fe-dopedMgO ; FeF,3- and FeF,4- clusters; and iron monomers and dimers isolated in noble-gas matrices. These yielded values for A R / R of -(8.72 k 1.02) x -(9.18 k 0.56) x and either -(7.12 +_ 0.59) x or -(8.65 & 0.71) x lo-,, depending upon the geometry assumed for the dimer. The average value is - ( 8 . 8 5 f. 0.9) x in reasonable agreement with the result in ref. 153.154 There has been a general review of methods for estimating the isomer-shift calibration constant, a: = As/Ap(O) [where 6 is the isomer shift and p(0) is the electron density at the iron nucleus].41 Charge densities at the iron nuclei in FeF,'-, FeF,4-, FeF,6-, FeC1,-, and FeCId2- have been calculated by means of the multiple-scattering method and used to arrive at a value of 01 = 0.35~1,~ mm s-1.155v The isomer shift for TiFe has been measured as - 0.145 k 0.007 mm s-l, and in conjunction with charge-density calculations for TiFe, Fe, Fe2+,and Fe3+ this yields a: = -(0.19 & 0 . 0 1 ) ~ mm ~ ~s-l.15' The contribution of many-body interactions to the charge density at iron nuclei in the configurations FeO, Fez+,and Fe3+has been studied by perturbation theory, in order to arrive at more accurate estimates of the isomer-shift calibration constant. The contribution was found to be significant in charge-density differences between FeO and Fez+ but small in differences between Fe2+ and Fe3+.158 Alloy-type Systems. Metals and intermetallic alloys are not discussed explicitly but the relevant papers are listed in the bibliography at the end of the chapter. This section deals with borides, carbides and steels, nitrides, silicides, phosphides, arsenides, and antimonides. An angular-dependence study on a single crystal of FeB has shown that the spins are oriented at an angle of 20" to the b-axis, and that the material is therefore a canted f e r r ~ m a g n e t . The ~ ~ ~ existence of two distinct structural modilb3

16' lb6

ls8 16' 168

J. L. K. F. de Vries, J. M. Trooster, and P. Ros, J . Chem. Phys., 1975, 63, 5256. A. Trautwein, F. E. Harris, A. J. Freeman, and J. P. Desclaux, Phys. Reo. ( B ) , 1975, 11, 4101. S. Larsson, E. K. Viinikka, M. L. D e Siqueira, and J. W. D. Connolly, Internat. J, Quantum Chem., Symp., 1974, 8 (Proc. Internat. Symp. At., Mol. Solid-state Theory Quantum Stat.), 145. M. L. De Siqueira, S. Larsson, and J. W. D . Connolly, J. Phys. and Chem. Solids, 1975, 36, 1419. E. V. Mielczarek and W. P. Winfree, Pfiys. Rev. ( B ) , 1975, 11, 1026. S. N. Ray, T. Lee,and T. P. Das, Phys. Reo. ( B ) , 1975, 12, 58. H. Bunzel, E. Kreber, and U. Gonser, ref. 1, p. 609.

Miissbauer Spectroscopy 41 7 fications, exhibiting different magnetic flux densities but similar Curie teniperatures, has been confirmed for this compound. The phase characteristics and magnetic properties of 45 transition-metal monoborides M,-,Fe,B have been studied over the temperature range 4.2-1000 K and the data discussed within the context of the rigid band model. The isomer-shift and magnetic-splitting data indicate that electron transfer from boron to the metal 3d band occurs in all cases, and the quadrupole splitting data are consistent with a strong ionic contribution to the electric field gradient at the 57Fe nuclei.lB0 Measurements on the intermetallic compounds (Fe,-,Co,),B (0 d x < 1) and (Fe,-,Co,)B (0 d x d 0.5) have shown that the moment on the iron is constant throughout lB2whereas it decreases i n the series (Fe,-,Mn,)Be, (0 < x < 1) each as x is increased.ls2 In the series (Fe,-,Mn,)B the magnetic moment associated with the iron falls to zero when the iron atom is associated with more than seven manganese nearest neighbours.le3 For ideal stoicheiometric Fe,PB, the Mossbauer spectrum is composed of two components, one from each of the two crystallographically non-equivalent iron sites Fe(1) and Fe(2). A detailed analysis of the spectra indicates that Fe5PB, is a simple ferromagnet with the tetragonal axis as the direction of easy magnetization. Spectra for nonstoicheiometric Fe,PB, contain a third component, assigned to Fe(1) atoms for which one of the neighbouring phosphorus atoms has been replaced by a boron atom .lS4 The Mossbauer spectrum of the intercalate C,FeCI, has been re-examined at room temperature and shown to be in good agreement with previous measurements. At 4.2 K the spectrum shows no sign of magnetic splitting, despite the fact that FeCl, itself is magnetically ordered at 7" < 15 K. The reaction of this material with potassium was shown to result in the formation of graphite-FeCI, intercalates and, eventually, the total conversion of iron(ir1) into cu-Fe.la5 Lamellar compounds of graphite with iron and other transition metals have been discussed elsewhere.ls6 Detailed temperature-dependence studies have been performed on deformed iron-carbon alloys to study the cementite recovery.1s7 Hydrogen-saturated austenitic stainless steels,lse the martensite iron-nickel-carbon system,leg and carbide phases formed as a result of tempering under y-irradiation of steels 170 have also been investigated. Spectra for the &-iron carbide and &-iron nitride solid solutions have revealed ordered distributions of interstitials. Only two iron environments were observed, and the variations of magnetic flux density lao

lel lflJ

Ia4

la7

lBR

lC9

170

D. B. De Young and R. G. Barnes, J. Chem. Phys., 1975, 62, 1726. L. Takacs, M. C. Cadeville, and 1. Vincze, J . Phys. (F), 1975, 5, 800. I. Vincze, M. C. Cadeville, R. Jesser, and L. Takhcs, ref. 1, p. 533. T. Shigematsu, J. Phys. SOC.Japan, 1975, 39, 1233. L. Haggstrom, R. Wappling, T. Ericsson, Y.Andersson, and S. Rundqvist, J . Solid Srare Chem., 1975, 13. 84. M. J. Tricker, E. L. Evans, P. Cadman, N. C. Davies, and B. Bach, Carbon, 1974, 12, 499. M. E. Vol'pin, Yu. N. Novikov, N. D. Lapkina, V. I. Kasatochkin, Yu. T. Struchkov, M. E. Kazakov, R. A. Stukan, V. A. Povitskii, Yu. S. Karimov, and A. V. Zvarikina, J . Amer. Chen;. SOC.,1975, 97, 3366. V. N. Gridnev, V. V. Nemoshkalenko, Yu.Ya. Meshkov, V. G. Gavrilyuk, V. G. Ptokopenko, and 0. N. Razumov, Phys. Status Solidi ( A ) , 1975, 31, 201. T. Sohmura and F. E. Fujita, Nippon Kinzoku Gukkaishi, 1975, 39, 374. J. Lauermannova, Kovove Mater., 1974, 12, 566. I. M. V'yunnik, Fiz. Met. Metalloved., 1975, 39, 1284.

41 8

Spcctw.scopic Propert ies

cv 1110 rgiiiz ic atid 0 yanome tn Nic Coriipo r ti is t

i t

and s-electron density at the iron nuclei, as a function of the number of ncarest neighbour interstitials, suggested that spd bands Mere formed, the hybridimtion being greater with carbon than with nitrogen.171 A detailed study of iron nitrogen solid solutions has revealed ncw environments which allow the accurate determination of the interstitial distributions in austenite and martensites. Thc influence of vacancies was detected in ~ l - F e , N . l The ~ ~ thermal decomposition and magnetic properties of Fe,C,.,AN,.8,,have been studied.173 Nitride phases formed on exposure of small iron particles to ammonia at 670 K are mentioned later (see refs. 392-394). Mossbauer and nuclear orientation studies on the alloys Co,-,Fe,Si (x = 0.13 or 1.0) have indicated that the paramagnetic moment is associated with the cobalt rather than the iron The magnetic properties o f the rare-earth iron silicides and germanides RFe,Si, and RFe,Ge, have been and the analysis of the Mossbauer spectra of FeSi and FeSb, in terms of a fluctuating electric field gradient has been mentioned.ll0 An unambiguous assignment of the components in the Mossbauer spectra of Fe,P to the two crystallographically non-equivalent sites, Fe( 1) and Fe(2), has been made from temperature-dependence measurements. From the magnetic flux densities observed at 15 K the magnetic moments at the two sites were deduced to be 1.14 and 1.78p ~ respectively. , The flux densities were found to decrease abruptly from about half the saturation value to zero at the first-order ferromagnetic-paramagnetic transition at 214.5 K, and there were also discontinuities in the isomer shifts. Ordering of metal vacancies i n a nonstoicheiometric sample of Fe,P was also i n ~ e s t i g a t e d177 .~~~~ Data have been reported at room temperature for 49 ternary pnictides with the marcasite structure, e.g. Cr,Fe,-,As,, Cr,Fe,-,Sb,, Fe,-,Co,As,, Fe,-,Co,Sb,, Fe,-,Ni,As,, and Fel-,Ni,Sb,.178 The system Fe,+,Sb (0.13 d x d 0.30) with the nickel arsenide structure has also been studied in the temperature range 10 < T / K < 625.179 67FeImpurity Sti~dies. Experiments with 57Fe+(3d04s) ions isolated in a xenon matrix have been discussed 180 (see also last year’s Report, p. 427). Mossbauer investigations on the liquid-crystalline systems 1,l ’diacetylferrocene in 4,4’-bis(octy1oxy)azoxybenzene and 4,4’-bis(heptyloxy)azoxybenzene, possessing the nematic and smectic mcsophases, have been discussed 181 and data on the latter reinterpreted.l*, 17l 17*

179

J. Foct, J. M. Dubois, and G. Le Caer, ref. 1 , p. 493.

J. Foct, ref. 1, p. 487. Y u . V. Maksiniov, 1. P. Suzdalev, K. A. Arents, and E. F. Makarov, Fiz. Met. Mrta/loued,

1974, 38, 1300. P. A. Montano, Z . Shanfield, and 1’. H . Barrett, Phys. Rev. (B), 1975, 11, 3302. E. IctrosmpicProperties of Inorganic and Organomeiallic Con1portnd.s

relaxation phenomena, and hyperfine interactions in FeCO, have also been discussed Data have been recorded for the a- and /3-forms of FeC204,2H20.256 In an oxidizing atmosphere this material decomposes directly to superparamagnetic a-Fez03, without the formation of any intermediate phases.257The products of decomposition of K3[Fe(C204)3],3H20 on exposure to U.V. radiation have been investigated by Mossbauer and other techniques, and arguments presented in favour of the view that the iron(r1)-containing final product is a polymer of composition (K2[Fe(C2O4),]},, rather than the dimer K,[Fe,(C,04)5].258 The thermal decomposition of diaquobis-salicylatoiron(I1) has been followed by Mossbauer spectroscopy and thermogravimetric techniques. Under vacuum conditions an amorphous bis-salicylate, Fe(C,,H40HCO2),, is formed at 41 3 K, becoming crystalline at 453 K. In air, only the crystalline bis-salicylate is formed at 413 K, and this loses one molecule of salicylic acid to give FeC6H40C02at 543 K.26D The Mijssbauer spectra of the iron boracites Fe3B,OI3X (X = C1, Br, or I ) have revealed the existence of three iron environments for the chloride and bromide and at least four sites for the iodide. The environments were found to differ with regard to the magnitudes of the magnetic hyperfine fields and their directions relative to the electric field gradient tensor. The observed magnetic flux densities were rationalized with calculations based on a ligand-field model.2so The iron-bromine boracite has been discussed independently,261and a series of natural and synthetic iron(u) phosphates of the homologous series Fe32+(P04),(H,O), have been studied.2R2Evidence has been presented for the existence of bivalent iron in K[FeCr(CN),] prepared from an aqueous mixture of K,[Cr(CN),] and Fe(NH4),(S04)2,6H20.268" Temperature-dependence studies on the hexammineiron(r1) salts [Fe(NH3),]X2 (X = C1, Br, I , Clod, or BF4;2s4 and NO3, SCN, or SO, 265) have revealed phase transitions which arc probably related to details of the molecular motion, not only of the NH3 molecules, but also of the anion X.2sa* 265 Substantial isotope effects have been observed in a study of the temperature dependence of the quadrupole splittings of [Fe(NH,),]X, (X = C1, BF,, or SiFJ and their deuteriated analogues. These effects, which are most pronounced for the BF4salt, are also thought to be related to the hindered rotation of the ammonia 1igands.266 a55 2b6

257 258

a68

2nL'

284

:e6 206

D. L. Nagy, I. D k i , and U. Gonser, Neurs Jahrb. Mineral., Monarsh., 1975, 101. F. Aramu, V. Maxia, and C. Muntoni, Lctt. Nuovo Cimento, SOC. Ital. Fis., 1975, 12, 225. S. Caric, L. Marinkov, and J. Slivka, Phys. Status Solidi ( A ) , 1975, 31, 263. G. G. Savelyev, A. A. Medvinskii, V. L. Shtsherinskii, L. P. Gevlitch, N. I. Gavryusheva, Yu. T. Pavlyukhin, and L. I. Stepanova, J. Solid Srate Chrm., 1975, 12, 92. J. Ladrithe and A. G . Maddock, ref. 1, p. 647. R. Link and W. Wurtinger, ref. 1, p. 581. R . Jagannathan, J. M. Trooster, and M . P. A. Viegers, 'Mossbauer Hyperfine Spectra of Fe-Br-Boracite', in 'Magnetoelectric Interaction Phenomena in Crystals', ed. A. J. Freeman and tf. Schmid, Gordon and Breach, London, New York, Paris, 1975, p. 155. E. Mattievich and J. Danon, ref. 1 , p. 562. W. U. Malik and K. D. Sharnia, Current Sci., 1975, 44. 661. L. Asch, G . K . Shenoy, J. M. Friedt, J . P. Adloff, and R. Kleinberger, J. Chem. Phys., 1975, 62, 2335. L. Asch, G . K . Shcnoy, J. M . Friedt, and J . P. Adloff, J.C.S. Dalton, 1975, 1235. B. Rrunot, Chrni. Phys. Letters, 1975, 32, 187.

429

Miissbauer Spectroscopy

A further example of slow relaxation in a high-spin iron(i1) compound has been observed for [Fe(papt),],C,H, [where papt denotes the terdentate ligand 2-(2-pyridyiamino)-4-(2-pyridyl)thiazole]. This compound actually shows a thermally induced high-spin (5T2) + low-spin (lA1) transition at higher temperatures, and a t 4.2 K 19% of the iron is also present in the ' A l state, as can be seen in Figure 2. Application of magnetic fields up to 40 kG is seen to produce effccts

-6

-4

-2

0

*2

V e l o c i t y / mm s-1

$4

*6

Figure 2 MGssbauer spectra of a ponder saniple of [Fe(papt),],C,H, at 4.2 K in longitudinal external fields [Reproduced by permission from 'Proceedings of the International Conference on the Applications of the Mossbauer Effect, Bendor (France), 1974', J. Phys. (Paris),Colloq. No. 6, Supplement to No. 12, Vol. 35, 1974, p. C6-4401

430

Spectroscopic Properties of Itiorgunic atid Organometallic Compounds

typical of the high-spin (“T,) ground state of iron(iI), except that the saturation value of the internal magnetic field is already evident in an external field of only 5 kG. It is this behaviour which is explained by assuming slow relaxation within the spin-doublet ground state split t o an extent less than 1 cm-l. The reason for slow relaxation lies in the smallness of the transition probabilities of spin-lattice relaxation for doublet ground The temperature and magnetic field dependences of the Mossbauer spectra of [Fe(2,2’-bipy)CI2] (prepared in solution) have shown the compound to be a ferroniagnet with a Curie temperature of ca. 4 K , an internal magnetic flux density of - 60 k G , and a positive quadrupole coupling constant. I n contrast, the methyl-substituted derivative [Fe(5,5’-Me,-2,2’-bipy)C12] (prepared by vacuum pyrolysis) appears to be a slowly relaxing paramagnet over the range 2-1 1 K , with Bijrt = -21 1 kG and e2qQ positive. These results are consistent with other measurements (magnetic susceptibility, far-i .r., and near-i. r.) which show [Fe(2,2’-bipy)CI2] to be a chain polymer containing six-co-ordinate Fe2+, whereas the dimethyl derivative is probably a dimer with five-co-ordinate FeZi. [Fe(2,2’-bipy)C12]prepared by low-temperature vacuum pyrolysis of [Fe(2,2’bipy),]CI, does not order sharply (as in the case of the solution preparation) but otherwise appears to have the same structure. It is suggested that high-temperature therniolysis results in partial breaking of the chloro-bridging within the polymer, to give a system of the same empirical formula but with a lower co-ordination for the Fe2’.26x Other iron(ir) complexes with nitrogen-donor ligands that have been studied by Mossbauer spectroscopy include the nietamagnetic compounds [Fe(py),CI,] and [Fe(’py),(NCS)n],26g the bis-[2-(2-pyridyl)benzimidazole]complexes [FeL,X,] (X = C1, Br, NCS, or N,-),,’O the dioximes [Fe{RC(:NO)C(:NOH)R),(3-X-py),] (R = Me or Ph; X = CONH2, COPh, CO,Et, CONHCH,OH, or CONEt,) whose ligands are physiologically the mixed-valence complex [Fe2 Fe”(OAC),(py)*] together with [Fe2’Fe3+(OAc),(H,0),],272 and some polyazaporphine complexes obtained by allowing FeCI, to react with the ligands 1,2,4,5-tetracyanobenzeneand t e t r a c y a n ~ e t h y l e n e . ~Work ~ ~ on some ‘picketfence porphyrin’ complexes which are considered to be models for oxygenbinding haemoproteins is discussed on p. 438. Mossbauer spectroscopy has also been used to assign probable structures to a number of five- and six-co-ordinate complexes of iron(1r) with the macrocyclic quadridentate ligand nteso-2,12-dirnethyI-3,7,11,17-tetra-azabicyclo[ll,3,l]heptadeca-1(17),13,15-triene (abbreviated to ms-CRH). The complexes [Fe(ms-CRH)X]PF6 (X = C1, Br, or I) have quadrupole splittings in the range 3.773.91 mm s-1, suggestive of five-co-ordination and a 5B2rather than a 6 E ground ?07

26R 2G9

2io

371

273 273

R . Zimmermann, G . Ritter, H . Spiering, and D. L.. Nagy, ref. 1, p. 439. W . M. Reiff, B. Dockum, M . A. Weber, and R. B. Frankel, Inorg. Chenr., 1975, 14, 800. S. Foner, R. B. Frankel, E. J. McNiff, W. M. Reiff, B. F. Little, and G . J. Long, ref. 56, p. 363. T. Shigeniatsu and Y. Sasaki, Bull. Itrsf. Clienr. Rcs. Kyoto Univ., 1974, 52, 658. D. G. Batyr, I. 1 . Bulgak, K . I. Turta, and R. A. Stukan, Kuord. Khim., 1975, 1 , 655. V. 1. Goldanskii, V. P. Alekseev, R . A. Stukan, K . 1. Turta, and A. V. Ablov, Fiz. Materinfy Metorlv. Koord. Khirn., Tezisy Dokl., Vses. Sooeshch., 5th, 1974, p. 127. N. I. Shapiro, I. P. Suzdalev, V. I. Goldanskii, A. I. Sherle, and A. A. Berlin, Teor. i eksp. Khim.,1975, 11, 330.

43 1

Mijssbarier Spectroscopy

state. The quadrupole splitting for [Fe(nrs-C'RH)OAc]PF, (2.40 niiii s - I ) is more characteristic of six-co-ordinate iron(i1) {exemplified by [Fe(rns-CRH)(N,),], for which the quadrupole splitting is 1.68 mni s-l}, and it is suggested that this complex features a quadridentate folded macrocyclic ligand and a bidentate Data have been recorded between 4 and 340 K for the complexes [FeL,](C104), (L = Me,SO, Ph,SO, or C6HbNO),and from the magnitudes of the quadrupole splittings it was suggested that the Me,SO and Ph2S0 complexes have singlet ground states, whereas the C6HSN0complex has a doublet ground state. In order to identify these states more precisely, the signs of the quadrupole coupling constants e2qQ were determined, and shown to be positive in each case, indicating that there are two fundamentally different types of distortion from octahedral symmetry in these solvates, arising from different steric requirements of the ligands. For the Me2S0 and Ph2S0complexes the ground state was thought to be I x y > and the distortion a compression along the tetragonal C, axis, whereas for the C6H6N0 derivative the ground state was thought to be essentially the doublet WV I x 2 - y2 - (Hi I xz >I, I(%)* I XY + (8)* I Y Z >I>, corresponding to an elongation along the trigonal C, axis. The study also yielded values for the axial and rhombic field splitting terms and spin-orbit and spin-spin coupling constants. None of the spectra showed the four-line patterns indicative of the type of phase transition discussed earlier for [Fe(H20),](C10,), and the related hexammine complexes (see refs. 243 and 264, respectively), Below 30 K the C,H,NO derivative gave asymmetric spectra indicative of slow spin-lattice relaxation. This was claimed to be the first observation of such an effect in an octahedral high-spin Fe2+ complex, and only the third known example of slow spin-lattice relaxation involving Fe2+. The other two cases referred to were the mineral gillespite (BaFeSi,O,,), where Fe2+is in a square-planar environment of oxygens, and the 1,&naphthyridine complex Fe(C8HBN2),(C1O1),, i n which Fe2+ is co-ordinated to all eight nitrogens (see last year's Report p. 441).2769 270 However, the new examples discussed on pp. 425,429 and 430 now bring this total to six. Data have also been recorded for a range of substituted pyridine N-oxide complexes [Fe(4-XC,H4NO)6](CI04)2 (X = MeO, Me, H, C1, or NOz) and compared with data for some other iron(ir) derivatives containing oxygen-donor ligands, e.g. [FeL6](C104), (L = TMSO, DPSO, or DMSO).277 Some iron(r1) oxinate complexes have been The six-co-ordinate complexes FeL2Br, and FeLBr, [L = cis-l,2-bis(diphenylphosphino)ethylene] have been studied by Mossbauer spectroscopy and magnetic susceptibility measurements and shown to contain high-spin iron@). The related complexes FeL2X2and FeLX, (X = C1, NCS, or N,) are discussed on pp. 435 and 444.270 The bis(dithiocarbamato)iron(rI) complexes [(Fe(S,CNR,),},] have been shown by their Mossbauer and reflectance spectra and magnetic susceptibilities

>

274 276

270

"'

zin

270

>

D. P. Riley, P. H. Merrell, J. A. Stone, and D. H. Busch, inorg. Chem., 1975, 14,490. J. R. Sarns and T. B. Tsin, inorg. Chem., 1975, 14, 1573. J. R. Sarns and T. B. Tsin, J . Chem. Phys., 1975, 62, 734. Y.Maeda, Y. Sasaki, and Y. Takashima, Inorg. Chim. Acta, 1975, 13, 141. H. F. Steger, J . Inorg. Nuclear Cltem., 1975, 37, 39. W. Levason, C. A. McAuliffe, M. M. Khan, and S. M . Nelson, J.C.S. Dalton, 1975, 1778.

432

Spectroscopic Piwperties of Itiorgariic nnd Organometaiiic Compounds

to form two classes. For R = Et, Pr", or Bun the complexes were shown to exist as diniers containing square-pyramidal iron, with strong intramolecular antiferromagnetic coupling. At 4.2 K clean quadrupole doublets (A x 4.2 mm s-l) were observed, consistent with the expected diamagnetic ground state, which was confirmed by the behaviour in an applied magnetic field. For R = Me or K2 = C4H8,polymeric structures with octahedral iron were suggested by the snialler quadrupole splittings (A x 2.5 mm s-l) and complex magnetic hyperfine splitting at 4.2 K in zero applied field.280The kinetics of the groundstate transformation in [Fe(NN '-dicyclohexyl thiourea),]( C104), have been studied by Mossbauer spectroscopy. The two forms differ only in the distortion from octahedral symmetry of the iron environment.281 Highspin Iron(iii) Compounds. Superparamagnetic relaxation effects observed in the spectrum of the canted antiferromagnet FeF, have been related to the observed critical behaviour of the small-angle scattered intensity.282 Fluoride phases formed on the surface of iron-nickel alloys have been studied (seep. 423).229 Miissbauer spectra of FeCI, vapour deposited at low temperatures have revealed the existence of two separate phases. These give quadrupole doublets above 6.5 K and magnetic hyperfine splittings below 6.5 K. Phase A is believed to be the dimer molecule Fe,CI,, and these are thought to link together end-to-end to form phase B. As the temperature is raised to 300 K phase A is transformed progressively into phase I3 and finally into the normal crystalline phase. A11 the phases show superparamagnetic relaxation effects below their magnetic transition temperatures. In contrast to the amorphous structures formed by the iron(I1) halides (see ref. 227), the vapour deposition of FeCI, leads to microcrystalline phases.283 The sublattice magnetization in FeBr, has been examined in detail below the critical region.2R4 Molecular orbital theory has been used to interpret the experimental quadrupole splitting of FeOC1.28S The thermal decomposition of Fe2(S04)3,7H20has been shown to proceed ilia the hexahydrate at 391 K, the tetrahydrate at 435 K, and the anhydrous salt at 478 K, finally to give ar-Fe,O, at 943 K.286 The relaxation-broadened Mossbauer spectra of the alums FeM(SO,),,l 2H20 (M = NH,, MeNH,, K , Rb, Cs, or TI) and Fe(N0,),,9H20 have been analysed i n terms of several overlapping Lorentzians to yield relaxation parameters. A correlation was found between the different types (a#) of alum and the characteristics of the spin r e I a ~ a t i o n . 2*8 8~ ~The ~ relaxation spectra of Fe(NH,)(S04),,12H20 have been discussed in terms of Redfield's theory.lo6 This material 180

2x3

284

2n5 2L6 ~7

ZRn

B. W. Fitzsimmons, S. E. Al-Mukhtar, L. F. Larkworthy, and R. R. Patel, J.C.S. Dalton, 1975, 1969. R. Latorre, J. A. Costamagna, E. Frank, C. R. Abeledo, and R. B. Frankel, ref. 1, p. 635. I-I. Shechter and D. Bukshpan-Ash, Phys. Reo. ( B ) , 1975, 11, 2673. F. J. Litterst, W. Broll, and G . M. Kalvius, ref. 1, p. 415. W. T. Oosterhuis, B. Window, and K. Spartalian, Phys. Rev. ( B ) , 1974, 10, 4616. A. Trautwein, R. Reschke, R. Zirnmerman, 1. Dkzsi, and F. E. Harris, ref. 1, p. 235. A. Bristoti, P. J. Viccaro, J. I. Kunrath, and D. E. Brandao, Znorg. Nuclear Chem. Letrers, 1975, 11. 253. T. Lohner, I. Dkzsi, D . L. Nagy, and A. M. Afanas'ev, Phys. Letters ( A ) , 1975, 53, 446. I . Dkzsi, T. Lohner, D. L. Nagy, and A. M. Afanas'ev, ref. 1, p. 449.

Miissbnuer Spectroscopy 433 has been shown to decompose to Fe,(SO,), and Fe,O, upon proton irradiation."l Data have been recorded for two iron(iii) sulphates in the jarositc group: H,OFe,[(OH),(SO,),] and K(Fe,.,Al,,,)[(OH),(SO,),]; these were shown to be antiferroniagnetic, with Nkel temperatures of 17.5 and 54 K , respectively.z53 The thermal decomposition of Fe(N03),,1.5N,0, (i.e. [(N,O,), +2{Fe(NO,),)-I) has been shown to proceed via [NO]+[Fe(NO,),]- at 303 K and mmHg, [Fe,O(NO,),] and (NO,)+[Fe(NO,),]- at 31 5-- 379 K, and [FeO(NO,)] at 379-479 K to Fe203at 573 K. The compounds [Fe,O(NO,),] and [FeO(NO,)] were both found to exhibit resonances at room temperature, a characteristic feature of polymeric lattices. Data were also recorded for M+[Fe(NO,),][ M = Me,N, NO2, N304, Et,NH,-, (x = 1-4)], M+[FeCI,]- [M = Et,NH,-, ( x = 1--4)], and [NO]+[FeX,]- (X = C1 or NO3). Single-line resonances were exhibited by all except the last two compounds, which gave sinall quadrupole sylittings attributed to the interaction of the highly polarizing NO t. cation with X.2*Q Relaxation effects have been studied in the Miissbauer spectra of Fe(NO,), and Fe(ClO,), frozen solutions and Fe(ClO,), crystal hydrates in zero external magnetic field and in various magnetic fields up to 80 kG. The relaxation timc in the frozen solutions was found to be field-dependent and rather long in high fields. In crystal hydrates the relaxation times turned out to be independent of field strength and much The existence of the ion [(H,O),FeOFe(H2O)J4+has been established by a combination of Mossbauer, i.r., and Ranian measurements on basic iron(rr1) nitrate and perchlorate solutions. Previous studies have favoured the existence of [(H,0)4Fe(OH)2Fe(H20)r]1 .,O1 In another study of frozen solutions of these salts, a phase transition, associated with a structural change from an amorphous to a more ordered state, has been Frozen solutions of iron(iI1) in perchloric, nitric, sulphuric, and hydrochloric acids have been studied at various acid Two magnetically ordered compounds, FeBO, and Fe,BO,, have been detected in the devitrification of an iron-containing borate glass of approximate composition Fe2O3,8B,O3. The latter was formed first and then converted into FeBO, at high t e m p e r a t ~ r e . ~ ~ ~ The effect of U.V. radiation on the organometallic Fe-DNA complexes 6-aminopurine-Fe, adenosine-3'-phosphate-Fe, and guanosine-3'-phosphate-Fe has been studied by Mossbauer Iron(ir1) complexes formed in aqueous acetic acid solutions have been studied as a function of pH; [Fe(0H)J3+ was detected at very low pH (0-1 3, but this gave way to the polynuclear species [Fe,(AcO),(OH),]+ and [Fe,(AcO),(OH),] in the pH ranges 1.5-3.0 and 3.0-4.0, respectively. Mixed iron-chromium +

28e

zoo

202 2u3

*OG

C. C. Addison, P. G. Harrison, N . Logan, L. Blackwell, and D . H. Jones, J.C.S. Dalton, 1975, 830. F. Sontheimer, D . L. Nagy, I. Dkzsi, T. Lohner, G. Ritter, D. Seyboth, and If. Wegener ref. 1, p. 443. J. M. Knudsen, E. Larsen, J. E. Moreira, and 0. Faurskov Nielsen, Acta Chem. Scand. ( A ) , 1975, 29, 833. F. A. B. Chaves and V. K. Garg, J. Znorg. Nuclear Cheni., 1975, 37, 2283. V. Ujihira and Y . Suzuki, Bunseki Kagaku, 1974, 23, 1028. J . Jach, J . Nonmetals, 1974, 2, 89. M. GreguSkovii, H . Cirak, and J . Novotng, ref. 1, p. 355.

434

Spec I 1.cis cop ic Froper I ies of /no rgrur ic r m I 0rgnm me trillic Conipoiri

d s

complexes were also Magnetic susceptibility and Mossbauer data have been discussed in tcrms of exchange interactions in the trjnuclear cluster coinpou nds [Fe:,(Ph CO2)5( 011)J( Ph C 0.) ,H 0, [0Fe,( P h CO2) H 20) 3]( Cl 0,),H,O, and [OFe,(CH,CNC02),(H,0),1(CI0,),6H20.2g7Iron(ir1) salts of ethylenediaminetetra-acetic acid, N-hydroxycthylethylenedianiinetriacetic acid, cyclohexylenedinitrilotetra-aceticacid, and nitrilotriacetic acid have been examined to determine the relative amounts of monomeric and diineric anions present i n the solid solution, polyelectrolyte, and ion-exchanger phases as a function of pH of the equilibrating solutions. In general, the dinieric species were found to be more prevalent as the pH was The photodecoiiiposition of K3[Fe(C,0,),],3H,0 has been re-examined (see p. 428).258 The 0x0-bridged dinuclear complexes [L,(NCS)FeOFe(NCS)L,]2’ ( L = I ,lophenanthroline or 2,2’-bipyridyl) have been prepared, and shown by Mossbauer measurements in applied magnetic fields to have singlet ground states (no augmenting fields were observed) and large asymmetry parameters (9 z 1). By contrast, the non no nuclear complex [FeL,(NCS),](NCS) was shown to be paramagnetic, with an S = $ ground state.*09 Other iron(m) complexes with nitrogen donor ligands that have been studied include tris(ethy1enediamine)iron(1ii) ~ u l p h a t e , the ~ ~ ~ six-co-ordinate complexes [Fe(ms-CRH)X,](BF,) (X = Cl or Br; ms-CRH is the macrocyclic ligand mentioned on p. 430),274 and co-ordination complexes of FeC1,,6H20 with amorphous butadiene-4vinylpyridine copolymer o r butadiene--styrene-4-vinylpyridine terpolymer vulcanizates.”l Data have been recorded for the complexes bis(dicyc1ohexyldithiophosphinato)iron(ni)X (X = C1, Br, or I).302 Spin-crossover Systems and Unrrsual Electronic Statey. The five-co-ordinate complexes [Fe(P,)X](BPh,) (X = Br or I ; P, = hexaphenyl-l,4,7,10-tetraphosphadecane) have been studied between 4.2 and 298 K and the results interpreted in terms of a singlet ( l A J + triplet spin equilibrium with a rate constant k > loBs-l. Only a single quadrupole doublet was observed, but from the decreasing magnitude of the splitting with increasing temperature it was concluded that the ‘ A , ground state must be mixed with a spin-triplet excited state via spin-orbit coupling. For the iodo-complex, the quadrupole splitting and isomer shift relative to nietallic iron were found to be 2.25 and 0.13 mm s-’, respectively, at 4.2 K , and 1.8 1 and 0.20 nim s-l, respectively, at 298 K. From a magnetic perturbation study at 4.2 K, the quadrupole coupling constant was shown to be positive, and a value of 9 z 0.8 was determined for the asymmetry parameter.,03 A unique magnetic series has been established using the 14-, 15-, and 16-membered niacrocyclic ring systems ( I ) and axial thiolate ligands. The 286 287

298 299 800

301 302 303

B. P. Nikol’skii, A. V. Kalyamin, V. A. Kuvshinov, V. V. Pal’chevskii, S. R. Tomilov, and Kh. M. Yakubov, Doklady Akad. Nauk S.S.S.R., 1974, 219, 659. L. N. Mulay and G . H . Ziegenfuss, ref. 5 6 , p. 213. G . E. Stein and J. A. Marinsky, J . Inorg. Nuclear Cheni., 1975, 37, 2421. V. K. Garg, P. G . David, T. Matsuzawa, and T. Shinjo, Bull. Cheni. Soc. Japan, 1975,48, 1933. A. N. Garg and P. N. Shukla, Indian J . Cheni., 1974, 12, 996. C. T. Meyer and M. Pineri, J . Polymer Sci.,Polymer Phys., 1975, 13, 1057. R. Y.Saleh and D. K. Straub, Inorg. Chini. Acfa, 1975, 13, 105. K. Konig, G . Rittcr, and H . A. Goodwin, Chent. Phyys. Letters, 1975, 31, 543.

Mossbauer Spectroscopy

435

complex Fe[14]N4SPh was shown to have an isomer shift typical of tetragonal low-spin iron(m)-N4 complexes, and to give, as expected, only a small augmenting magnetic field of flux density - 70 kG when placed i n an applied field of flux density 80 kG. The pyridine adduct Fe[14]N4(SPh)(py) was also shown to have a spin doublet ( S = 3) ground state. By contrast, Fe[lG]N,(SCH,Ph) gave an isomer shift and quadrupole splitting similar to those obtained for high-spin tetragonal iron(1ii)-N4 complexes, and accordingly gave a large augmenting field of flux density -450 kG in an applied field. For Fe[l6]N,SPh the various parameters were intermediate between those for Fe[l4]N,SPh and Fe[16]N4(SCH,Ph), and the complex was therefore thought to contain iron in a spin quartet ( S = 8) ground The magnetic behaviour of the substituted 1 ,lo-phenanthrolineiron(i1) complexes [FeLJ(C1O4), (L = 2-Me-phen, 2-MeO-phen, 2-Cl-phe11,or 2,9-Mc,phen) has been examined in the temperature range 4.2-300 K, and shown to depend markedly on the nature of the cu-substituent. The methyl- and methoxysubstituted derivatives were both found to exhibit teniperatiire-dependent high-spin + low-spin transitions, whereas the other two complexes were shown to remain in the high-spin state throughout. I t is interesting to note that the presence of H in the a-position generates low-spin behaviour over the entire temperature range. As shown in Figure 3, the resonance of the high-spin component is split into two doublets corresponding to the 5 E and 5A1 states. The temperature dependence of the transitions was analysed theoretically, taking into account trigonal and rhombic distortion, spin--orbit coupling, and covalency, and a possible mechanism was proposed.3o5 Substituent effects on the spin equilibrium have also been studied in some iron(1i) salts containing the sexidentate ligand tris-{4-[(6-R)-2-pyridyl]-3-aza-3-butenyl]amine(R H or Mc)."O" A magnetic cross-over has been observed in the series of six-co-ordinate iron(1i) complexes FeL,X, and FeLX, (L = Ph,PCH:CHPPh2; X = CI, Br, NCS, or N,) as X is altered. The complexes having X = NCS and N, were both found to be low-spin ( S = 0), whereas the chloro-complex was found to exist i n a temperature-dependent high-spin + low-spin equilibrium, and the broinocomplex in a high-spin ( S = 2) Data have been recorded for six complexes of iron(nr) with thiosemicarbazones of substituted salicylaldehydes of the type NH,[Fe(Rthsa),],nH,O (R = 3-N02, 305

S. Koch, R. H. Holm, and R. B. Frankel, J . Amer. Cliern. SOC.,1975, 97,6714. J. Fleisch, P. Gutlich, K . M. Hasselbach, and W. Muller, ref. 1, p. 659. M. A. Hoselton, L. J. Wilson, and R. S. Drago, J. Amer. Chem. Soc., 1975, 97, 1722. 15

Spectr*oscopicPropcrtirs of ltiorgnnic aiid Organametallic Conipoimls

436

-\F)

5-N02, 5-C1, 5-Br, 5-Me, and 3,5-di-C1). At 80 K all were shown to be in the low-spin state, and this was preserved at 300 K for all except the 5-nr- and 3,5-di-CI-complexes; the latter were found to exist as mixtures of low-spin and high-spin

o.*,,

,

99.0 99.6 -

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99.4 99.2 -

99.0 100.099.5

99.0 C

.-0 ln .-ul E

ln C

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90.5

-

98.0-

97.0 -

133 K

97.5

96.5

-

+-

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,-

I'

d

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4,

98.0-

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96.0-

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V e l o c i t y / m m s-1 Figure 3 Mussbairer spectra of [Fe(2-Me-phen),](CIO,),. At 4.2 K and 133 K the resonance of the high-spin component is split into two doublets corresponding to rite 6E and 6 A , states [Reproduced by permission from 'Proceedings of the International Conference on the Applications of the Mossbauer Effect, Bendor (France), 1974', J. Phys. ( P a r i s ) , Colloq. No. 6 , Supplement to No. 12, Vol. 35, 1974, p. C6-6601 K. I. Turta, A. V. Ablov, N. V. Gerbeleu, R. A. Stukan, and C.V. Dyatlova, Russ. J . Inorg. Chem., 1975, 20, 8 2 (Russian original Zhur. ncorg. Khirn., 1975, 20, 150).

Miissbauer Spectroscopy 437 The Massbauer effect has been used to study the phase transition in the region of room temperature in a solid solution of metal-free phthalocyanine and phthalocyanineiron(~r).~~~~ 30g In last year’s Report (p. 449) a mixed-crystal technique for inducing magnetic hyperfine splitting in bis-(”’-diet hyldit hiocarbaniato)iron(rrI) bromide [abbreviated to Fe(ethdtc),Br] was described. It involved the substitutional introduction of a small amount of the 57Fe-enrichedparamagnetic bromide into the isomorphous lattice of the ferromagnetic chloride. The technique clearly has limited applicability because of the need for substitutional replacement of host by guest molecules. However, it has now been shown that this requirement can be relaxed when the ground Kramers’ doublet of the guest complex is a I k & ) state, and the method was demonstrated by a study of the bis-dimethyl analogue [Fe(methdtc),Br] dissolved in [Fe(ethdtc),Cl] to the extent of 20 mol%. The high concentration of the dopant as well as the differences in the molecular structure between the host and guest molecules excluded any possibility of substitutional replacement, but the formation of a true solid solution was proved by the absence of the [Fe(methdtc),Br] quadrupole doublet from the spectra, as well as by the lowering of the ordering temperature to 2,145 K in the mixed crystal compared with 2.43 K in pure [Fe(ethdtc),CI]. The magnetic flux densities observed at the nuclear sites in the guest and host molecules were respectively 250 and 335 kG.310 Further work on the [Fe(ethdtc),Br][Fe(ethdtc),CI] system has shown that the magnetic transition temperature decreases only gradually from T = 2.43 K as the proportion of the bromocomplex is increased, until the concentration reaches 90%, when the ordering temperature drops rapidly to T < 0.3 K . This was taken as evidence that the direction of the exchange field remains unaltered and that the exchange integral between the chloro and bronio molecular units must be comparable in magnitude to that between two chloro molecules.311 Hyperfine interactions in some related iodide compounds have been and the temperature dependence of the quadrupole splitting for some dithiocarbamato- and diarsine-iron(1v) chelates has been analysed successfully on the basis of a theoretical model for iron(rv) ions in a strong ligand field.313 Biological Comporrnds. Several reviews on biological compounds have already been referred to (see refs. 8, 18, 28, 29, 45, 46, and 77-80). Doubts have been expressed about the validity of the calibration procedure used by Moutsos, Adams, and Sharma (1974; see last year’s Report, p. 449) to calculate the isomer shift of iron(rr1) ha emir^.^^^ A procedure used in the past for evaluating electric field gradients in non-metals has now been extended to a study of the quadrupole splitting of iron(II1) in haemin. The value calculated theoretically was shown to agree well with the experimental value of +0.78 & 0.03 mm s-l if values of a(Cl-) = 2 A3 and a(N) = 1 A3 were used ylo

311

sla

313 s14

B. Dudreva, R. Pirintchieva, and S. Grande, ref. 1, p. 633. B. Ts. Dudreva and R. K. Pirinchieva, Bulg. J . Pliys., 1975, 2, 126. A. Malliaris and D. Petridis, Chem. Phys. Lerfers, 1975, 36 117. A. Malliaris and A. Simopoulos, J . Chem. Phys., 1975, 63, 595. D. Petridis, A. Simopoulos, A. Kostikas, arid M. Pasternak, ref. 1 , p. 262. R. M . Golding and K. J. Jessop, Austral. J . Chem., 1975, 28, 179. K. J. Duff, J . Chem. Phys., 1975. 63, 2259.

438

Spectroscopic Properties of Iitorgniiic mid Orgariometallic Conipoirnds

for the polarizabilities of C1- and N.3*5The electric field gradient at the iron nucleus in chloro-haemin has also been studied theoretically, and it has been shown that the nearest-neighbour carbon atoms must be taken into account as well as the chlorine and nitrogen. The effect of the 3p-orbitals of iron was also shown to be important.S1s Iron(r1) porphyrin complexes regarded as models for the active site of oxygenbinding haemoproteins have been synthesized, and characterized fully by Mossbauer spectroscopy and several other techniques. All complexes featured the 'picket-fence porphyrin' rneso-tetra-(a,a,a,a-o-pivalamidophenyl)porphyrin ( a , a , a , a - T p i ~ P P ) .318 ~ ~ ~The * compound [Fe(O,)(N-Me-imid)(o,o,a,a-TpivPP)] (imid = imidazole) was studied over a wide range of temperature, and a pair of peaks with a temperature-dependent quadrupole splitting and linewidth were observed. The results were interpreted in terms of a model, consistent with previous X-ray studies, which provides for relaxation effects as the molecule assumes two possible conformational states. The energy separation of the two conformational states, their respective electric field gradient tensors, and the relaxation rate at each temperature were all determined.319 The large quadrupole splitting observed in the Mossbauer spectra of oxyhaemoglobin and oxycytochrome P-450 are thought to be anonialous for lowspin iron(n), and it has been suggested in the past that these complexes, while formally Fe'I-O,, are best described in terms of an Fe1I'-O,- configuration in which two unpaired electrons couple to give a diamagnetic ground state. However, theoretical calculations for a variety of possible geometries of the oxyhaemoglobin compound have now indicated that large quadrupole splittings are in fact expected for the Fe"-O, configuration. The electric field gradient was also calculated for a model high-spin deoxy-iron(I1) haemoglobin complex. In this model the oxygen ligand was removed, the imidazole ligand retained, and the iron moved out of the mean plane of the pyrrole nitrogen by 0.42 A, consistent with a recent X-ray analysis of a similar compound. The results yielded a value for the quadrupole splitting of 2.61 mm s-l, which compares favourably Similar calculawith the experimental low-temperature value of + 2.28 mm SKI. tions for a model oxy-P-450 compound, constructed by replacing the axial imidazole by SMe-, gave results which were less c0nc1usive.~~~ The electronic charge distribution at the iron atom in oxyhaemoglobin has been studied inde~endently,~~' and the electronic structures of d e o x y h a e r n o g l ~ b i n ,322 ~ ~nitric ~~ oxide haem0globin,~2land carbonyl haemoglobin 321 have been investigated. The related deoxymyoglobin 323 and carbonyl myoglobin 324 have also received

+

322p

81e 317

3229

R. R. Sharma and P. Moutsos, Phys. Rev. (B), 1975, 11, 1840. R. R. Sharma and P. Mastoris, ref. 1, p. 359. J. P. Collman, R. R. Gagne, H. B. Gray, and J. Hare, J. Amer. Chem Suc., 1974, 96, 6522.

J. P. Collman, R. R. Gagne, C. A. Reed, T. R. Halbert, G. Lang, and W. T. Robinson, J. Anrer. Chem. Soc., 1975, 97, 1427. 819 K. Spartalian, G. Lang, J. P. Collman, R. R. Gagne, and C. A. Reed, J. Chem. Phys., 1975, 63, 5375. rao G. H. Loew and R. F. Kirchner, J. Amer. Chem. SOC.,1975, 97, 7388. 321 V. Kothekar, Proc. Indian Nut. Sci. Acad., Part A , 1974, 40,112. 8a* A. Trautwein and F. E. Harris, Theor. Chim. Acra, 1975, 38, 65. 323 H. Eicher, F. Parak, D. Bade, and J. Tejada, ref. 1, p. 363. 334 A. Trautwein, Y. Maeda, F. E. Harris, and H. Formanek. Theor. Chim. Acra, 1974, 36, 67. 318

Mossbauer Spectroscopy

439

attention. From a least-squares fit to the temperature dependence of the quadrupole splitting the following energy-level scheme was deduced for the iron(r1) ion in deoxygenated sperm-whale myoglobin : SBz (0 cm-l), l A l (60 cm-l), 6 E (106 cm-l), and 3E (809 ~ m - 9 .The ~ ~carbonyl ~ complex of sperm-whale myoglobin was shown to have a quadrupole coupling constant of *e2qQ = +0.363 mm s-l, and on the basis of MO calculations this was shown to be consistent with an Fe-C-0 angle of ca. 135". The iron atom was thought to be situated in the haem The electronic structure of iron has been shown to be the same for anhydrous haemoglobin and its isolated a and /3 328 The observation that both subunits contain iron in the high-spin (S = 2) and low-spin (S = 0) states, in similar proportions and with similar Mossbauer parameters, argues strongly against a model proposed earlier requiring the Q: and /3 subunits to have different spin states. A possible interpretation of the origin of the two spin states was discussed, and their quadrupole splittings were analysed in detail to give the electronic structure of their low-lying e i g e n ~ t a t e s . ~ ~ ~ The low-spin nature of iron(1rr) in haem haemopexin has been indicated by e.s.r. studies and corroborated by Mossbauer ~ p e ~ t r ~ Anaerobically ~ ~ ~ p y . ~ ~ reduced samples of cytochrome P-450from Pseudomonas putida have been studied in applied magnetic fields and shown to contain iron in an environment of very low (triclinic) symmetry, resulting in a large zero-field splitting of the electronic ground state. The electric field gradient tensor was shown to have a large asymmetry parameter, and a principal axis that was rotated substantially from the frame defining the zero-field splitting. The study emphasized the power of high-field Mossbauer spectroscopy as a tool for investigating the structures of high-spin iron(r1) compounds, and demonstrated that it can substitute for magnetic susceptibility Similar measurements on chloroperoxidase from Caldariomyces fumago have shown that the ligand structure about the haem iron is possibly identical to that in cytochrome P-450,whereas horseradish peroxidase and deoxyhaemoglobin gave high-field Mossbauer spectra that differed considerably from each other and also from that of cytochrome P-450,suggesting a different arrangement of ligands in each case.32Q Cytochrome-c,, a bacterial electron-transporting protein from various species of sulphate-reducing bacteria, contains four haems per molecule. This results in a rather high iron density compared with other biological molecules, and the possible effects of this on the magnetic properties of the compound have now been investigated by Mossbauer spectroscopy. At 4.2 K only a quadrupole doublet with broadened lines was observed, consistent with rapid spin-lattice relaxation as a result of the significant haern-haem interactions. As the external magnetic field was increased from zero to 600 G, strongly reduced relaxation was observed, but no external field dependence was detected for fields greater than 8a6

3J6 327 y28

Y . W. Chow and A. Mukerji, Biochem. Biophys. Res. Comm., 1975, 62, 989. G. C. Papaefthymiou, €3. H. Huynh, C. S. Yen, J. L. Groves, and C. S. Wu, J . Chem. Phys., 1975,62, 2995.

A. J. Bearden, W. T. Morgan, and U. Muller-Eberhard, Biuphys. Res. Comm., 1974,61,265. P. M. Champion, J. D. Lipscomb, E. Munck, P. Debrunner, and I. C. Gunsalus, Biochemistry, 1975, 14,4151.

P. M. Champion, R. Chiang, E. Munck, P. Debrunner, and L. P. Hager, Biochemistry, 1975, 14, 4 159.

440

Spectroscopic Properties of Inorganic and Organonietallic Compounds

600 G , indicating that the neighbouring iron(rrr) ions have different g axes from one a n ~ t h e r . ~ ~ O Well-resolved paramagnetic hyperfine structure from high-spin iron(ri1) ions has been observed in the Mossbauer spectra of 57Fecomplexed by enterobactin, an iron-transport protein found in many enteric bacteria. Spectra were observed over a range of temperature (4.2-77 K) and applied magnetic fields (0-6 kG), and were well explained on the basis of a spin Hamiltonian with rhombic symmetry including a fourth-order term in the electronic 332 Some other naturally occurring iron-transport complexes such as ferrichronie A, deferaximine, myobactin P, and transferrin, together with some inorganic hydroxamate model complexes, have given Mossbauer and e.s.r. results which are well explained by a spin Hamiltonian model for the electronic state with rhombic symmetry, and not the trigonal symmetry suggested by X-ray structure determination^.^^^ Paramagnetic hyperfine structure has also been observed in the spectrum of [57Fe]lactoferrin, indicating a long spin-relaxation time. The two metal-binding sites were shown to be equivalent and to contain iron(ii1) ions with a magnetic flux density per unit spin of 223 kG.333 Photoinduced processes have been studied in rhodopsin and photoreceptor mem b ~ a n e . ~ ~ ~ A preliminary account has been given of important new experiments designed to look for recoil-free effects in non-frozen bacterial cells. The measurements were carried out with the bacterial sources, comprising 67Co-doped enterochelin in E. coli cells, maintained at 3 " C . At this temperature a recoil-free effect of ca. 0.03 ? O.OOSo/,and linewidth 3 mm s-l was observed during the first 24 hours, but disappeared thereafter. The effect was tentatively attributed to t 7 C nuclei ~ undergoing diffusive motion across the cell membrane, and rough estimates of the diffusion constants were made.335The application of Mossbauer spectroscopy to the study of the dynamic properties and catalytic activity of the enzymes a-chymotrypsin and serum albumin has also been The Mossbauer spectra reported last year (see last year's Report, p. 451) for the high-potential iron-sulphur protein (HiPIP) from Chromatium 337 and the ferredoxin from Clostridium pnsteurianunr 338 have been discussed further. The data for the latter, taken at 4.2 K in a field of 20 kG parallel to the y-ray direction, were interpreted quantitatively in terms of a model in which each of the two iron-sulphur clusters within the molecule contains one electron, but with no cluster-cluster interaction. Data for a crystalline sample of oxidized ferredoxin were also Measurements on the super-reduced form of 337p

330

331 332

s33

334

330

JJs

K. Ono, K. Kimura, T. Yagi, and H . Inokuchi, J . Chem. Phys., 1975, 63, 1640. K. Spartalian, W. T. Oosterhuis, and J. B. Neilands, J . Chem. Plzys., 1975, 62, 3538. W. T. Oosterhuis and K. Spartalian, ref. 1 , p. 347. J. Ladriere, R. Coussement, and B. Theuwissen, ref. I , p. 351. G. R . Kalamkarov, V. E. Prusnkov, M . A. Ostrovskii, R. A. Stukan, and V. I . Goldanskii, Dokludy Akud. Nuuk S.S.S.R.,1974, 219, 1245. E. Giberman, Y . Yariv, A. J. Kalb, E. R. Bauminger, S. G. Cohen, D. Froindlich, and S. Ofer, ref. 1, p. 371. E. N. Frolov, G. I . Likhtenstein, 0. W. Relonogova, W. A. Trukhtanov, arid V. 1. Goldanskii, ref. 1 , p. 358. D . P. E. Dickson, C. E. Johnson, C. L. Thompson, K. Cammack, M . C. W. Evans, D. 0. klall, K. K. Rao, and I J . Westx, ref. 1, 11. 343. H. Eicher, F. Parak, L. Bogner, D. Bade G. M. Kalvius, K. Gcrsontle, and H. L. Schlaak, ref. 1, p. 367.

Mossbauer Spectroscopy

441

HiPlP have indicated that the iron atoms are i n ii similar valence state to those i n the reduced ferredoxin from Cfostridiuni pusteurianum, with possibly some lack of equivalence between the iron atoms within the four-iron M ossbauer spectroscopy has helped to characterize the ferredoxin from Bacillus steorothermopliilirs as a four-iron-four-sulphur f e r r e d o ~ i n and , ~ ~ data ~ on yeast aconitase from the cells of Cundidu IipoljJticuhave suggested the presence of two high-spin iron(rr1) ions in an antiferromagnetically coupled dinuclear complex, similar to the two-iron ferredoxins, together kith a small amount of high-spin i r o n ( i ~ ) .The ~ ~ ~molybdenum-iron protein from Azotobacter vinelundii has been shown to contain a total of four different types of iron Mossbauer spectra have been recorded for different parts (mycelia, spores, and sporangiophores) of the fungus Pliycomyces blakesleean~sgrown in an agar medium with h7Fe. The iron was found to be present in two forms, one of which resembled that of iron in the growth medium and the other being ferritin. The amount of iron in the former state was observed to decrease relative to the amount of iron in the latter state in going from mycelia to the sporatigiophores to the sporangia themselves, thereby demonstrating the progressive conversion of iron for different parts of the Phyconzyces. At low temperature the iron atoms were shown to be antiferromagnetically clustered within a ferritin molecule, and the size of the clusters could be inferred from the superparamagnetic behavio~r.~~~ Low-spin and Covalent Complexes. Quadrupole splittings calculated from p.q.s. values have been plotted against values observed experimentally for 81 iron(ir) compounds. A least-squares analysis of the data gave a correlation coefficient of 0.992, a slope of 1.01, and an intercept of 0.03 mm s-l, thc latter being very close to the expected values of 1.00 and 0.00 mm s-l, respectively. Agreement between the predicted and observed values was within 0.2 nim s-l for 90% of the compounds, discrepancies being most pronounced for carbonylcontaining complexes.344 A correlation between the Mossbauer quadrupole splitting and the separation of the cyanide stretching frequencies in the i.r. for the alkali-metal ferricyanides M,[Fe(CN),],xH,O ( M = H, Li, or Na) has been discussed in ternis of interactions between the alkali metal and the cyanide ligand.345 Mossbaucr studies on frozen aqueous solutions of alkali-metal hexacyanoferrates have also shown that the alkali metal associates with the cyanoferrate anion, and that this interaction is hindered by the addition of glycerol or quaternary phosphonium halides. Glycerol is thought to decrease the interaction by increasing the viscosity, whereas the phosphonium cations achieve the same effect by themselves associating with the cyanoferrate anions.34s The thermal decomposition of the alkali-metal 339 340

D. P. E. Dickson and R. Cammack, Biochern. J., 1974, 143, 763. R. N. Mullinger, R. Camniack, K. K. Rao, D . 0. Hall, D . P. E. Dickson, C . E. Johnson, .I. D. Kush, and A. Siniopoulos, Biocheni. J., 1975, 151, 75. T. Suzuki, Y . Maeda, H . Sakai, S. Fujinioto, and Y. Morita, J . Biochenr. (Tokyo), 1975, 78, 55s.

I!. Munck, H . Rhodes, W. H. Orme-Johnson, L. C . Davis, W. J. Brill, and V. K . Shah, Hiocltinr. Biophys. Actci, 1975, 400, 32. K . Spartalian, W. T. Oosterhuis, and N. Smarra, Bior,him. Biophys. Acta, 1975, 399, 203. :W C i . M. 13ancroft and K . D. Butler, Inorg. Cliiiii. Acfcr, 1975, 15, 57. W' A . N. Garg, Z.Nururforscli., 1975, 30b, 96. :L'2ti S. Papp, P. Kvintovics, F. Nagy, and A. Vertcs, Magyar KPm. Folybirat, 1975, 81, 211. 3.1:1

442

Spectroscopic Properties of Inorganic and Organometaliic Compounds

hexacyanoferra te(1II) complexes Li3[Fe(CN),],4H20, Na, [Fe(CN),], H 2 0 , and M,[Fe(CN),] (R = Rb or K) have been studied up to 923 K. The presence of water was found to lower the decomposition temperature and also to favour the formation of Fe,O, at higher temperature. The end-product of the decomposition of the anhydrous complexes was shown to be metallic iron, whereas the hydrated complexes gave the corresponding alkali-metal ferrite. A mechanism for the decomposition was The effects of bombarding the potassium hexacyanoferrates with protons have also been and ligandreplacement processes in the solid-state system FeSO,,xH,O-KCN were referred to earlier (see p. 427).248 The pyrolysis preparation of iron(1i) hexacyanoferrate(rr1) (i.e. ferrous ferricyanide) has been monitored by Mossbauer spectroscopy 34D and it has been suggested that published experimental data on the pyrolysis of Berlin Blue can be explained by the formation of iron(I1) hexacyanoferrate(r1) intermediate^.^^^ The positive sign of the magnetic field at the iron nucleus in Ni,[Fe(CN),], has been confirmed by measurements at 4.2 K in various applied magnetic fields.351 The orientation of the electric field gradient tensor at the iron nucleus in a single crystal of Na2[Fe(CN),(NO)],2H20 has been determined by use of a polarized Mossbauer source of 57C0 in iron metal. A value of the recoil-free fraction along the direction of observation (normal to the 011 face), which was required for the calculation of the line intensities, was first determined from the line broadening to bef = 0.354 rt 0.020. The theoretical intensity ratios of the component lines were then calculated for various values of 7 (the asymmetry parameter) and /3 (the angle between the principal axis of the electric field gradient and the n-axis) and good agreement was obtained only for Semi-empirical SCF-MO /3 = +(39 k 2") and 7 < 0.05, with e2qQ calculations have been carried out for the complexes [Fe(CN),LI3- (L = PhNO, HzO, NH3, or NO), [Fe(CN),(N0)I2-, and [Fe(CN),(NO2)I4- and used to interpret the Miissbauer quadrupole splittings and to infer probable orientations for the Ph and NO,- groups in [Fe(CN),(PhNO)l3- and [Fe(CN),(NO2)l4-, respectively. The study emphasized the importance of including all the iron 3d- and 4p-orbitals in the calculations and of considering neighbouring-atom Electronic and Mossbauer spectral parameters have been correlated with the limiting SA-1rates of ligand loss in aqueous solution for the complexes [Fe(CN),L]"- (L = H 2 0 , NH3, pyridine, pyrazine, carboxylate, N-methylpyrazi nium, or dimet hyl or tetrame t hy lene s ulphoxide).354 The bonding characteristics of various carbene groups have been studied in a number of iron(i1) isocyanide carbene complexes of the types [Fe(CNMe),(carbene)](PF,), and [Fe(CNMe),(carbene),](PF,),. Partial isomer shifts and partial quadrupole splittings were derived for the carbenes, showing them to be 3p7 348

sps sLo sG1

383

353

354

D. Raj and J. Danon, J . Inorg. Niiclear Cfiem.,1975, 37, 2039. M . Kopcewicz and A. Kotlicki, Radiation EJCcts, 1975, 24,267. R. Robinette and R. L. Collins, J . Coorclination Chem., 1974, 4, 65. V. I. Goldanskii and R . A. Stukan, Koorci. Khini., 1975, 1, 137. J. Chappert, B. Sawicka, and J. Sawicki, Pfiys. Stritus Solidi (B), 1975, 72, K139. T. C. Gibb, Cfiem.Phys. Iktrcrs, 1975, 30, 137. A. Trautwein, F. E. Harris, and I. Dezsi, Tfieor. Chim. Ada, 1974, 35, 231. H. E. Toma, E. Giesbrecht, J. M . Malin, and E. Fluck, Znorg. Chim. Acta, 1975, 14, 11.

Mossbauer Spectroscopy 443 very good o-donors and poor n-acceptors relative to other neutral ligands, such as MeNC. The signs of the quadrupole coupling constants were shown to be negative and positive, respectively, for [Fe(CNMe),{C(NH,)NHMe}](PF,), and [Fe(CNMe),((CNHMe),N,HPh}](PF,),. The point-charge model was used to explain the larger quadrupole splittings for the compounds containing chelating carbenes, and the unusual quadrupole splittings for trans- and cis[Fe(CN),(o-phen),] and K [Fe(CN),(o-phen)] .355 Data for the compounds

V CN‘

Y

Figure 4 Co-ordinate system for the complex H[Fe(bipy)(CN),],2H20 and the relatioe energies of the cubic tzu(r*)orbitals deduced from the Mossbauer dutu

IFe(CNR),-,CIL,I(CIO,), [Fe(CNR)&,](ClO,),, and [Fe(CNR),CI,] [L = PPh(OEt),, PPh3; R = alkyl or aryl; x = 0, 2, or 31 have also been analysed in terms of a point-charge model and correlated with the cyanide stretching frequencies.35s The perturbation of the cubic 2Tzaground term in the complexes [Fe(bipy),(CN),I(ClO,), [Fe(CN),(phen),1(C104),H [Fe(bi~y)~(CN),1,2H,O, and H [Fe(CN),(phen)],2H20 has been investigated by means of a detailed study of the temperature dependence of the quadrupole splitting in the temperature range 80-300 K, coupled with e.p.r. and magnetic susceptibility data. For the trigonally distorted complex [Fe(bipy)Z(CN)P]z(C:104),the cubic 2T,, ground term was found to exhibit an axial splitting of about lOOOcm-l, with a smaller superimposed rhombic splitting and a spin-orbit coupling constant of about 150 cm-l; in trigonal quantization the ground term is 2A, corresponding to a ‘hole’ in the I z2 orbital. The complex H[Fe(bipy)(CN),],2H20 was shown to exhibit a tetragonal distortion of ca. 400 cm-l, with a somewhat smaller superimposed rhombic distortion and a spin-orbit coupling constant of between 100 and 150 cm-l. The relative energies of the cubic t z g (n*)orbitals deduced from the data, and the co-ordinate system for the complex, are shown in Figure 4.367 Data have also been reported for the complex [FeL,(CN),] containing the 2-(2-pyridyl)benzimidazole ligand L,270and for a series of tris-(1,Z-di-imine)iron(r1) chelates.”* Data for some low-spin iron(irr) complexes containing a 14-membered macrocyclic ring system are discussed on p. 434.304

>

3G5

3Go

G. M. Bancroft and P. L. Sears, Inorg. Chem., 1975, 14, 2716. L. Di Sipio, S. Calogero, G . Albertin, and A. A. Orio, J . Organott1etallic C/wnt., 1975, 97, 257.

3G7

36n

P. B. Merrithew, C.-C. Lo, and A. J. Modestino, Inorg. Chem., 1975, 14, 242. K. Schlosser, E. Hoyer, and D. Arnold, Spectrochint. Acta, 1974, A30, 1431.

444

Specfroscopic Properties of Itiorgniiic and Organonietallic Compounds Mossbauer and i.r. measurements have been recorded for the low-spin complexes trans-[FeClL,(L’)]+[BPh,l- {L = [(EtpP)CH2],; L‘ = organonitrile, e.g, MeCN, PhCN, or PhCH,CN, or dinitrile, e.g. malononitrile or succinonitrile} and trans-[FeL2(L’),1~+[BPh41z(L = [(Et,P)CH,],, L’ = alkyl nitrile), and discussed in terms of the a-donor and n-acceptor properties of the l i g a n d ~ . ,The ~ ~ complexes [FeL,X,] and [FeLX,] (L = Ph,PCH:CHPPh2; X = NCS or N,) have been shown to contain iron in the S = 0 state, and [FeCl,L,][FeCl,], the product from the reaction between L and FeCl,, was found to contain iron in the S = 4 state in the cation.279 Systematic variations in the isomer shifts and quadrupole splittings of a series of iron carbonyl complexes [Fe(CO),L,] [L = AsPh,, SbPh,, PPh,, P(OPh),, PBu,, P(OMe),, PCNMe,),, or CNPh] have been discussed in terms of the relative u- and w-bonding properties of the ligands. The a-bond strength was found to decrease in the sequences CNPh > P(OMe), > PBu, > P(NMe,), and P(OPh)3 > PPh, > AsPh, z SbPh,. Contrary to previous assumptions, it was suggested that there is not always ii correlation between a-donor and n-acceptor properties of l i g a n d ~ . ,Data ~ ~ for a series of tetracarbonyl complexes [Fe(CO),L] [L = (Me,C),-,P(MMe,),; x =: 0-3; M = Si or Sn] have been shown to be inconsistent with the widely discussed presence of ( p d)n- interactions in the P-M bond.361 The spectra of the adducts [(Me,N),AIO(Me,N)CFe(CO),], and [(Me,N),TiO(Me,N)CFe(CO),] have shown that the carbenoid ligands occupy the axial positions in a trigonal-bipyramidal configuration and that the formal oxidation number of the iron remains unchanged compared with that in Fe(CO),. The reaction of these carbenoid complexes with EtOLi in THF was found in each case to lead to the formation of [Li0(Me2N)CFe(CO),],2THF, with retention of the basic structure of the starting Data have been recorded for a series of 12 w-ally1 iron carbonyl complexes, and discussed in terms of forward co-ordination, n-back-donation, and molecular g e ~ n i e t r y . ~ ~ ~ Interesting new line-broadening effects for the complexes [Fe(q-C,H,)(CO),L] {L = S(CH,), or SiC1,Me) have been interpreted in terms of hindered rotation about the Fe-S or Fe-Si bond. Although other possible relaxation processes were not ruled out, the hindered-rotation treatment led to a barrier height which was smaller for the Fe-S bond (ca. 30 cal) than for the Fe-Si bond, consistent with the molecular geometries. A maximum rotation frequency of cu. 15 MHz was deduced from the temperature dependence of the linewidth for the S(CH2)4 complex. Data were also recorded at 96 K for the complexes having L = SMe,, SEt,, SPP,, SBu”,, or PPhg.364 Parameter-free MO calculations, based on the Fenske-Hall model, have been carried out on representative complexes of the types [Fe2(CO)6X,] [where X denotes both the (B-B)-non-bonded (SMe), and (NH,), ligands and the corresponding (B-B)-bonded S, and cis-MeN=NMe ligands] and [Fe,(CO),--f

3a0

362

304

J. M. Bellerby and M. J. Mays, J.C.S. Dalton, 1975, 1281. 11. Mosbaek, Acra Cheni. Scand. ( A ) , 1975, 29, 957. J. Ensling, P. Gutlich, and L. Rosch, Z . A‘aturforsch., 1975, 30b. 850. J. Pebler and W. Petz, Z . Nnturforsch., 1974, 29b, 658. H. C. Parakkat, P. J. Ouseph, R . 1.. Vonnahme, and D. H. Gibson, J . f n o t g . Nirclrur Chcnr., 1975,37, 2340. T. Sawai, J. P. Martin, I . S. Butler, and D. Simkin, ref. 1 , p. 247.

Mossbauer Spectroscopy 445 (PR2),ln (n = 0, 1 -, or 2 -), and correlated with the available Mossbauer data on species of these types.366 Data have been recorded for the complexes [Fe,(CO),(L-L)] (Figure 5 ) and their monosubstituted derivatives [Fe,(CO),L(L-L)] and [Fe,(CO),(L-L)(L-L)'] [where (L-L) and (L-L)' represent the fluorocarbon-bridged

Figure 5 The solid-state structure of [(f,fars)Fe,(CO),] (Reproduced by permission from Cunud. J. Chern., 1975, 53, 2232)

ligands (2), acting as bidentates and unidentates, respectively, and L = PPh3, P(OPh),, or SbPhJ. Magnetically perturbed spectra were recorded for several of these compounds and enabled the various lines to be assigned unambiguously

(2) a; R 1 = Rz = Me,As, I I = 2, 3 or 4 b; ,R1= RZ = Ph,P, n = 2or 3 c ; R1 = Me,As, R2 = Ph,P, n = 2 or 3

to the individual iron atoms FeA and FeB. These measurements also showed the quadrupole coupling constants ezqQ to be negative for Fea and positive for FeB, and this observation was argued to be consistent with the existence of an FeA -+ FeB dative bond. In addition, the monosubstitution on FeA was shown to take place trans to the FeA-Fw bond and cis to the two Group V atoms.s6s The complexes [Fe,(CO),{HC2But,(CO)>1,367 [Fe2{C(NC6H,,),>(CO),1,366 [Fe2(Co),{Co(NPh)2>l,366 [Fe2(CO),{C(NPr)3}l,366and [Fe,(CO),{C(NC6Hii)8}PPhJ s68 have also been studied. The structure of the trinuclear hydride complexes [Fe,(CO),H(SR)] (R = Pri or But) has been solved by a combination of Mossbauer spectroscopy and single-crystal X-ray diffraction studies. The Mossbauer spectra of the two compounds were shown to contain two quadrupole-split doublets of relative intensity 2 : 1, consistent with the equivalence of two of the three iron atoms. The X-ray analysis of [Fe,(CO)BH(SPri)]revealed basically a C,,arrangement *@a yoo

B. K. Teo, M. B. Hall, R. F. Fenske, and L. F. Dahl, Znorg. Chem., 1975, 14, 3103. L. S. Chia, W. R. Cullen, J. R. Sams, and J. C. Scott, Canad. J. Chem., 1975, 53, 2232. E. Sappa, L. Milone, and G. D. Andreetti, Znorg. Cliim. Acra, 1975, 13, 67. E. von Meerwall, J. Worth, W. Greenlee, and M. F. Farona, Specrroscupy Letters, 1974, 7 31 I .

446

Spectroscopic Properties of Iiiorgunic aiid Organonietallic Compounds

for the Fe3(C0)9S moiety, with the irons forming a near-equilateral triangle capped by a triply bridging sulphur atom. The three-fold symmetry of this fragment strongly suggested that the unique hydrogen was triply bridging on the triangular face opposite the SR group. However, because this conclusion was at variance with the Mossbauer results, it was decided to make a careful search for the missing hydrogen atom, using low-angle data preferentially to enhance the hydrogen positions in difference Fourier maps. In this way the presence of the doubly bridged hydrogen, suggested by the Mossbauer data, was clearly revealed.36BThe M ossbauer spectra of the trinuclear cyclopentadienyl complexes [Fey(~-C5H,),(CO),(S)(SR)](R = But or CH,Ph) have been shown to contain only two resonance lines, but the peak at lower velocity is slightly broader and less intense than the other component. Inequivalence of the iron environments is therefore indicated, but the individual components which contribute to the quadrupole doublet were not sufficiently resolved to allow the intensity ratio of 2 : 1, required by the proposed structure, to be visually confirmed.370 Several mixed-metal carbonyl systenis have been studied by Mossbauer s p e c t r ~ s c o p y . ~The ~ ~ -reaction ~~~ of [FeCo,(CO),,H] with phosphorus donor ligands was shown to lead to the substituted derivatives [FeCo,(CO),,..,HL,] [L = PPh,, PPh,Me, PEt,, P(OPh)3, or P(OPr),; x = 1-31 by successive substitution of one carbonyl group at cobalt, whereas reaction with the diphosphine (Ph2PCH2)2gave two isomers, one of which featured carbonyl substitutions at the iron atom.371 The products [Fe(CO),(SnX,)] from the reactions of [Fe,(CO),] with SnX, [X = C1, Br, (MeCO),CH,, MeCOCH,COCF3, (CF,CO),CH,, MeCOCH,COPh, or (PhCO),CHz] were all shown to be associated into dimers in the solid, but to exist as five-co-ordinate monomers in frozen pyridine Data were also presented for the compounds [SnX,{M(q-C,H,)(CO),)(Fe(q-C,H,)(CO),)] (M = Cr, Mo, or W ; X = C1, Br, or [Fe(q-C,H,)(CO)L(SnCI,Ph,-~)] ( x = 0-3; L = C O or PPh,), and [Fe(q-C,H,)(CO),-,LZ(SnCl3)] [x = I , L = PPh,, PEt,, or P(OPh),; x = 2, L = P(OPh)3].374 A Mijssbauer study of the ferroceniuni salt [Fe(q-C,H,),]+[FeCI,]- has shown that the structure is probably polymeric, with the anion i n a planar configuration.375 A comparison of the Mossbauer spectrum of [2]ferrocenophanethiazine 1,l-dioxide (3), in which the q-C,H, rings are tilted by 23" relative to one another, with spectra of ferrocene derivatives in which the rings are less tilted or parallel and antiprismatic has shown that substantial ring tilt can occur without the bond energy being affected.376 R. Bau, B. Don, R. Greatrex, R. J. Haines, R . A. Love, and R. D. Wilson, Inorg. 1975, 14, 3021.

s70 571

s7a

37b

y78

C/mii.,

R. J Haines, J. A. de Beer, and R. Greatrex, J . Organornetallic Chem., 1975, 85, 89. C. G. Cooke and M. J . Mays, J.C.S. Dalton, 1975, 455. A. B. Cornwell and P. G. Harrison, J.C.S. Dalton, 1975, 2017. R . J. Dickinson, R. V. Parish, P. J . Rowbotham, A. R. Manning, and P. Hackett, J.C.S. Dalton, 1975, 424. G . M. Bancroft and A . T. Rake, Jnorg. Cfiim. Acta, 1975, 13, 175. R. A. Stukan, A. A. Koridze, and V. E. Prusakov, Zzvest. Akad. Nuuk S.S.S.R., Ser. khim., 1974, 2419. R. A. Abramovitch, J. L. Atwood, M . L. Good, and B. A. Lampert, Jnorg. Chew., 1975, 14, 3085.

Miissbairer Spectroscopy

447

7

Ii"

Fc

L

i;io

N

H

(3)

Mossbauer spectroscopy has been used to determine the iron(ii)/iron(iii) ratios in some mixed-valence, semiconducting, ferrocene-containing polymers, prepared by oxidation of polyvinylferrocene, polyferrocenylene, and polyethynylferrocene with dichlorodicyanoquinone, iodine, or tetracyanoquinodimethane. The isomer shifts and quadrupole splittings were respectively ca. 0.78 mni s-1 and 2.48 mm s-l for the ferrocene units and ca. 0.78 mm s-l and 0.2 mm s-l for the ferrocenium units."" An impressive study of electron transfer in oxidized biferrocene, biferrocenylene, and [ I , llferrocenophane systems has been reported. Early work on systems of this type was discussed in some detail in Volume 7 of this series. The conipound biferrocenium+tca-,2tcaa (4) (tca- stands for trichloroacetate and tcaa for trichloroacetic acid] was shown to give Mossbauer spectra at 300 and 4.2 K (Figure 6) that are interpretable in terms of a superposition of two quadrupolesplit doublets (A = 2.176 and 0.392 nini s-l at 300 K) for a mixed-valence

+

71

t-

..L,'

I

I

Fc

l-.c

Fc

Me (7)

iron(rI)-iron(irr) species and one doublet of lower intensity for a ) averaged-valence species. Singly oxidized 1 ',6'-di-iodobiferrocene ( 5 ) was found to give only one doublet, with a quadrupole splitting (A = 1.284 mm s-l at 300 K) intermediate between that found for the iron(rr) and iron(ir1) sites in biferrocenium, and similar to the value of 0.903 mm s-l obtained for the averaged-valence species. The 377

C , U. Pittman and Y . Sasaki, Chem. Letters, 1975, 383.

448

Spectroscopic Properties of Inorganic and OrganonietaNic Compounds

intervalence transfer rate is therefore greater than ca. lo7 s-’ for this species. The biferrocenyleniuin cation (6) was also shown to give spectra typical of averaged valence species, and in this case the intervalence transfer rate is so great (> lo1’ s-l) that only a single type of iron centre is detectable in the X-ray

0.0 0.1

0.2

0.3 0.u

a

h

0.5

Y

0.6

C 0

.-

0.7

L

0.0

* a 0

VI

d

3.0

5.0 6.0

1.0 I

-y.o

-y.o

I

-2.0

I

I

I

I

I

-1.0

0.0

1.0

2.0

3.0

1

V e l o c i t y /mm 5-1 Figure 6 67Fe Mossbauer spectra for biferricenium+tca-,2tcaa at 300 and 4.2 K. The velocity scale is referenced to the 67Co/Cusource (Reproduced by permission from Inorg. Chem., 1975, 14, 2331)

photoelectron spectrum. The unusual temperature dependence of the Mossbauer spectrum of 1,12-dimethyl[l,l]ferricenophanium+I,- (7; n = 1) has been reinvestigated, and it is now suggested that the inner doublet for the iron(m) site exhibits paramagnetic relaxation effects at very low temperatures. The 2,3-dichloro-5,6-dicyanobenzoquinone salt of dioxidized 1,12-dimethyl[l,l Iferrocenophane (7; n = 2) was shown to be diamagnetic and is therefore thought to feature a direct iron(m)-iron(m) interaction. From a measurement in an applied magnetic field the asymmetry parameter was found to be very large (7 z 0.8),

Mossbauer Spectroscopy 449 and this was interpreted in terms of a distortion of the ferriceniuni centres as a result of the direct iron-iron interaction. In the light of this important observation it was suggested that direct exchange-type interactions probably occur also in the other systems which show evidence for rapid intervalence transfer, and that superexchange interactions via the ring moieties are less likely to be responsible.378 Mossbauer spectra for the y-arenebis-(7-cyclopentadienyliron) cations [Fe2(bipheny1)(q-C5H,)zlz+and [Fe2(’pyrene)(7-C,H6),]2+have been found to consist of a sharp doublet at both 300 and 4.2 K, and are thus similar to those for the 7-arene-7-cyclopentadienyl cations.379 Data for the bis-(1-substituted borabenzene)iron complexes (8) have indicated that the borabenzene ligands are more electronegative than the cyclopentadienyl rings of ferro~ene.~~O

Oxide and Chalcogenide Systems containing Iron.-Several reviews relevant to this section have already been mentioned (see refs. 19, 32, 34, 47, 67, and 68).

Binary Oxides and Hydroxides. Mossbauer spectroscopy has indicated the formation of wustite, Fe,-,O, in calcined samples of iron dispersed in silicomolybdenum blue. The amount of wustite was observed to increase, relative to iron and Fe203,with increase in temperature, and it was concluded that wustite is formed by the reaction of iron and Fe203.381 The technique of conversion-electron Mossbauer spectroscopy mentioned earlier (see p. 414) has been used in several studies involving iron-containing s~rfaces.~ The ~ ~early - ~ ~stages ~ of the oxidation of plain carbon steels have been monitored and the potentiality of the technique in elucidating the nature of new surface and sub-surface phases formed on massive solid samples has been demonstrated. It was estimated that, with currently available equipment, the presence of ca. 1Ol6 atoms cm-2 of 57Fe,submerged under or in the surface, may be readily Oxide films prepared on iron by plasma anodizing383 and the surface structure of an iron film prepared by evaporation in a high vacuum 3R4 have also been investigated by measurement of the conversion electrons emitted after Mossbauer excitation. A study of the oxidation of an iron foil of thickness 9.3 pm, at a pressure of 680Torr and a temperature of 573-873 K, has shown that the iron is oxidized to Fe30, at 673 K, and finally a78

J7Q

saO *81

9na yn3

384

W. H. Morrison and D. N. Hendrickson, Inorg. Chem., 1975, 14, 2331. W. H. Morrison, E. Y. Ho, and D. N. Hendrickson, Inorg. Cheni., 1975, 14, 500. A . J. Ashe, E. Meyers, P. Shu, T. von Lehmann, and J. Bastide, J . Amer. Chem. SOC.,1975, 97, 6865. 1’. 0. Voznyuk, V. N. Dubinin, V. V. Kuz’movich, and N. A . Ivkina, Fiz.-Khim. Mckh. Liofil’nost Dispersnykh Sist., 1974, 12. J. M. Thomas, M. J. Tricker, and A, P. Winterbottom, J.C.S. Furuduy II, 1975, 71, 1708. 1’. L. Gruzin, V. N. Gorokhov, and Yu. V. Petrikin, Zocadskuyu Lab., 1975, 41, 984. T. Toriyama, M. Kigawa, M . Fujioka, and K . Hisatake, Proc. Infernut. Vucrrunl Congrciss, bth, 1974, 733.

450

Spectroscopic Properties of Inorganic and Organometnllic Cotnpounds

to a-Fe20, at 773 K . The temporary appearance of a-Fe203 in the initial stages of the oxidation was attributed to the existence of two competitive diffusion processes of Fe2+through the Fe304phase and 02-through the a-Fe203 Passive films grown on iron by chemical and electrochemical oxidation in acidic, neutral, and alkaline solutions,386and processes which take place on the iron electrode during cycling in alkaline have also been investigated. A technique for growing epitaxial films of 57Fe-enriched a-Fe203 for Mossbauer diffraction experiments has been The magnetic properties of ultrafine (1-100 nni) iron oxide particles have been investigated by X-ray diffraction, magnetization measurements, and Mossbauer spectroscopy, and effects have been observed which cannot be accounted for by the phenomenon of superparamagnetism alone. It was claimed that there are two groups of particles: those with small relaxation times (7 < 10-lo s), which give a well-resolved paramagnetic doublet, and those with larger relaxation times (T > lopHs), which give six-line patterns. Apparently, with lowering of temperature, increase in particle size, or application of a magnetic field there is a changeover from the first type to the second. The paramagnetic phase x-Fe,O, is thought to exist for particles smaller than Q, z 8 _+ 1 nm; with increase in particle dimension this phase changes into ferromagnetic y-Fe,O,, and on further growth the antiferromagnetic phase a-Fe203is formed (d z 30---40 n n ~ ) . ~The * ~ effect of decreasing particle size o n the Morin transition temperature has been studied for a-Fe,O, prepared in different ways.39oIt has been shown that for y-Fe203micropowders in magnetic fields of 50-90 kG the average angle which the cations make with the applied field increases as the particle size decreases, suggesting that surface ions are more highly canted than those in the bulk."l A study of a-Fe,O, mixed with active carbon powder has shown that texture cannot be induced in this material even in magnetic fields as high as 50 kG. This was attributed to the low anisotropy of the susceptibility, coupled with the high specific frictional energy for a-Fe203.235 Mossbauer spectroscopy has been used, along with other techniques, to study small particles of metallic iron dispersed on a magnesium oxide support. Samples reduced by hydrogen were shown to consist of metallic iron, magnesium oxide, and Fez clusters i n magnesium oxide, whereas oxidized samples contained either a-Fe,O, or y-Fe,O,, sometimes in the superparamagnetic state.3vzChanges taking place in the surface, catalytic, and magnetic properties of this catalytic f

3x6

386 387

3138 3SQ 990

391

soa

H. Ohashi, M. Koizunii, and T. Morozumi, Huhkuido Daigaku Kogahuba Kcnhyu Ifukoku, 1974, 72, 145. H. Ebiko, H. Yamamoto, W. Suetaka, and S. Shimodaira, Proc. Internat. Congr., M r t . Corros., 5th, 1972 (publ. 1974), 285. 1. M . Geronov, T. Tomov, and S. Georgicv, J . Appl. Electrochem., 1975, 5 , 351. I . Sakamoto, T. Kinoshita, N. Hayashi, and B. Furubayashi, Japan J . Appl. Phys., 1975, 14, 715.

Yu. F. Krupyanskii and I. P. Suzdalev, Societ Phys. J.E.T.P., 1974, 38, 859 (Russian original Zhur. eksp. teor. Fiz., 1974, 65, 1715). Yu. F. Krupyanskii and I. P. Suzdalev, Soviet Phys. Solid State, 1975, 17, 375 (Russian original Fir. Twrd. Tclu, 1975, 17, 588). A. H. Morrish and P. E. Clark, Trudy Mezhdunur. KonJ Magn., 1973 (publ. 19741, 2, 180.

M. Boudart, A. Delbouille, J. A. Dumesic, S. Khammouma, and H. Topsoe, J . Catalysis, 1975, 37, 486.

Miissbauer Spectroscopy

45 1

system during the ammonia synthesis were studied in 394 The reduction of haematite in hydrogen at 908 K has been The recently reported /%form of Fe203, which is obtaincd by vacuum dehydration of /3-FeOOH, has been studied by Mossbauer spcctroscopy and shown to have a Nee1 temperature lying between 300 and 380 K and a magnetic field at 4.2 K with an average flux density of 495 kG. Above the NCel temperature the spectrum consists of a broad asymmetric doublet composed of peaks having a continuous distribution of velocities, consistent with the presence of five- and six-co-ordinated Fe3+. However, a proportion of tetrahedral Fe3+ is not ruled out, and a possible concentration range of from 0 to 40% was estimated. The spectrum of /i?-iron(rir) oxide hydroxide was reinvestigated and shown t o be consistent with octahedral Fe3+. It was suggested that the high proportion of ions on the internal surfaces of the tubular structure results in a nonstoicheiometric surface anion excess, and the conventional formula p-FeOOH was reformulated as /3-FeOZ(OH),-,,, where x z 0.9. Four models of the anion vacancy distribution in P-Fe,O, were considered within the framework of the tubular structure retained during dehydration, and a defect structure was proposed in which all the internal Fe3+ ions are five-co-ordinate whilst the surface Fe3+ ions are tetrahedrally c o - ~ r d i n a t e d . ~ ~ ~ It has been shown that the products obtained when dilute solutions of FeCI,, are boiled for short periods resemble the well-known amorphous gel, and appear to be structurally similar to a- and p-Fe00H.397 The boiling of more concciitrated solutions for prolonged periods produces poorly crystalline a-Fe203 and C Y - F ~ O O H398. ~ ~ ~ * The binary oxide magnetite (Fe304) has continued to attract attention, primarily because of the electronic transition which is known to occur in this spinel in the temperature region in the neighbourhood of the Verwey point (Tv z 119 K). According to Verwey (1947), above Tv an electronic hopping takes place between neighbouring Fe3+ and Fez+ octahedral ( B ) sites which occupy the alternate (001) planes along the c-axis, and below Tv magnetite undergoes an ionic order-disorder transition which inhibits the electronic hopping and contributes to the insulator properties of the oxide. New data above Tv on Fe,O, and on the related spinels Fe[M,Fe,-,]O, (M = Lit, Ni2+, Al", or Sn4+; x = 0.05-0.20) have been interpreted similarly in terms of electron hopping within the B-site s ~ b l a t t i c e and ,~~~ electron hopping has also been reported to occur in superparamagnetic Fe30, microcrystals.4no However, on the basis of a critical review of the available experimental data it has been suggested that a band model is more appropriate than a localized hopping model for the conduction electrons in Fe,O, above 393 394

3D6

396 3B8 399 4OO 401

J. A. Dumesic, H. Topsoe, S. Khammouma, and M. Boudart, J . Catal-vsis, 1975, 37, 503. J. A. Dumesic, H . Topsoe, and M. Boudart, J . Cafalysis, 1975, 37, 513. M. J . Graham, D. A. Channing, G . A. Swallow, and R . D . Jones, J . Marerials Sci., 1975, 10, 1175. A. T. Howe and K. J. Gallagher, J.C.S. Faraday I , 1975, 71. 22. K. Kauffman and F. Hazel, J . Znorg. Nuclear Chem., 1975, 37, 1139. K. Kauffman and F. Hazel, J . Colloid Interface Sci., 1975, 51, 422. C . Blaauw, C. Boekema, F. Van der Woude, and G. A. Sawatzky, Proc. Internat. Con/: Pliys. Semicond., 12th, 1974, 583. H. Topsoe, J. A. Dumesic, and M. Boudart, ref. 1, p. 41 I . B. J. Evans, ref. 56, p. 73.

452

Natural crystal

Figure 7 67 Fe Miissbauer spectrum of'synthetic arid natural magnetite (Reproduced by permission from Solid State Coniin., 1975, 17, 621)

Perhaps the most interesting new piece of work on magnetite is that of Buckwald and Hirs~h,~O, in which the line profiles in the temperature region near the Verwey point were investigated in greater detail and more quantitatively

3

Figure 8 Rutio AB2 A,, of absorption maxima shown in Figure 7, plotted as a function ojteniperature. The ordinate is 011 a cubic scale (Reproduced by permission from Solid State Conim., 1975, 17, 621) .m2

Is of Itrorganic ntrd Oi*g:rrtiotnetrillicConipoulirls

Data have been recorded for impurities in NaX zeolite, and thc filtration of tin atoms from a gallium melt by zeolite has been studied.56c" The effects of tin impurity atoms on the electrical and optical properties of the glassy arsenic selenides AsSe,.,, AsSe,.,, and AsSe, have been studied,5o0" and the crystal-glass transitions in the chalcogenide semiconductors As,S,, As,Se,, As2Te,, TIASS,, TI AsSe,, and TIAsTe, have been Crystal-glass transitions have also been studied in the germanium compounds Ge,.,,Te,.,, and G ~ G ~ A S , . ~ ~ ~ The Mossbauer emission spectrum of lI0Sn formed by successive elcctroncapture decays of 119))1Te i n Ht11101)LTe06 has indicated that tin is stabilized in the 4 oxidation state only.57oThe Mossbauer emission spectrum of llgSSn resulting from electron-capture decay of llSSb in the basic oxalate [Sb"'(OH)(C,O,)] has been shown to consist predominantly of tin(i1) resonances, together with a small amount of tin(iv). This was thought to indicate that local radiolysis of the oxalate ions does not play an important role in determining the final state of the lleSn Mossbauer emission and absorption spectra have been recorded for the benzyltin compounds PhCH,SnX (X = F, CI, Br, I , O H , or PhCH,), and compared with spectra recorded on products resulting from at1 external irradiation of the same compounds by 6oCo. From the data i t was concluded that the internal irradiation following the isonieric transition of 118naSnis far more effective than the external irradiation in disrupting the local environment of the tin atom.672

+

Tin(ri) Compounds.-A model has been suggested for the interpretation of tin-1 19 Mossbauer data for tin(rr) compounds in terms of the tin valence electrons. The model accounts for the positive signs of the quadrupole coupling constants and for the variations in the Mossbauer parameters of (triligand)stannates(Ii) as the cation is changed. It also explains why approximately linear relationships are found between the Mossbauer isomer shifts and quadrupole splittings for particular series of (triligand)stannates(~).~~~ The Mossbauer spectrum of SnCI, has been re-examined and shown to comprise an unresolved quadrupole doublet, rather than simply a single line; the new result is more consistent with the known distortion of the tin environment. Data were also reported for a- and /3-SnW04 and for Sn(SO,X), (X = F or CI), and it was pointed out that in all of these compounds the 5s electrons participate in the bonding and thereby lower the isomer shift below the value expected for a bare 5s2 c o n f i g ~ r a t i o n .The ~ ~ ~ isomer shift has been shown to 6~

668

668

670

671 67a

673 K74

V. N. Bogomolov, A. I . Zadorozhnii, and N. A. Klushin, Socief Phys. Solid Slate, 1975, 17, 1627 (Russian original Fiz. Tverd. Telu, 1975, 17, 2452). P. P. Seregin, V. P. Sivkov, and L. N. Vasil'ev, FIZ.Tekhn. Poluprovodn., 1974, 8, 2270. P. P. Seregin, M. A. Sagatov, T. F. hlazets, and L. N. Vasil'ev, Phys. Sratus Solidi ( A ) , 1975, 28, 127. F. S. Nasredinov, B. T. Melekh, L. N . Vasil'ev, and L. N. Seregina, Sovier PJiys. Solid Slcitc, 1975, 17, 413 (Russian original Fiz. Tuerd. Tela, 1975, 17, 633). M. A. Sagatov, P. P. Seregin, E. Yu. Turaev, and L. N. Vasil'ev, Tezisy Dokl.-Vsrs. Konf. Khitii. Svyari Poluprooodn. Polumetollukh, 5th, 1974, 103. S. Ambe and F. Ambe, Radiochim. Acfa, 1973, 20, 141. S. Ambe and F. Ambe, Inorg. Nuclear Chen~.Letters, 1975, 11, 139. B. Mahieu and Y. Llabador, ref. 1, p. 329. J. D . Donaldson, D. C. Puxley, and M. J. Tricker, J . Inorg. Nuclear Chent., 1975, 37, 655. J. G. Ballard and T. Birchall, Cunutl. J. Chem., 1975, 53, 3371.

471 decrease in going from the tin(i1) halides SnCI, and SnBr, to the complexes MSnXs,H2O, and this was attributed to s-p mixing.575 The SnCIa2- anion has been isolated as the barium salt and studied by Mossbauer spectroscopy; a polynieric structure could not be ruled out for the anion.67s The caesium tin(ir) and Cs,SnBr, have been found to give bromides CsSnCI,-,Br, (x = 0-5) qiradrupole splittings at 80 K which decrease with increasing bromine content, indicating a trend towards a more highly symnietrical tin environment. For Cs,SnBr, a very narrow resonance line was observed at 4.2 K and its isomer shift was consistent with the presence of longer Sn-Br bonds in this hexagonal structure compared with those in the perovskite CsSnBr,. Data were also reported for tin(ir) in the mixed lattice formed between Cs2Sn1"Br, and CsSnl'Br,. In this system tin(i1) is introduced into the CS2Sn1"B~6structure without destroying its cubic unit cell; the materials are coloured, and show increased electrical conductivity because of the population of conduction bands by ns2 electrons. The Mossbauer spectra showed the tin(ii) to be in a distorted Miissbatier Spectroscopy

Progressive replacement of methyl by trifluoromethyl groups in the series of bis(pentane-2,4-dionato)tin(i1) complexes [Sn(OCR1:CHCOR2),] (R' = R2 = Me; R1 = Me, R2 = CF,; or R1 = R2 = CF,) and their I : 1 derivatives with 2,2'-bipyridyl and 1 ,lo-phenanthroline has been shown to cause,an increase in isomer shift and a corresponding decrease in quadrupole splitting. These trends were rationalized in terms of Bent's isovalent hybridization theory, according to which the tin uses hybrid orbitals of greater 5 p character in bonding to the more electronegative ligands, thus allowing the non-bonding pair of electrons on tin to become concentrated in an orbital of increased 5s character. Mossbauer resonances were not observed for these compounds at room temperature, which suggests that they are not By contrast, the Mossbauer spectra for (p-MeC,H,OSn),O and the tin(I1) bisphenoxides Sn(OR), (R = p-MeC,H,, nr-H2NC,H4,or 3,5-Me2C6H3)have been found to persist at room temperature, suggesting that these compounds have polymeric lattices in which the adjacent tin atoms are bridged by oxide and phenoxide atoms in an infinite array. Data were also recorded for the compounds Sn(S,COMe), and Sn(S,CNEt,), and were consistent with tetrahedral and trigonal-bipyramidal environments, respectively, for the tin Pseudo-trigonal-bipyramidalco-ordination at tin has also been suggested for some tin(n) derivatives of alkyl acetoacetates, 4-phenylbutane-2,4-dione, 1,3-diphenyIpropane-l,3-dione, cyclohexane-l,2- and -1,3diones, and 2-hydroxycyclohepta-2,4,6-trien1 Data have also been reported for the tin(r1) arylcarboxylates, Sn[O,CR],, and arylsulphonates, H2NC6H4,ButC6H4, Sn[O,SR], (R = Me, Et, Ph, MeCgH4, ClC6H4,BTCBH~, 02NCBH4, C,,F5, or C10H,),6a1and for the alkoxides Sn(OR), (R = Me, Et, or B U ) . ~ *The ~ complexes [Mn(CO),(Sn(OCR1:CHCR20),)] (R1 = R2 = Me or 675

676 677

67H G70

6Hn G81 [IRa

M. Mishima, M. Idogaki, and H . Negita, Sliiinane Daigaku Bunrigakubu Kiyo, Rigakka Hen, 1974, 73. M. Goldstein and P. Tiwari, J. Znorg. Nuclear Chem., 1975, 37, 1550. J. D. Donaldson, J. Silver, S. Hadiiminolis. and S. D. ROSS,J.C.S. Dalton, 1975, 1500. P. F. K. Ewings, P. G . Harrison, and D. E. Fenton, J.C.S. Dalton, 1975, 821. P. F. R. Ewings and P. G. Harrison, J.C.S. Dalton, 1975, 2015. A. B. Cornwell and P. G . Harrison, J.C.S. Dalton, 1975, 1722. P. F. R . Ewings and P. G. Harrison, J.C.S. Dalton, 1975, 1717. R. Gsell and M. Zeldin, J . Inorg. Nuclear Chem., 1975, 37, 1133.

472

Spectroscopic Propert ics oj‘ Ino rgmr ic and Orgnnomef rrlfic Compounds

CF3; R1 = Me, R2 = Ph or CF,), which formally contain tin(ii), have been shown t o give isomer shifts characteristic of tin(rv), and it is therefore suggested that the isomer shift of p-Sn should not be used a s an arbitrary dividing line between tin(rr) and t i n ( i ~ ) . ~ ~ ~ The complex Sn(NMe,),, prepared by amination of anhydrous SnCI, with LiNMe,, has been shown t o contain tin(rr) (6 = 2.80 k 0.05 relative to SnO,) and to have an unusually large quadrupole splitting (A = 3.17 k 0.05 mm ~ - l ) . ~ 8 4 The adducts SnX,L [X = CI, Br ; L = NN’-ethylenebis(acetylacetoneiniine), NN’-ethylenebis(salicylideneimine), and 2,2’,2”-triaminotriethylaniine] have been shown to contain tin(ii) in a tetrahedral environment, with the neutral oxygendonor ligands acting as bis-unidentate ligands and creating a polymeric network. A four-co-ordinate monomeric structure was favoured for the complex SnBrL [HL = N-(2-hydroxyphenyl)pyridine-2-carboxaldimine], although formally threeco-ordinate species could not be entirely ruled O U ~ . ~ ~ ~ The complex [Sn(r]-CGHG)(AICI,),],c~H~ has been shown by X-ray diffraction to contain tin(ri) in a pentagonal-bipyramidal geometry, with five equatorial chlorine ligands, one axial chlorine, and the other axial position occupied by the centre of a benzene ring; the remaining benzene is far removed from the metal and appears t o be only a molecule of solvation. Rather surprisingly, the Mossbauer spectrum of this complex was found to consist of only a single line (8 = 3.93 k 0.10 mms-l relative t o BaSnO,), and this was rationalized in terms of a qualitative M O scheme in which the 5s electrons occupy an almost spherical environnien t.68s The nido-metalloborane salts of [Sn(B,,H,,)C1,]2- prepared from the reactions of [ A S P ~ , ] ~ [ B ~ ~and H ~ , [PMePh,],[B,,H,,] ] with SnCI, have been shown to contain tin(ri), whereas the ion [Sn(BloHl,)CI,Me,]2-, prepared from the corresponding reactions with Me,SnCI,, was shown to be a tin(rv) complex.587

Tin(iv) Compounds.-Organometallic and Other Morionriclear Compounds. A general correlation between the ll9Sn Mossbauer quadrupole splitting and Sn 3d ESCA linewidths has been noted for the tin(rv) compounds Me,Sn, (CH, :CHCH,),Sn, Me3SnC1, Me,SnBr, Me,SnCI,, Ph,Sn, CI,Sn(BzAc),, PhCISn(BzAc),, PhCISn(BzBz),, Ph,Sn(BzBz),, Ph,Sn(BzBz),, Ph,Sn(BzBz), Me,Sn(BzAc),, and M e , s n ( B ~ B z ) , . ~The ~ ~ correlation suggests that ligandproduced electric field gradients can broaden the Sn 3d line by -0.15 eV. Mossbauer spectra have been recorded for Ph,Sn, Ph,SnCI, Me,SnCI,, Ph,SnMn(CO),, [ Me,N J[Ph,SnCI,], [{ Fe(q-C5H5)(CO),),SnC12], [Me,Sn(OH)NO3],, Ph,SnL [HL = (PhCO),CH,], and Me,SnL, [HL = (MeCO),CH,]. Tn some cases unexpectedly large resonance effects (ca. 1%) were observed, indicating that it is dangerous t o associate the observation of a room-temperature resonance with the existence of a polymeric structure. From the GoldanskiiKaryagin asymmetry in the room-temperature spectrum of Me,SnL, [HL = (MeCO),CH,], the difference in the mean-square vibrational amplitudes parallel 68s

6n4 K8B 6R7

A. R. Cornwell and P. G. Harrison, J.C.S. Dalron, 1975, 1486. P. Foley and M . Zeldin, Inorg. Chon., 1975, 14, 2264. G . C. Stocco, G . Alonzo, N. Bertazzi. and F. Di Bianca, Gazrerra. 1975, 105, 355. P. F. Rodesiler, E. L. Amma, and T. Auel, J. Amer. Chrm. SOC., 1975, 97, 7405. N. N. Greenwood and B. Youll, J.C.S. Dalton, 1975, 158. G. M. Bancroft, I. Adams, H . Lampe, and T. K. Sham, Chem. Phys. Lerrrrs, 1975, 32, 173.

Miissbairer Spectroscopy 473 and perpendicular to the Me-Sn-Me axis was shown to be 2.8 x 10-lHcmz, in good agreement with the value determined from X-ray crystallography (2.92 x 10-ls cm2).680Data have been reported for a series of 35 ortho-, meta-, pora-, 2,6-, and poly-substituted arylmethyltin compound^.^^^ The benzyltin compounds [(PhCH,),SnX] and [(PhCH,),SnX,] (X = C1 or H) have been studied, and spectra for frozen solutions of Na[SnPh,] have been interpreted in terms of equilibria involving the separate ions with both contact and solvent-separated ion pairs.691 Solvolysis of the complexes Me,-,SnCl, (x = 0-3) in H 2 S 0 4or FS0,H has also been examined.6Q2Frozen solutions of the t i n tetrahalides have been and equilibrium constants have been determined for tetraiodotin-trimethylisopropoxysilane and tetrabromotinacetic anhydride s01vates.~~~ The structural formulation (XeF,),SnF,, in which the SnF,2- anion has a distorted octahedral configuration, has been proposed for the adduct 2XeF,,SnF, on the basis of Mossbauer and i.r. Mossbauer spectra of the mixed phases M,[(Sn,Te)X,] [M = K, Rb, Cs, or NH,; X = C1 or Rr] have shown that the tin environments are similar to those in the hexahalogenostannates(~v).~~~ The polyhedral metalloborane ion [(B,,H,,)Me,SnC12]2-, prepared from the reactions of [P~,AS],[B,,,H,~] and [Ph,MeP],[Bl0H,,] with Me,SnCI,, has been shown to contain t i n ( ~ v ) . ~ * ~ The salt Na,[Sn(OH),] has been suggested as a possible Mossbauer source material; it is easily prepared by dissolving a-stannic acid in NaOH, has a high recoil-free fraction, and gives a narrow emission The spectrum of tricyclohexyltin hydroxide has indicated that this complex has the same hydroxobridged polymeric structure as its methyl analogue.698A study of the temperature dependence of the recoil-free fractions and quadrupole splittings of the complexes (Bu,Sn),SnX (X = SO,, SeO,, or CrO,) has shown them to have non-polymeric structures.699The donor character of oxygen in species containing Si-0 bonds has been studied in a series of adducts with SnI,.600 Comparison of the llaSn Mossbauer data for carboxylates of the type [ Me,SnOCOR] with lZISbdata for the related complexes [Me,Sb(OCOR),] has revealed linear correlations between the respective isomer shifts and quadrupole coupling constants, the implications of which were discussed. The intercept of the plot of e2q& us. e2qQbndid not pass through the origin, presumably because 6q(’

681

68:3

68b

G97 Guy On0

G. M. Rancroft, K . D . Butler, and T. K. Sham .J.C.S. Dalton, 1975, 1483. 11. J. Kroth, El. Schumann, H . G. Kuivila, C. D. SchatTer, and J. J. Zuckerman, J . Amer. C‘hem. Soc., 1975, 97, 1754. T. Birchall and A. R. Pereira, J.C.S. Dalton, 1975, 1087. T. Birchall, P. K . H . Chan, and A. R. Pereira, J.C.S. Dalton, 1974, 2157. K . Burger, E. Fluck, and A. Vertes, Fiz. A f u t . Motarly Koord. Khim., Tezisy Dokl., Vses. Soreshi.h., 5th, 1974 (publ. 19741, p. 13. A Vkrtes, S. Nagy, 2. Czako-Nagy, and E Csakvary, J . Phys. Chem., 1975, 79, 149. V. Z. Zarubin and A. S. Marinin, Russ. J . tnorg. Chfzm., 1974, 19, 1599 (Russian original Zhur. neorg. Khim., 1974. 19, 2925). J . D Donaldson, S D. Ross, J . Silver, and P. J . Watkiss. J.C.S. Dalton, 1975, 1980. L. Gumnerova. God. So$i. Unio., Fiz. Fcrk., 1970-1972 (publ. 1973), 379. Y . K. Ho and J . J. Zuckerman, J . Organonletalliu Chent., 1975, 96, 41. €3. Saiio and Y . Mekata, Chem. Letters, 1975, 155. B. Csakvari, E. Csakvari, P. Gomory, and A. Vkrtes, J . Radioanalyr. Chem., 1975, 25, 275.

474 Spectroscopic Properties of Inorganic and Organometnilic Compounds the compounds are not isoelectronic, and in consequence it will not be possible to make a direct conversion of p.9.s. values from tin to antimony compounds of similar structure unless the compounds are also isoeIectronic.sO1 Data have been recorded for the five-co-ordinate /3-diketonatotri(organo)tin complexes Me,SnL and Ph,SnL (HL = acac, benzoylacetone, or dibenzoylmethane) and shown to be consistent with the mer and cis structures for the methyl and phenyl complexes, respectively.s02 The temperature dependence of the recoil-free fraction has been studied in the temperature range 78-140 K for seven organotin(1v) tropolonates, and the data have been correlated with Raman data in the lattice-mode region to yield a selfconsistent assignment of the intermolecular intra-unit-cell vibrations in the solids, and a value of the effective vibrating molecular mass. From the latter data the complexes were inferred to be monomeric in the solid state, with relatively weak intermolecular bonding forces between adjacent molecules. The tropolonate ligand is thought to act as an anisobidentate moiety, with both oxygen atoms bonded to a single metal centre.s03 The new pseudo-chalcogeno-oxoacyltin compounds R1,SnOCY R2 and R1,Sn(OCYR2), [Y = NCN or (CN),, R2 = Me or Ph] have been shown by Mossbauer and i.r. studies to have structures in which the anionic ligands form bridges, with 0 and N, or N and N, acting as donor A simple additivity model has been proposed which accounts for the change in quadrupole splitting as a function of C-Sn-C bond angle in all but two of 19 MezSn'" compounds known to contain distorted six-co-ordinate or fiveco-ordinate structures. The two exceptions were Me,SnCI, and Me,Sn(NO,),, both of which are better classified as distorted tetrahedral structures. New data were reported for [Me,Sn(OH)NO,], and Me,Sn(NCS),O, in which the tin atoms are f i v e - c o - ~ r d i n a t e . A ~ ~magnetically ~ perturbed Mossbauer study has revealed that the 1 : 1 adduct of salicylaldehyde with Me,SnCI, has a quadrupole coupling constant of &e2qQ = 3.3 mm s-l, consistent with a Me-Sn-Me bond angle of > 109" and trigonal-bipyramidal geometry.606 Detailed temperature-dependence studies have been carried out on 24 complexes of the types SnCl,L, and SnCI,L, where L is a nitrogen-, phosphorus-, sulphur-, or oxygen-containing donor ligand, and Goldanskii-Karyagin effects were observed for L = Ph2N2, C4H80, Et,O, and (C2H4),0,. The studies yielded information about the donor properties of the ligands, the signs of the electric field gradients at the tin nuclei, and the molecular dynamics of the

+

tin Structural studies have been carried out on a series of 24 triorganotin derivatives of substituted pyridines and related ligands. For the 2- and 3-pyridone derivatives the quadrupole splittings were shown to be in the ranges 801 602

809

eo0 806 6n*

607

R . G . Goel, J . N. R. Ruddick, and J. R . Sams, J.C.S. Dafron, 1975, 67. G. M. Bancroft, B. W. Davies, N. C. Payne, and T. K. Sham, J.C.S. Dalton, 1975, 973. A. J. Rein and R . H. Herber, J . Chent. Phj~s.,1975, 63, 1021. H . Kijhler, L. Neef, L. Korecz, and K. Burger, J . Organometallic Chern., 1975, 90, 159. T. K. Sham and G . M . Bancroft, Znorg. Cheni., 1975, 14, 2281. D. Cunningham, I. Douek, M. J. Fraser, M. McPartlin, and J. D. Matthews, J . Organomeraflic Cliern., 1975, 90, C23. V. A. Varnek, E. N. Yurchenko, V. A. Kogan, L. N. Mazalov, Yu. K. Maksyutin, 0. Kh. Poleschuk, A. S. Egorov, and 0. A. Osipov, Zhur. srrukt. Khim.,1975. 16, 359.

Miissbairer Spectroscopy 475 3.09-3.38 and 2.92-3.22 mm s-l, respectively, consistent with trans-[R,SnX,] configurations. For the 2-pyridyl alcohol and 2-pyridyl aldehyde oxine derivatives the quadrupole splittings were smaller (2.63-2.93 mm s-l), consistent with some distortion from planarity of the R,Sn groups. Much lower splittings (1.602.27 mm s-l) were observed for the derivatives of 2-thiopyridone and 8-hydroxyquinoline, and these were each thought to have a cis-[R,SnX,] arrangement. Triorganotin esters of 2-pyridylcarboxylic and 2,6-pyridydlicarboxylic acids gave very large quadrupole splittings (3.77-3.89 mm s-I) and were thought to possess the six-co-ordinate mer-[R,SnX,] stereochemistry.60a Data have also been reported for a wide range of [R,Sn(NCS),] complexes with neutral ligands containing oxygen donor for complexes of Me,SnCl,,slo Bu,SnCl,,610and SnCI,slo~ellwith nitrogen donor ligands, and for the novel 1 : 1 adducts formed between triorganotin chlorides and isocyanates and the terdentate chelating agents 3-[2-(1,IO-phenanthrolyl)]-5,6-diphenyl-l,2,4-triazineand 3-[Z-(1 ,lo-phenanthrolyl)]-5,6-dimethyl-l,2,4-tria~ine.~~~ The solid-state configurations of the azido and mixed azidothiocyanato complex anions [Ph,Sn(N,),]- and [Ph,Sn(N,)(NCS)]- have been shown to possess trigonal-bipyramidal structures with equatorial SnPh, arrangements, whereas the diorgano-complexes [Me,Sn(N,),],and [Ph,Sn(N,),(NCS),]2- were shown to have trans-octahedral structures; the NCS- ligands were ”bonded to tin@) in all cases.s13 It has been shown that the SchifT-base complexes SnX,(LH,) [X = Br, C1, or I ; LH2 = NN’-ethylenebis(salicylaldimine), NN’-ethylenebis-(2-hydroxyacetophenone imine), or NN’-o-phenylenebis(salicylaldimine)] do not have the ionic form [SnCl,(LH,)]Cl, suggested by Van den Bergen et a/. (1970) for the solution species; the complexes [SnX,L] were also The N-substituted N-(triphenylstanny1)-cyanamides CF,C(O)(CN)NSnPh,, MeOC(O)(CN)NSnPh,, PhS02(CN)NSnPh,, and MeC(CO)(CN)NSnPh, have been shown to give large quadrupole splittings, and are thought to contain tin with a co-ordination number greater than four.616 The isomer shifts for the organotin thiolates Bu,SnSR and Bu,Sn(SR), (R = Me, Ph, or C,F,) have been shown to be relatively insensitive to the nature of the mercapto-group, but the quadrupole splittings were found to differ from one another. The values for the methylthio- and phenylthio-derivatives were consistent with tetrahedral geometry, whereas the values for the bulky pentafluorophenylthio-derivatives,being larger, suggested a higher co-ordination number.s1s Other sulphur complexes studied include the (2-arylthio-1-halogenoethy1)triphenyltin products [(4-Y-2-0,NC6H3SCH,CHS)SnPh3] (Y = H, X = Cl

On’

m3 614

Ole

P. G. Harrison and R. C. Phillips, J. Organometallic Chem., 1975, 99, 79. F. P. Mullins and C. Curran, Canad. J. Chem., 1975, 53, 3200. M. Mishima, M. Nakamura, I. Makoto, and I. M. Masao, Shimane Daigaku Bunrigukubu Kiyo, Rigakka Hen, 1974, 79. 0 . Kh. Poleshchuk, Yu. K. Maksyutin. and I. G. Ordov, Fiz. Mar. Merody. Koord. Khim., Tpzisy Doklady, Vses. Sooeshch., 5th, 1974 (publ. 1974), p. 131. F. E. Smith and B. V. Liengrne. J. Organornefallic Chem., 1975, 91, C31. R. Barbieri, N. Bertazzi, C. Tomarchio, and R. H. Herber, J. Orgunometallic Chem., 1975, 84, 39. J. N. R. Ruddick and J. R. Sams, J. Znorg. Nuclear Chem., 1975, 37, 564. E. J. Kupchik and J. A. Feiccabrino, J. Organometullic Chem.. 1975, 93, 325. C. 1. Balcombe, E. C. Macmullin, and M. E. Peach, J. Znorg. Nuclear Chem., 1975, 37, 1353.

476

Spectroscopic Propcvtics of lriorgntiic nrid Organometrillic Cott1pound.y

or SCN; Y = Me or NOz, X = the substituted 1,2-dithiole-3-thione (= L) compounds [SnX,L,] (X = CI or Br);618 and the complexes SnX,L (X = C1, Br, or I ; L = MeSCH,CH,SMe).619 Data for the latter were compared with results on the complexes SnX,R (X = CI or Br, R = MeOCH,CH,OMe) and shown to be consistent with hard and soft acid-base theory."'" Mossbauer and i.r. data for the phosphorus acid amides [R,P(Z)N Me,],SnX, (I) (R = Ph, Z = 0 or S, X = CI or Br; K = Et, Z = S, X = CI or Br) and [R,PNMe,],SnCI, (11) (R = Ph or CI) have indicated that the ligand is bonded to tin via the phosphorus atom, whereas, in ( I ; R = Ph, Z = 0, X = CI or Br) the ligand donates through the oxygen atom, and in ( I ; R = Ph or Et, Z = S, X = C1 or Br) it donates through the sulphur atom. In (11; R = CI) it coordinates through the nitrogen atom and i n (11; R = Ph) through the phosphorus The organophosphorus compounds (60 in all) [Rl2R2P(Y)]SiiX4-*R,~ and [K1R2P(Y)Y],SnX, (where R', R2,and R3 are alkyls; Y = 0 or SMe; X = halogen) have also been studied.621 The isomer shift for the cubic pyrophosphate SnP,O, has shown it to be one of the most ionic compounds of quadrivalent tin known.622 Conipoirnds with Tin-Metal Bonds. This year many more papers than usual have dealt with compounds containing tin bonded to another metal. Apart from the study o n the five-co-ordinate tin compounds R,SnOH,R,MX (R = Me, M = Pb, the X = N,; R = Me, M = Sn, X = NCS; R = Ph, M = Sn, X = tin is bonded to a transition metal, and is four-co-ordinate. In a study of partial quadrupole splittings in 92 four-co-ordinate tin(iv) conipouiids, Bancroft and Butler have plotted calculated quadrupole splittings against the observed values and have noted that in 90% of the cases the agreement between the two is within the acceptability limit of 0.4 mms-I suggested by Clark et 01. (1972). In addition, the slope and intercept obtained from the plot were found to be close to the expected values of 1.00 and 0.00 mm s--l, respectively. Among the exceptions were very distorted cornpounds such as [SnMX,] [X = CI or Br; M = Fe(r]-C,H,) or Mn(CO),]. The effects of distortions werc considered and 'absolute' p.9.s. values were calculated from the known structure data for certain cotnpounds. However, the use of these p.9.s. values did not improve the agreement between predicted and observed quadrupole ~ p l i t t i n g s . ~ ~ , Discrepancies between calculated and experimental quadrupole splittings have also been noted for the compounds [Fe(r]-C,H,)(CO),-,L.(SnPh,-nCl,J] [n = 0-3; x = 1 for L = PPh,, PEt,, or P(OPh),, and x = 2 for L = P(OPh),] and for some phosphine-substituted compounds containing tin-cobalt bonds, and these were attributed to variations i n the s-character of the Sn-M (M = Fe or Co) Parish and co-workers have observed similar discrepancies in H1l)

6f1

6p3

J. L. Wardell, J.C.S. Dalron, 1975, 1786. F. Petillon and J. E. Guerchais, J . Inorg. Nuclcar Chcnr., 1975, 37, 1863. W. T. Ayers, M. F. Farona, and D. L. Uhrich, Spectroscopy Letfers, 1974, 7 , 637. 1. Ya. Kuramshin, Sh. Sh. Bashkirov, A. A. Muratova, R. A. Manapov, A. S. Khramov, and A. N. Pudovik, Zhur. obshchci Khitn., 1975, 45, 701. R . A. Manapov, I. Ya. Kuramshin, A . A. Muratova, and A. N. Pudovik, Zhur. obshchci Khim., 1975, 45, 1975. C.-H. Huang, 0. Knop, D. A. Othen, F. W. D. Woodhams, and R. A. Howie, Canad. J. Chmi., 1975, 53, 79. N. Bertazzi, G. Alonzo, F. Di Bianca, and G C. Stocco, Inorg. Chirn. Acta, 1975, 12, 123.

Mossbauer Spectroscopy 477 a study which included a wide range of compounds involving tin bonded to transition metals, e.g. [SnX,{M(y-C5H5)(CO),>1, [SnX,{M(q-C,H,)(CO>,),], [SnX2{M(71-C,H5)(Co),)(Fe(y-C,H,)(CO),)1 (M =: Cr, Mo, or W ; X = C1, Br, or I), and have also concluded that further refinement of the point-charge model is not Tin-119 data have been recorded for the products of the reactions between Fe,(CO), and SnX, [X = CI, Br, (MeCO),CH,, MeCOCH,COCF,, (CF,CO),CH2, MeCOCH,COPh, or (PhCO),CH,] discussed earlier (see p. 446). These materials exist as the diniers [Fe(CO),(SnX,)], in the solid, but as the basestabilized monomers [Fe(CO),(SnX,L)] in frozen pyridine solution. Low values of the isomer shift in the latter were discussed in terms of substantial synergic Sn Fe o- and Fe -+ Sn n - b ~ n d i n g . ~Other ’ ~ iron-containing organotin complexes studied include [Fe(C0),PBut,_,(SnMe,),1 (x = 1--3) and [Fe(CO),SnX,]- (X = halogen).s24 As mentioned earlier, the complexes [Mn(CO),{Sn(OCRl: CHCR20),)] (R’ = R2 = Me or CF3; R1 = Me, R2 = Ph or CF,), which formally contain tin@), have been shown to give isomer shifts characteristic of t i n ( ~ v ) .Data ~~~ have also been recorded for 16 complexes of the type [Mn(CO),-,L,(SnR,)] ( x = 0 or 1 ; R = Me, Et, Pr, Bu, C1, Br, or I ; L = PPh3, AsPh,, or SbPh,) G25 and for the novel tin-manganese complexes [Sn,X,{Mn(CO),},] (X = H, CI, or Br).626 Data for 1 1 complexes of the types [SnCl,(Ni(rl-C,H,)L),_,1 (L = CO or PPh,; x = 2 or 3) and [SnC13(Ni(y-C5H5)L,)],S(S = solvent molecule) have shown that [Ni(y-C,H,)(PPh,)] is the best donor of the first-row transitionmetal moieties and that the Sn-Ni bond has the highest tin s-character. It was also found that co-ordinated SnCI, can be distinguished from un-co-ordinated SnC1,- from the values of the isomer shift, and that the solvent molecules are not bonded to the tin atom in these complexes.627 The isomer-shift data have also indicated high tin s-character in the tin-zinc and tin-cadmium bonds in the complexes [SnPh,{MCl(tmed))] (M = Zn or Cd; tmed = NNN’N’-tetramethylethylenediamine), [(SnPh,),(Zn(tmed)}], and [(SnPh,),(CdL,)] (L2 = tmed, 2,2’-bipy, or o-phen).s28 Measurements have been made in applied magnetic fields, of flux density 50 kG, for the complexes [M(CO),LCl(SnCI,R,-,)I (M = Mo or W ; L = 2,2‘bipy, o-phen, or dithiahexane; R = Me or Ph; x = 1-3), all of which contain chlorine-bridged M-Sn bonds. For x = 2 or 3 the quadrupole coupling constants were shown to be positive (e2qQ > 0) and the asymmetry parameters small (7 z 0), and, taken in conjunction with the trends in isomer shift and quadrupole splitting, these results indicate that tungsten is a better o-donor than molybdenum. On the other hand, the complex [M(CO),LC1(SnClPh2)] was shown to have a negative e2qQ and a large 7, which were interpreted in terms of --t

OZ4

A26

62R

H. J. Odenthal, T. Kruck, and K. Ehlert, Z . Naturforsch., 1975, 30b, 696. S. Onaka and H . Sano, Bull. Chem. SOC.Jupan, 1975, 48, 258. K. D. Bos, E. J. Bulten, J. G . Noltes, and A. L. Spek, J . Organometallic Chem., 975, 92, 33. G. M. Bancroft and K . D. Butler, Cunad. J . Chcm., 1975, 53, 307. R. Barbieri, L. Pellerito, N. Bertazzi, G . Alonzo, and J. G . Noltes, Inorg. Chin?.Acta, 975, 15, 201.

478

Spectroscopic Properties o j Inorganic and Organometallic Compounds

a trigonal-bipyramidal arrangement featuring the molybdenum and the two phenyl groups in the equatorial positions. The large 7 was attributed to geometrical constraints imposed by the bridging chlorine.62n Spectra for the salts [M(CO)4(diphos)(SnC13)]+[SnCI,0H2]- (M = M o or W) and related compounds have each been shown to contain a singlet from the anion and a doublet from the cation, with intensities in the ratio 1 : 1. The data are therefore consistent with the formulation of these compounds as ionic salts and not as 2 : 1 Lewis acid-Lewis base a d d u ~ t s . ~ , ~ Data have also been reported for the platinum-metal complexes [M(SnXZ)JW(M = Pt", Pd", Ir'", Rh', or Ru"; X = C1, F, Cz04,or OH; x = 2 or 3) and related c o m p o ~ n d s . 632 ~~~9 Oxide and Chalcogenide Systems containing Tin.-The diffusion and reactivity of the molecules SnO, Sn,02, Sn30,, Sn40,, and higher polymers isolated in solid nitrogen have been investigated, using both Mossbauer and i.r. spectroscopy, and the changes in the concentrations brought about by annealing at temperatures up to 36 K have been followed quantitatively. The results were compared with three models and indicated that SnO, and probably to a lesser extent Sn,O,, are appreciably mobile at 34 K. At this temperature the diffusion coefficient of SnO in a-N2 was shown to be between m2 s - l , and 4 x which is of the same order of magnitude as the value determined previously for Sn atoms in a - N , at 34 K (see last year's Report, p. 468). Aggregates of tin(rr) oxides remaining after evaporation of the nitrogen were also studied and shown to be stable to oxidation up to 270 K. At 4.2 K the Mossbauer parameters of the final tin(ii) material (8 = 2.83 mm s-l relative to BaSnO,, h = 2.0 nim s-') were found to be different from those of both previously known forms of bulk Sn0.633 The partial reduction of tin(iv) oxide to a tin(1r) species (probably a carbonate) when carbon monoxide is adsorbed on to the oxide surface has been shown by the transmission i.r. technique and confirmed by Mossbauer spectros c o ~ y The . ~ ~use ~ of Mossbauer spectroscopy in the non-destructive analysis of tin ores for S n 0 2 has been A minimum in the resonance area has been observed, in agreement with lattice dynamical theory, at the polymorphic transformation in the BaSn0,BaTiO, Measurements on the phases Sn~?s(M2-,,Sn4,f)07_,_,,,2(M = Nb5-+or Ta") have indicated that the Sn2+ is not actually at the cubic 3m site of the ideal pyrochlore structure, and this was confirmed by X-ray diffraction on the phase Sn:It76Tal.s6Sn~~406.54*637

W. R. Cullen, R. K. Pomeroy, J. R. Sams, and T. B. Tsin, J.C.S. Dalton, 1975, 1216. W. R. Cullen and R. K. Pomeroy, Inorg. Chcm., 1975, 14, 939. w 1 V. A. Varnek, E. N. Yurchenko, G. L. Elizarova. A. I. Shan'ko, L. G. Matvienko, P. Ci. Antonov, and Yu. N. Kukushkin, Koord. Khim., 1975, 1, 161. m 2 E. N. Yurchenko, V. A. Varnek, G. L. Elizarova, L. G. Matvienko, and M. S. loffe, Koord. Khim., 1975, 1, 1406. A. Bos and A. T. Howe, J.C.S. Farnday I I , 1975, 71, 28. Bs4 E. W. Thornton and P. G. Harrison, J.C.S. Faraduy I, 1975, 71, 461. P. A. Pella and J. R. DeVoe, J. Radioanal,,*t.Chem., 1975, 25, 185. 6 3 8 S. Solacolu, E. Barbulescu, D. Barb, and M. Morariu, Rev. Roumaine Chim., 1975, 20, 69. 697 T. Birchall and A. W. Sleight, J. Solid Stnfc Clieni., 1975, 13, 118. e2B OSo

Miissbauer Spectroscopy 479 Other tin oxides which have been studied by Mossbauer spectroscopy includc Z 1 i , S n 0 , , ~the ~ ~ solid solution (Mg,Sn0,)z-[Mg3(B0,),1,_, (0.01 d .Y G 1 ),63* t in-containing alkali borate glasses 6 3 0 and alkali-free aluniinoborosilicate glasses,e41 platinum-tin-aluminium oxide mixed aluminium-tin oxide coatings which impart colour to aluminium surfaces,643and the tinsubstituted yttrium iron garnets Y3--rCazSrisFe5--20,2 (see also p. 456).jul4:% 6 4 4 Data have been recorded for a wide range of tin chalcogenides, including the binary compounds SnS,, Snse,, and Sns,, the ternary systems M,SnS6 and M8SnSe6, the quaternary phases M,M’SnS,, M,M’SnSe,, MCrSnS,, and MCrSnSe, (M = Cu or Ag; M’ = M n , Se, Co, Ni, Cu, Zn, Cd, or Hg), and the mixed chalcogenides PbSnS,-,Se, ( x = 0 or 1 ) and Cu,SnS,-,Se, ( x = 0-3).045 The chalcogenide spinels CuCr,-,Sn,S, have also been studied independently, and very large niagnetic flux densities have been observed at the tin nuclei, in some cases ca. 580 kG at 80 K.”j” Closely related studies on I’OSndoped chalcogenides are discussed on p. 469, and preliminary values have been reported for the temperature dependence of the recoil-free fraction of l19S11 in the superconducting spinel CuRhl.or,Sno.osSer.637 Measurements on several thiostannates, selenostannates, and selenothiostannates of the alkali metals and alkaline-earth metals have indicated that discrete dinieric SnzSe4-,tetrahedral SnS,,-, dimeric Sn2S7+, and related selcnoions exist in the solids. The isomer shifts for the selenothiostannate series Na,SnS,-,Se,, Na,Sn,S,-,Se,, and Na,SnS,-,Se, were found to vary continuously from thiostannates to selenostannates with no indication of substantial line broadening, implying a statistical disordering of both the sulphur and selenium atoms over the available The lattice dynamics and hyperfine interactions of tin in the intercalation compounds TaS,,Sn and TaS,,Sn* have been studied in the temperature range 78-295 K. In both compounds the tin was shown to exist in the bivalent state and to act as an electron donor. The charge distribution in TaS,,Snt was found to be cubic, whereas TaS,,Sn gave a quadrupole-split spectrum with a GoldanskiiKaryagin asymmetry in the line intensities. The Mossbauer temperatures were The intercalation compound estimated to be 185 and 283 K, NbSe,,Sn* has been shown to give only a single resonance line, with an isomer shift consistent with metallic behaviour intermediate between that of the superconducting TaS,,Sn and the weakly metallic non-superconducting TaS2,Snt.050 P. A. Ioffe, A. A. Baklagin, and V. A . Kozlova, Zhur. neorg. Khim., 1975, 20, 1712. K. P. Mitrofanov, L. P. Benderskaya, S. I. Reiman, and V. T. Krongauz, Vestnik Moskov. Univ., Fiz., Astruriomi)v, 1975, 16, 487. R 4 0 N . A. Eissa, E. E. Shaisha, and A. L. Hussiun, J . Nun-Cryst. Solids, 1974, 16, 206. u1 I. D. Tykachinskii, Ya. A. Fedorovskii, N. G. Dzhakhva, A. I. Ovchinnikov, and A. D. Tsyganov, Neorg. Matcrialy, 1974, 10, 2198. Oa2 R. Bacaud, P. Bussitre, F. Figueras, and J. P. Mathieu, Compt. rend., 1975, 281, C, 159. 6 4 ~ i Ch. Janot and P. Delcroix, ref. 1 , p. 501. 644 R. Hrichova, J. Lipka, and J. Cirak, Sb. Vys. Sk. Chem.-Technol. Prare, Mineral., 1974, G16, 49. 645 M . Katada, J . Sci. Hiroshiriia Univ., Ser. A : Phys. Chem., 1975, 39, 45. 040 H. Sekizawa, T. Okada, and F. Ambe, Trudy Mezhhrnar. Konf. Magn., 1973 (publ. 1974), 2, 152. 6 4 7 P. P. Dawes, N. W. Grimes, and D. A. O’Connor, J . Phys. (C), 1974, 7 , L387. e18 S. Ichiba, M. Katada, and H . Negita, J . InorR. Nuclear Chem., 1975, 37, 2249. 6oo R. H. Herber and R . F. Davis, J . Clieni. Phys., 1975, 63, 3668. 0 6 0 N. Karnezos, L. B. Welsh, and M. W. Shafer, Phys. Rro. ( B ) , 1975, 11, 1808. 638

480

Spectroscopic Pi-opertirsof' Itiot-gmic mid Orgartometallic Compounds

Other t i n chalcogenide systems studied by Mossbauer spectroscopy include the solid solutions I'b,. .Sn,Se 6 5 1 and Pb,-,Sn,Te,G52 and the binary telluride SnTe. The latter was studied over the temperature range 300-500 K , and the results were discussed i n terms of the properties of the two highest valence band edges in S ~ T C . ~ ~ ~ 6 Other Elements

Main-group Elements.-Gernzatiirrnz (73Ge). The experiments to observe the highresolution 13.3 keV resonance in '%e, discussed in last year's Report (p. 480), have now been described in full detail. The resonance ef'fect was shown to be sensitive to lattice damage by proton irradiation and to lattice strain induced by silicon-germaniuni epitaxial mismatch. The effect was observed in microcrystalline powders as well as in elemen tal single crystals. The sharpest resonance observed to date has an uncorrected depth of 2.37(14)% and an experimental linewidth of 0.01 38(13) nim s--l, which is the narrowest Mossbauer resonance ever observed at room t e n i p e r a t ~ r e6.5 ~ 5 ~~~ Krypton (83Kr). I t has been pointed out that a factor of Z was accidentally omitted from previous calculations of the ratio of the quadrupole moment of the first excited state (f = $ + ) to that of the ground-state ( I = ;+). The result should have been 1.98 and the reported value of Q ( $ ) should have been 0.535 barn.s5a The ratio Q(Z)/Q(!) has been estimated in an independent study of 83Kr in hydroquinone to be 1.99 k 0.05 barn, in excellent agreement with the corrected value given above. Line broadening observed in the spectra of 83mKr in rubidium halides was attributed to lattice defects arising from the internalconversion processes preceding the recoil-less y-ray emission in the alkali-metal halide sources. Quadrupole interactions, reported earlier by Krasnoperov and attributed to the existence of highly charged krypton atoms, were not detected.657 Mossbauer studies on 83Kr in solid krypton at 4.2 K have shown that the recoil-less fraction of a solid krypton source is about 40% lower than that of a solid krypton absorber, and this has also been attributed to after-effects caused by the highly converted 32 keV y-ray decay which precedes the 13.3 keV transi tion.668 Tin (l17Sn). The Mossbauer effect of the 159 keV transition in l17Sn has been observed for the first time, and the half life was found to be Ti = 0.270(17) ns. Recoil-free fractions were determined for S n 0 2 and Pd,Sn, using this resonance, and compared with the values obtained with the 23.8 keV resonance in lleSn.O Antimony (121Sb). Data have been recorded for the antimony(ii1) complexes M2SbF6(M = K, Rb, Cs, or NH,), RbSbF4, and MSb4F13(M = K , Rb, or Cs), ~1

652

V. P. Savel'ev, Z. M. Latypov, and V. P. Zlornanov, Russ. J. Inorg. Chenz., 1975, 20, 1119 (Russian original Zhur. neorg. Khim., 1975, 20, 2006). I. N. Nikolaev, A P. Shotov, A. F. Voikov, and V. P. Marin, Pis'ma Zhur. eksp. reor. Fit., 1975, 21, 144.

6b3

956

1166 668

S. T. Lin and G . M . Rothberg, J . Nonmetuls, 1973, 1, 335. L. Pfeiffer and R. S. Raghavan, ref. I , p. 203. L. Pfeiffer, R. S. Raghavan, C. P. Lichtenwalner, and A. G. Cullis, Phys. Rev. (B), 1975, 12, 4793. S. L. Ruby and H. Selig, Phys. Rev. ( B ) , 1975, 12, 1991. B. Kolk, Phys. Rev. ( B ) , 1975, 12, 1620. B. Kolk, Phys. Reo. ( B ) , 1975, 12, 4695.

Miissbaiier Spectroscopy 48 I MSbCIl', (hl -= Na, K, Rb, Cs, or NH4), R;I,SbSO,F, ( M = Na or K), M,SbC,04F3,2H20 (hl = K , N l i 4 , or C204), NaSbNO,F,,H,O, and M2SbC131-, ( M = Kb, Cs, or Nl14). The unshared electron pair was shown to be slereochemically active in all of the complexes and distributed along the z-axis of thc electric field gradient tensor. For the fluoride complexes the isomer shift was independent of the nature of the outer-sphere cation, M, indicating that these materials probably form isostructural series. However, within the series MSbCIF3, different isomer shifts were observed, indicating that individual members are probably not isostructural. The complexes Rb,SbCI,F, antl Cs2SbCl3F, each appear to contain two non-equivalent antimony(1ir) environm e n t ~ Data . ~ ~ have ~ also been recorded for the antimony(ri1) fluorides MSb,F, (M = Na, K, Rb, or Cs) and Cs,SbF,.6Ro The isomer shifts in the antiniony(v) complexes MSbFs (M = Li, Na, K, Rb, Cs, or NH,) have been discussed in terms of a varying electron transfer from the cation to the SbF,- molecular ion. The isomer shift was shown to increase slightly from the rubidium to the sodium salt, signifying a decreasing s-electron density at the antimony nucleus in that order. This trend was thought to arise essentially from a decrease in the population of the 5s valence orbital.0G1The electronic structure and chemical bonding in the semiconducting solid solutions (NH4),[Sb,Snl-,Cl6! ( x = 0.02, 0.06, 0.08, 0.19, 0.24, or 0.28) have been investigated at 77 K, and in each case the presence of both antimony(i1i) and antiniony(v) was Variations in the isomer shift and quadrupole coupling constant at the lZISb nucleus in the series Me,SbX,_, ( x = 0, 1, 2, or 3 ; X = C1, Br, or I) have been discussed in terms of the molecular geometries, the changes in ionicity of the Sb-X bonds, and the extent of intermolecular interactions. The Townes-Dailey approximation and a point-charge model were used as a basis for the analysis of the data.6R3 The predicted ratio of - 1 : 2 for the quadrupole coupling constants e2qQ of cis- and trans-octahedral diorganoantimony(v) complexes has been observed for the first time i n the compounds [Ph,SbCl,(ox)] and [Ph,SbCl,(acac)] (Iiox = 8-hydroxyquinoline, Hacac = acetylacetone). The oxalate derivative was shown to have an asymmetry parameter of 77 = 0.75, consistent with a C-Sb-C angle of either 76" or 104*, probably the An antimony-121 Mossbauer study of a series of bis(ha1ogenoacetato)trimethylantimony complexes is discussed on p. 473. Six antimony(iI1) compounds of the type [SbX,L,] (X = C1 or Br; L = substituted I ,2-dithiole-3-thione) have been shown to have positive quadrupole coupling constants e24Q, consistent with an excess of p-electron density along the z-axis, as illustrated (9). The Sb-L bond was found to be very weak, with the 1159 V. P. Gor'kov, R. L. Davidovich, G. V. Zimina, L. A. Sadokhina, F. Kh. Chibirova, antl V. S. Shpinel, Koord. Khirn., 1975, 1, 561. S. E. Gukasyan, V. P. Gorkov, L. A. Sadokhina, F. Kh. Chibirova, and V. S. Shpinel, Zltur. strukt. Khim.. 1975, 16, 207. Oo1 J . P, Devort and J. M . Friedt, Chem. Phys. Letters, 1975, 35, 423. 662 G . V. lonova, E. F. MakaroL, S. P. lonov, and A. Yu. Aiexandrov, Tezisy Dokl.-Vses. KonJ Kliitn. Svyazi P o l u p r o i d n . Polenlctullrrkh, 5th, 1974, 106. 663 J. P. Devort, J. P. Sanchez, J. M. Friedt, and G. K. Shenoy, ref. 1, p. 255. m 4 J . N. R . Ruddick and J. R. Sams, Inorg. Nuclear Cliem. Letters, 1975, 11, 229. 680

482

Spectroscopic Proper I ies of

Iii organic a t

id Organomet allic C'o tnpo ir rids

AV?:

donor abilities of the sulphur ligands decreasing in the sequences C,H,S, > C,H,S4 > CI0HBOS3,and C3H2S3> C,,HsS,.sle Data have been reported for the so-called random rutiles CrSbvO,, FeSbvO,, and GaSbvO,, the trirutiles MgSb"',O, and CoSbVO,, and the distorted trirutile C U S ~ ~ ~ OI t, was . * ~pointed ~ out that the work of Wooten et a/. (1974, see last year's Report, p. 483), which included all but two of these compounds, was reported after the experimental work in ref. 665 had been completed, The presence of antiniony(v) has been confirmed in the oxides GaSbO, and In,-,Sb,O,,, ( x z l),66s whereas the compound [Sb(C,O,)(OH)] has been found to contain only a n t i i n o n y ( i r ~ ) .The ~ ~ ~application of Mossbauer spectroscopy to follow the incorporation of antimony into calcium halogenophosphate phosphors has been discussed, and demonstrated for fluorapatites and chlorapatites activated, respectively, with antimony and manganese.668 Previous Messbauer studies have shown that the material thought to be antimony(v) sulphide actually contains only antimony(rr1). However, it has now been shown that a covalent antimony(v) sulphide can be synthesized in the /I-decay of l2lrnSnIvin SnS,. In this nuclear reaction the daughter antimony(v) is isoelectronic with the parent tin(rv) state. This is in contrast with the situation found in the electron-capture decay of 119Sb''1in Sb2S3,where tin(rv) dominates over the isoelectronic tin(ri) state in the products. The result is consistent with the conclusion drawn from mass spectrometric studies on gaseous systems, that the ionization effect of the Auger cascade following electron-capture decay is much stronger than that of the electron shake-off process accompanying /I-decay.sse The Mossbauer spectra of SbSBr, SbSeBr, SbSI, SbSeI, and SbTeI at 4.2 K have been discussed in relation to available structural data. The quadrupole coupling constant e2qQ was found to decrease for the iodides in the order SbSI > SbSeI > SbTeI, becoming negative for the latter. The positive sign for SbSI was attributed to an excess of p-electron density in the lone pair on antimony, and replacement of S by Se and Te was thought to reduce this excess p r o g r e s s i ~ e l y . Measurements ~~~ on the antimonide Nb,Sb,Te, have enabled the antimony to be assigned to the XI1 site in the crystallographic formula [T3(X~),(XII)~].'~~ 666

w7 668

670

O71

J. D. Donaldson, A. Kjekshus, D. G . Nicholson, and T. Rakke, Acta Chem. Scand. ( A ) , 1975, 29, 803. M. B. Varfolomeev, M. N. Sotnikova, F. K. Chibirova, and V. S. Shpinel, Russ. J Inorg. Chem., 1975, 20, 655 (Russian original Zhur. neorg. Khim., 1975, 20, 1163). S . Ambe, J . Inorg. Nuclear Chem., 1975, 37, 2023. V. Fraknoy, P. Gelencser, B. Levay, and A. Vertes, J . Luminescence, 1975, 9, 467. S. Ambe and F. Ambe, J . Chem. Phys., 1975, 63, 4077. J. D. Donaldson, A. Kjekshus, D. G . Nicholson, and J. T. Southern, Acra Chern. Scand. ( A ) , 1975, 29, 220. J. D. Donaldson, A. Kjekshus, D. G . Nicholson, and J. T. Southern, Acta Chem. Scand. ( A ) , 1974, 28, 866.

Miissbauer Spectroscopy 483 Resolution of the overlapping profiles from the two distinct antimony sites in Mo3Sb, has been achieved by application of a Fourier-transform treatmen t . 6 7 1 However, it has not proved possible to distinguish the two different sites known to exist in the compounds NbSb, and TaSb,.s72 Data have also been reported for the antimonides TiSb and VSbz873 and the Heusler alloys N ~ , - , C U , M ~ S1 3~’ ~ . ~ ~ ~ Tellitriunz (lZ5Te). A very large internal magnetic field of flux density +857 k 9 kG has been observed at 125Tedaughter nuclei in sources of the ferromagnetic Heusler alloy Pd,Mn125Sbat 4.2 K. The positive sign of the field was established from measurements with the source in an applied magnetic field. This result yielded a value for the nuclear g-factor ratio of gea/ggr = - 0.2270 5 0.0015, which, when combined with the known ground-state g-factor gJr= - 1.77666 k 0.00006, gave a value for the excited-state g-factor of g,, = +0.403 & 0.003.s76 The magnetic hyperfine fields and recoil-free fractions at the 12hTedaughter nuclei in sources of lZ5I implanted in iron have been investigated.s77 Mossbauer absorption spectra have been recorded at 4.2 K for 12”e dimers, 125TeC14, and 126TeFeisolated in noble-gas matrices. The isomer shifts were found to be +0.34 k 0.07, 1.0 5 0.1, and - 1.54 5 0.05 mm s-l, respectively, relative to the Iz5Sb/Cusource, and these values were combined with the results of Dirac and Fock calculations of electron densities to yield estimates of the change in the mean-square nuclear-charge radius, A. The values ranged from A = (2.0 k 0.4) x fm2 to (3.4 k 0.7) x fm2, depending o n the assumptions of the electronic configuration of tellurium in TeFe.678 The anisotropy of the recoil-free fraction has been studied at 80 K in single crystals of tellurium metal and a-TeO,. For tellurium metal the recoil-free fraction in a direction parallel to the c-axis of the crystal was found to be greater than that perpendicular to the c-axis by a factor of 1.58 k 0.21, whereas for or-TeO, the factor was shown to be 0.85 If: 0.07.e79The Debye temperature and Mossbauer fraction for 125Temetal have been calculated theoretically.68o Thin films of amorphous lz5Te have been studied,eR1and the diffraction of the 35.6 keV y-quanta in a tellurium single crystal has been discussed.682 New data have been recorded for a number of tellurium compounds, and the isomer shifts have been plotted against the isomer shifts for similar iodine

+

67a

07a

674 676

676

07? 67n

eno 681

683

L. Brattas, J. D. Donaldson, A. Kjekshus, D . G. Nicholson, and J. T. Southern, Acfa Ckem. Scand. ( A ) , 1975, 29, 217. J. D. Donaldson, A. Kjekshus, D. G . Nicholson, and T. Rakke, J. Less-Cornmon Metals, 1975, 41, 255. L. J. Swartzendruber and B. J. Evans, ref. 1 , p. 265. S. T. Tamaev, Kh. Kh. Valiev, S. M. Irkaev, and R. N. Kuz’rnin, ‘Str. Svoistva Primen. Metallid., [Mater. Simp.], 2nd, 1972’ (publ. 1974), ed. I. I. Kornilov and N. M. Matveeva, Nauka Moscow, p. 96. P. Roolchand, M. Tenhover, S. Jha. G . Langouche, B. B. Triplett, S. S. Hanna, and P. Jena, Phys. Letters ( A ) , 1975, 54, 293. H. De Waard, S. R. Reintsema, and S. A. Drentje, ref. 1, p. 295. P. H. Barrett, P. A. Montano, H. Micklitz, and J. B. Mann, Phys. Rev. ( B ) , 1975. 12, 1676. A. A. Opalenko, 1. A. Avenarius, R. P. Vardapetyan, and R. N. Kuz’min, Phys. Status Solid; ( B ) , 1975,72, K125. R. M. Powell and P. Martel, J . Phys. and Chem. Solids, 1975, 36, 1287. N . A . Blum and C. Feldman, ref. 1, p. 401. V. S. Zasimov, R. N. Kuz’min, and A. Yu. Aleksandrov, Soviet Phys. Solid State, 1975, 17, 2044 (Russian original Fiz. Tuerd. Telu, 1975, 17, 3083).

484

Spectroscopic Properties of Itioi*gcinic and Organometa flic Compomcls

compounds. The results are shown in Figure 12, which reveals a roughly lincar relationship for pairs of compounds that are both isoelectronic and isostructural. Pairs such as TeCI, and I2CI6,and TeO, and KIO,, which are not isoelcctronic but merely have similar chemical character, can be seen to deviate slightly from the linear relationship, and it was suggested that these deviations occur because

8 ( ' 2 ~ 1 1 l n : r n s-'

Figure 12 Isomer shifts for telluriut?i conipoiuids relative lo 125Sb(C~) plotted aguitist shifis ,for siitiilur iodine cotnpoutids relutise to "'ZnTe. Circles, ref. 682 ; squares, I>. Jung and W . l'rifthaiiser, Phys. Rer., 1968, 175, 512; triangles, S . L. Ruby and G . K . Shenoy, ihid., 1969, 186, 326. Solid symbols indicate pairs of isoelectronic ions, and the stmight line is a descriprioti of these points. The underlining of' H,TeO, und ZnTe indicutes t h t they were used as sources relative to u standurd absorber in un lZsI e.vpcrittient. The configuratiotis indicated on the right ordinate are approxiniute configurations of the bonding in the tellirriuiri compounds [Reproduced by permission from 'Proceedings of the International Conference on the Applications of the Mossbauer Effect, Bendor (France), 1974', J . PIiys. (Paris),Colloq. No. 6, Supplement to No. 12, Vol. 35, 1974, p. C6-2271

the bonding in the tellurium compounds is more ionic than in the iodine analogues. It was also shown that a plot of isomer shift against quadrupole splitting yields a good linear relationship for almost all of the tellurium compounds studied, regardless of the bonding configuration; however, the reason for this is not underst ood.'jS3 The alkyltclliiriuni(iv) halides Me,TeX, have been found to give isomer shifts which are less positive than those for the unsubstituted TeX, compounds, consistent with a lowered s-electron density at the tellurium nuclei in the former. Quadrupole splittings in the range 7---10 nirn s-l were observed for these compounds. The parameters for the compound Me,TeI, were shown to be consistent with the prescnce of telluriun~(iv).684Data have also been reported for the aryltellurium-(11) and -(Iv) compounds RTeX, R,Te, R,Te,, RTeX,, and R,TeX, (R = Ph, p-MeC,H,, p-MeOC6H,, or p-EtOC,H,; X = Cl, Br, or 6By

Y. M a h n i u d , P. Boolchand, S. S. H a n n a , arid B. B. Triplett, ref. 1, p. 227. K . V. Smith, J. S. T h a y e r , a n d €3. J. Zabransky, Inorg. Nuclear Chem. Letters, 1975, 11, 441. F. J. Berry, E. H. Kustan, and B. C . Smith, J.C.S. Dalton, 1975, 1323.

Mussbarier Spectroscopy 485 I T e Mossbauer spectra have been measured for a number of complexes of t el I u r i u ni( 11) and t e I1 ur i i t ni( I v) u i t h s~i 1 ph iir-con t i t i n i n g 1i ga iid s . The t cl I u r i LI m ( I I) coniplcxes, which includcd [Te{(MeO),PS,},], [Te(SCH,CI-i,CO,H),], bl,['re(S,O,),] (M = Na or Rb), [Te(EtLNCS,)], [Te(MeOCS,),], and trtrns-[Tc{SC(NMe,),),(S,O,Ph),], were found to exhibit large quadr upole splittings of 12.4-15.2 mni s-l and isomer shifts (relative to I2,I/Cu) of +0.33--0.91 mni s-l. These data were interpreted as evidence for the involvement of some 5s character in the bonding for several of the compounds, consistent with the interpretation of X-ray diffraction data. The tt.lluriuni(iv) compounds included the monoclinic and orthorhombic forms of ~ I . ~ ~ . ~ - [ ' T ~ C ~ , ( S C ( N the M ~ ,sewn-co-ordinate ),),], species [Te{(K,NCS,),

*LS.OO ----7

I2 5 . 0 0

7-

-- -

1 -

i ?!I

-2u.ou

Velocitylmm

I

-1~1.00

1

r

-

!O.OU

- - -

I

(1.90

:u.

au

5-1

Figure 13 (c)

l n Q I MusJbauer spectra at 4.2 K of (a> I(pyridine),CIO,, (6) I(thiourea),l, I(acetate),, and ( d ) 1,04; the contponent with the larger yuadrupoie coupling constant

is assigned to the I 0 cation, and the other component to the TO,- anion

(Reproduced by permission from J . Cheni. Phys., 1975, 62, 4343)

1C1, IBr, RSI, and certain halogen-amine complexes. The comparisons revealed that IC12-, [ICl(py)], and [Iby),] t all have similar Mossbauer parameters, indicating that py and CI- probably have similar donor characteristics when

co-ordinated to I+ in a three-centre four-electron bond. Figure 13c shows the frozen-solution spectrum of the unstable material, previously reported as [I(acetate),], formed when iodine is oxidized with fuming nitric acid in acetic anhydride. The dominant resonance is that of an iodine(ii1) species with parameters similar to those of I,C16, and i t is therefore suggested that the molecule be formulated as the dimer [I,(acetate),], in which two acetate groups are bridging. The spectrum of 1,04 (Figure 13d) was remeasured and found to

Spectroscopic Properties of Iiiorgmic arid Organometullic Cornpounds

48 8

be identical with that reported by Grushko (1969); two components were detected and the complex was formulated as the salt (IO+)(103-).694 On the basis of their Mossbauer parameters, molecular complexes formed between iodine and various organic solvents have been shown to fall into three groups. The strength of the I,-complexant bond was found to increase i n going from n-solvents through alcohols and ethers to a n i i n e ~ . ~ ~ ~ Recoil-free fractions for the 26.8 keV transition in lz9I have been calculated, using the simple shell model, for the alkali-metal iodides MI (M = Na, K , or Rb), and shown to agree well with those determined experimentally.696Covalency effects in the transition-metal di-iodides MT2 (M = Mn, Fe, Co, or Ni) have been elucidated by analysis of the 1291 hyperfine interactions, and some of the main results are summarized in Table 2. The magnetic hyperfine fields observed

Table 2

Coualettcy atid hyperfine-interaction prrrameters for the trorrsition-metal di-iodides MTz ( M = Mn, Fe, Co, or Ni)

c o ??lpounci Mnl,

Fel, (A-site)

COT, NiI,

Ionic character a

(%) 77 73 67 64

Transferred

field B / k G ( & 5) I40 191

130 263

f,,

(%) 4.0 4.9

6.7 6.5

f\

(%)

0.59 0.80 0.54 1.1

“ T h e ionic character o f the M-I bond, estimated from the isomer shift and quadrupole splitting data, using the Townes and Dailey approximation; b v c the amounts of covalent spin density transferred from M to the iodine 5p and 5 s orbitals, respectively.

below the Nee1 points were shown to arise mainly from the isotropic Fermicontact term B , = %rpl%p(0),fs, where p(0) is the 5s electron density at the iodine nucleus and .fb is the amount of spin density transferred from the magnetic The spin arrangement in antitransition-metal ion to the iodine 5s ferromagnetic Nil, (TN = 75 K ) has been studied independently from measurements of the combined electric quadrupole and magnetic dipole interactions, and shown to be collinear, with moments alternating in direction among the various ( I 00) planes.6aB“ Measurements of transferred hyperfine interactions in iron(rr1) bisdithioand hyperfine interactions at 129J carbamato-iodides have been referred impurities in the ferromagnetic tellurides Cr,Te,, CrTe, and Cr,Te have been stud ied.6NX Xenon (lZ9Xe). The magnetic hyperfine interaction at 129Xehas been studied by 5 x implanting 12anrXe activity in iron foils at dose rates of 5 x and 1 x lOI5 xenon atoms per cm2. The Mossbauer spectra, recorded with the 39.6 keV resonance, revealed a range of flux densities corresponding to xenon atoms embedded at various lattice sites, the relative population of which was 806

6oB

C. H . W. Jones, J . Chem. Phvs., 1975, 62, 4343. S. Bukshpan, C. Goldstein, T. Sonnino, L. May, and M. Pasternak, J . Chem. Phys., 1975, 62, 2606. Sneh and B. Dayal, Phys. Status Solidi ( B ) , 1975, 70, 341. J. P. Sanchez, J. M. Friedt, and G. K . Shenoy, ref. 1, p. 259. M. Pasternak, S. Bukshpan, and T. Sonnino. Solid State Comm., 1975, 16, 871.

Miissbairer Spec f rosropy

489

found to be dependent on dose. The component corresponding to the largest flux density, B = 1480 & 80 kG, was attributed to substitutional xenon impurities. A value of g,,/g,, = -0.25 5 0.04 was deduced for the ratio of the excited- and ground-state g - f a c t o r ~700 .~~~~ Cnesiirni (133Cs).Information about the lattice sites of implanted xenon impurities has also been obtained from Mossbauer measurements with the 81 keV resonance i n 133Cs 701

Transition Elements.-Nickel (61Ni). Measurements with the 67.4 keV resonance of OlNi have yielded information about the vibrational, magnetic, and electronic properties of hexagonal NiS in both the semi-metallic antiferromagnetic phase and in the metallic Pauli-paramagnetic phase which exists above the transition temperature, Tt = 265 K . A decrease in the recoil-free fraction was found to occur at the semi-metal-to-metal transition, corresponding to a change in the Debye temperature of about 20%. The relative decrease in the magnetic hyperfine field with temperature was given by the relationship [B(O) - B(T)]/H(O)= aT2, as expected for single-electron excitations in itinerant antiferromagnets. The electric field gradient was shown to decrease both with temperature and with increasing content of nickel vacancies, and it was suggested that mechanisms responsible for the changes in electronic structure might also promote the transition to the metallic The magnetic structures and phase transitions in NiS1.B3have also been studied by 61Ni Mossbauer spectroscopy in the temperature region 4.2 < T/K 6 50. Between 30.9 K and the Ntel point ( 7 ' ' = 44.5 K ) the magnetic moments on the nickel ions were shown to be aligned parallel to the local trigonal symmetry axis of the cubic pyrite structure. Below 30.9 K two distinct nickel environments were detected, and these were characterized by magnetic moments aligned at angles of 77" and 39" to the symmetry axes at the two sites. The critical temperatures for the two sites differed slightly from one another and were found to be (30.9 k 0.1) and (30.2 L 0.1) K, respectively. In the lowtemperature region NiS,.,, and NiS,.,,, gave essentially similar results to those described for NiSl.g3,but the NCel temperatures were much higher. In the region between 50 K and T N ,significant line-broadening was observed, but it was not possible to tell whether this was caused by a static distribution of magnetic moments or by electronic relaxation effects.703 Zinc ("Zn). The electric quadrupole interaction in 67Zn0has been determined using a novel frequency-modulation technique, instead of the conventional velocity-modulation method. A source containing 67Gain a ZnO single crystal was mechanically oscillated with varying frequency by a quartz crystal, and the resulting f.m. sidebands of the 93.26 keV y-ray were thereby swept across the 699

70n

7n1 702

7u3

M. van Rossum, G . Langouche, H. Pattyn, G. Dumont, J. Odeurs, A. Meykens, P. Boolchand, and R. Coussement, ref. I , p. 301. M. van Rossum, G. Langouche, H . Pattyn, G. Dumont, J. Odeurs, A. Meykens, R. Coussement, and P. Boolchand, ref. 56, p. 460. S. R. Reintsema, S. A. Drentje, P. Schurer, and H. de Waard, Radiation Eff.,1975, 24, 145. J . Fink, G. Czjzek, H . Schmidt, K . Ruebenbauer, J. M. D . Coey, and R. Rrusetti, ref. I , p. 675. G . Czjzek, J. Fink, H. Schmidt, G. Krill, F. Gautier, M. F. Lapierre, and C. Robert, ref. 1, p. 621.

490 Spectroscopic Properties of Inorganic and Organometallic Compour1d.y absorption lines of a ZnO absorber maintained at 4.2 K. The frequency separations of the ground-state triplet were measured to be v 1 = 361.2 & I .O k H z and v2 = 723 k 4 kHz. From these values the quadrupole coupling constant was estimated to be e‘qQ = 2.408 k 0.006 MHz, and the asymmetry parameter 7 = 0.00(+_:.065}.704 Rrrtlieniirm (OORu). A general method for the extraction of hyperfine parameters (not magnetic) for mixed transitions ( M l , E2) between 8 and 4 states of Miissbauer nuclei has been given. A least-squares routine is used to fit a theoretical spectrum directly to thedata points, adjusting the hyperfine parameters to obtain an optimum fit. The method was applied to the unresolved six-line quadrupole-split spectrum of RuO, to give e?qQa/h = - 3 3 . 7 f 0.9 MHz, e2qQe/h= 101 ? 2.7 MHz, 7 = 0, 6 = -0.23 f 0.1 mm s-l relative to ruthenium metal, and I’ = 0.57 +_ 0.03 mm s-l.’05 A detailed investigation at 4.2 K of the O9Ru nuclear quadrupole interaction in P-RuCI, has yielded a value for the ratio of the quadrupole moments of Qev/QPr= +3.06 +_ 0.10, and for the quadrupole coupling constant of e2qQex= 1.38 2 0.03 nim s-*. /3-RuC13 has a distorted octahedral coordination about the ruthenium and, although the structure is not known unambiguously, the X-ray powder pattern has indicated that it belongs to one of four closely related space groups, in each of which the geometry corresponds very closely to a dominant trigonal elongation of the octahedra. The iZu configuration of lou-spin rutheniuni(l~i) therefore becomes (/$,)i(r!q)l with an electron ‘hole’ in the singlet level, and on this basis q should be positive. It therefore follows that Qex and Qur are also positive. The positive value obtained for Qcx/QRragrees well with two earlier estimates from the same laboratory (see Table 3), and with the value derived in ref. 705.706

+

Table 3 Miissbauer parameters from the least-squares fitting of 9 0 R spectra ~ nt 4.2 K Compound

/%RuCI,

Co,RuO,

(NBLI”,)[RuCI,N] RuO,

QexIQur

+3.06 (10) 2.94 (4) + 2 . 8 2 (9) $0.300 (17)

+

e2qQex a

+ 1.38 (3)

- 1.456 (20) +3.19 ( 1 1 ) + 1.393

r a

0.25 (1) 0.269 (4) 0.24 (3) 0.57 3)

a Values in mm s--I, 6 being relative to ruthenium metal at 4.2 K ; ratio; value fixed; data from ref. 705.

8a

-0.642 (2) -0 567 ( 1 ) +0.081 (10) - 0.23 ( I )

62

h

2.70 2.70 2.64 (17) 2.70

’ 6‘ is the E 2 / M 1 mixing

Ruthenium catalysts supported on AI,O, and SiOz have been studied by 9gRu Mossbauer spectroscopy. RuCI,, 1-3Hz0 was found to undergo a chemical change when impregnated on Al,03 but not on a SiO, support. Catalyst satnples impregnated with RuCI, were found upon calcination to contain small crystallites of RuO,. On reduction these samples were observed to contain sniall particles of metallic ruthenium, but no compound formation from reaction of 704 706

?06

G . J. Perlow, W. Potzel, R . M . Kash, and H . de Waard, ref. 1, p. 197. D. C. Foyt, M . L. Good, J. G . Cosgrove, and R. L . Collins, J . Inorg. Il’irtlrar Chnz., 1975,

37, 1913.

F. M . Da Costa, T. C. Gibb, R. Greatrex, and N. N. Greenwood, Chem. Phys. Letters, 1975, 36, 655.

Mossbauer Specfroscopy

49 1

ruthenium with the support was detected. The technique was found to be very sensitive to the metal particle size, no effect being observed for very small ruthenium particles supported on Si0,.707 The magnetic and structural properties of the solid-solution series SrFe,Ru1-,03-, (0 d x d 0.5) have been studied by 57Fe and 9 g R ~ Mossbauer spectroscopy, and the main features of the work have already been discussed in Section 4. A novel feature of the study was the unambiguous detection of the ruthenium(v) oxidation state in an oxide lattice. Thus, in the spectrum of S r F e 0 . 6 R ~ ~ 0 .a5 0unique 3 magnetic flux density of 529 kG was detected; this is substantially higher than in SrRuO, and in the phases having low iron content. The isomer shift of +0.116 mm s-l is also more positive than in any of the typical R u 4 +oxides, and is of the order of magnitude expected for Ru5+. This oxidation state has a 4d3 configuration, with S = #, and resembles Fe3' in that the magnetic flux density should vary little with change in environment. The flux density of 529 kG corresponds, therefore, to about 176 kG per unpaired electron. On this basis, the flux density at Ru4-' with S = 1 should be 352 kG, which is in very good agreement with observation, and lends support to the belief that SrRuO, has a canted-spin structure, rather than a reduced-moment fer r oni a gne t i sni . 39 The electron density at the nuclei of g 9 R ~lgaIr, , ls5Pt, and le7Au impurities in a palladium matrix has been found to decreasc on hydrogenation of the matrix; possible mechanisms for this behaviour were Hafniim (177Hf). An on-line Mossbauer experiment on metallic li7Hf has shown that the recoil does have an influence on the environment of the active ion in its final position. The electric field gradient was found to be - 7 . 3 ? 0.6 mm s-l in a recoil site, compared with -5.65 k 0.10 mm s-l in a normal site. No such effects were observed in Hf02.709

Tungsten (lsoW, lSzW). Using Mossbauer conversion spectroscopy, t h e ratio of the quadrupole moments of the first excited states in lS0W and lSzW has been determined as 1s0Q/182Q= 0.976(30). The isomer shift of the first excited state in lH3Wwas also measured, and a value of -0.05 x lo-* > A ( R ~ ) / ( R ~>> -0.28 x estimated for the fractional change i n the mean-square nuclear charge radius on excitation. By virtue of the excellent statistical quality of the spectra it was possible to derive a value of 2/3 = 0.0165(9) for the interference parameter of the 100 keV E2 transition in I8W,for the L-shell.lo Theoretical interpretation of 182WMossbaiier spectra for various tungsten(1v) octacyanides has indicated that the quadrupole coupling constants, e2qQ, arise from partial cancellation of the dominant contribution from the d 2 configuration by effective population of the nominally empty metal cl-orbitals through ligand -> metal a-bonding. Predictions that e?yQ should be negative in dodecahedral [W(CN),14- and positive, with a smaller I e2qQ 1, in square-antiprismatic [W(CN)J- were confirmed experimentally. On this basis [W(CN)J4- was assigned a dodecahedral structure in Li, [W(CN)E],nH,O and square-antiprismatic in Cd2[W(CN)J,8H,O, and the solid-state structures of dodecahedral 7u7 7nLI 7u0

C. A. Clausen, tert. and M . L. G o o d , J . Curalj*siT,1975, 38, 92. L. lannarella, F. E. Wagner, U. Wagner, and J. Danon, ref. 1 , p. 517. C. Jeandey and P. Peretto, Phys. Status Solidi ( A ) , 1975. 28, 529.

492

Spc'ctr.oycnopic. Pwpesties 0.1 Itloryratiic nun Organornetcl//ic COnip0lmci.s

K,[W(CN),] and square-antiprisnlatic H,[W(CN),] were found to be retained in frozen solutions. The quadrupole coupling i n dodecahedra1 [(EtNC),W(CN),] was also discussed. For tungst en(v) derivatives the quadrupole coupling constants were negligibly small, indicating that the above-mentioned cancellation is virtually exact in the d1 configuration. A crude empirical value of 16 m m s--l for I tp24(2 I due to one cl-electron was estimated. The effect o n the tungsten(1v) coupling constants of distortions from ideal geometry was Tntzttrlirni (IH1Taj. The teniperature dependence of the 6.2 keV resonance i n IR1Tahas been studied for sources of lNIWin tungsten or tantalum host$. The measurements covered the temperature range 15-457 K and for lHIW(W) showed substantial deviation from the anonialously large linear dependence observed previously at higher temperatures. Subtraction of the second-order Doppler shift revealed a residual temperature dependence closely proportional to the thermal expansion of tungsten. For lslW(Ta) a more nearly linear temperature dependence was observed, and the analysis was much less ~traightforward.~" The pressure dependence of the isomer shift has been studied for lslTa impurities i n hosts of tantalum, tungsten, and platinum ;712 a review of the effect on the hyperfine interactions of changes in atomic volume induced by the application of high pressure has already been referred to.20 Measurements have been made on the &-phase of the Ta-H and lRITaimpurities in the disordered alloys Nb,-,Ta, (x = 5.0 -90.0 atom ZJ have been studied.;14 Perturbed angular y-y correlations have been investigated for lelTa impurities in PbHfO3,'I6 BaTi0,,715SrTi0,,715and HfC.716 Iridium (lon1r). A single-line source for Mossbauer spectroscopy with the 73 keV resonance i n ls31r has been described ; it consists of the cubic osmium-niobium alloy (5.0 atom lQ2Osjand is suitable for repeated neutron irradiation to yield the l g 3 0 sprecursor. Well-resolved quadrupole-split spectra were recorded with this source and absorbers of organonietallic conipounds which might have been expected to give very low recoil-free fractions, e.g. [Ir(Ph,PCH,CH,PPh,),O,][PF,], for which the percentage absorption was 2%.717 Measurements on a series of 13 four-co-ordinate iridium(1) complexes of the type [Ir(CO)(PPh,),X] have shown that the Mossbauer parameters remain essentially constant for a wide variety of ligands X, the other ligands adjusting to maintain the isomer shift of the iridium close to that of iridium The applicability of the additivity model for the low-spin da configuration has been assessed in a study of 1 5 iridium(m) complexes. Unlike the iridiuni(1)

., 421 Apostolova, M., 415 Appcl, R., 141, 142. 147, 150, 151, 152, 156, 257, 259, 265, 269 Appeloff, C. J., 231 Aprahamian, J., 464 Arai, J., 501 Aramu. F., 428 Araneo, A., 377 Arata, Y., 3 Arbuzov, B. A., 160 Arduini. A. L., 385 Arents, R. A.. 418 Aresta, M., 350, 374 Arhart, R. W., 18 Arias d e Pasqual, M., 382 Arif, S. K., 410, 501 Arisman, R. K., 223 Aritonii, M., 78, 134, 244, 378 Arkhipenko, D. K., 212, 217 Armishaw, K. F., 213 Armit, P. W., 86, 305 Armitage, I. hl., 30 Armon, H., 496 Armor, J. 25, 369 Armstrong, L. Ci., 396 Armstrong, R . L., 167, 177 Arneri, R., 341 Arnold, D. E. J., 157, 258,443 Arnold. K., 95 Aronovich, 1'. hl., 77 Arons, R. R., 114 Arrington, C. A., 195 Arrington, D. E., 270 Arsenin, K. I., 395, 399 Arsent'eva, V. P., 310, 399 Arshavskaya, E. V., 20, 44 Arshinova, R., 157 Artamonova, S. G.. 79 Arthur, J. W., 217 Aruldhas, G.. 220 Asano, A., 505 Asch, L., 428, 499 Ashby, E. C., 78, 79, 229, 230, 233

Author Index Ashe, A. J., tert., 23, 188, 449 Asher, I. M.. 208, 288 Ashikhinia, T. Ya., 380 Aslanov, Kh. A., 153 Gsprey, L. B., 204, 301, 320 Astakhov, A. V., 464 Astheimer, L., 300 Astruc, D.. 23 Atamanenko, I . D., I22 Atchekzai, H. R., 735 Gthanassiadis. G . , 501 Atkins, P. W., 92 Gtkins. K. M..34. 333 Attalla, A., 1 1 1 Attig, T., G., 56, 80, 310 Attorresi. M.. 210 AtWood, 'J. la:, 446 Atzmony, V., 501. 502 Auber. M . W., 364 Aubke, F., 145, 194, 267, 268, 274 Augustin, G., 21 Augustin, H., 293 Auel, T., 472 Ault, €3. L., 194 Ault, B. S., 192, 193, 228, 229 Auniann, R., 21, 48 Avakyan, N. P., 20 Avdeef, A., 286 Avenarius, I . A., 483 Averbeck, H., 21 Averill, B. A., 407 Avilina, V. N., 382 Avraamov, Y u . S.. 456 Avtomonova, A. E., 251 Avvakumov, E. G.. 505 Awerbouch. O., 153 Aydin, M., 501 Ayers, W. T., 254, 476 Aymonino, P., 212, 263, 385 Azheganov, A. S.. 170 A ~ i z o v A. , A., 60 AZman, A., 193 Baasner, B., 196 Baba, S., 310 Babeshkin. A. M... 422., 423._ 462, 463 Babikova, Yu. F., 414, 456 Babushkina. T. A.. 124. 128 Bacaud, R., 479 Bach, 13., 41 7 Bach, R . D., 76 Rackus, J. J. M., 58 Bade, D., 438, 440 Ratzel, V., 27, 347 Biiverstam, U., 501 Ragdasar'yan, A. K h., 290 Baggett, N., 44 Bagnall, K. W., 103, 296, 319, 321, 381 Bahadur, D.. 422 Bahirov. E. A., 379 Baier, H., 257 ' Baierl, P., 192 Bailev. D.. 37. 132 Bailey: P. 'M.,'87 Rain, A . D., 163 Bainbridge, J., 413 Bairamov, B. Kh., 208 Baird, M. C., 18, 87 Baisa, D. F., 175 Baishiganov, E., 290 Bajpai, B., 254 I

,

Bakeeva, R. F., 153 Baker, C., 226 Bakhshiev, N. G., 190 Baklagin, A. A., 479 Bakum, S. I., 133 Balabanova. E. A., 235 Balahura, R. J., 30 Balashov, D. H., 177 Balasubramanian, D., 64 Ealch, A. L., 57, 79, 98, 304, 352 Ualcornbe, C. I., 252, 475 Bald. J. F.. iun.. 137. 241 Baldokhin,'Yu. V., 501 Haldwin, G. C., 405 Balicheva, T. G., 173, 225, 288. 308. 372. 386. 391 Halimann, 'G., j 7 Balko, B., 412 Ballard, D. G. H., 7 Ballard, J. G . , 470 Balloomal, L., 251 Balog, M., 290 Balshaw, H., 224 Bami, H. L., 304 Banadeo, H., 220 Banciu. A. C.. 371 Banck,. J., 14 Bancroft, G. M., 144. 441, 443. 446. 463. 472. 473. 474. ' 477' Bandaev, S. G.. 40 Bandekar, J., 222 Banditelli, G., 362 Banerji, S. K., 402 Banks, E., 117, 263 Bansal, C., 463, 501 Baraban. J. M., 33 Barabash, A. I., 175 Baracco, L., 320 Baran, E. J., 212, 213, 233, 238. 263. 385 Baranetska'ya, N. K., 12 Baranovskii, I. B., 307, 356, 36 I Baranovskii, V. I., 303 Barb, D., 407, 41 I , 423, 478. 50 1 Barbanel, Yu. A., 205, 276 Barbieri, It., 254, 353, 475, 477 Barhulescu, E., 478 Harclay, J. A., 501 Barnes, A. J., 191, 200 Barnes, J. C., 63 Barnes, R. G., 417, 426 Barnett, G . H., 337 Barnett. K. W.. 1 I . 391 Rarraclough, 6. Gl, 200 Barrau, J., 143, 241 Barrett, P. H., 418, 419, 483, 503 Rarron, L. D., 360 Bart, J. C. J., 294 Barta, C., 221 Bartczak, T. J., 159 Bartel, K., 313, 334 Bartener, Ci. M., 457, 461 Bartet, B., 128 Barth, R. C., 148 Barthel, C., 196 Barthelat, M., 263 Bartke, T. C., 186 Barton, T. J., 385 '

Author Index Barvinok, M. S., 380 Baryshok, V. P., 173 Base, K., 127, 232 Bashkirov, Sh. Sh., 454, 460, 461, 476, 501 Ihshkov, B. I., 287, 386 Basile, L. J., 206 Hasler, W. D., 111 Basoon, S. A., 209 Basosi, R., 95 Bass, J . L., 212 Ilassindale, A. R., 90 Bassler, H.-J., 156, 265 Bastian, V., 151 Bastide, J., 23, 449 Hastow, T. J., 169 Batail, P., 23 Batalova, N. R., 369 Rates, C. A., 2 Bates, J. H., 194, 195. 216 'I8 Hates, R. D., jun., 85, 93 Ratista. A., 352 Battiston, G., 343 Battistuzzi. R.. 317 Battu, R. S . , 384 natyaev, I. M., 392 Hatyr, D. G., 358, 359, 430 Hau. R.. 446 H a u h x , 7 M., 151, 152, 159, 2 64 Dauer, G., 84, 241 Bauer, P., 263, 270 Bauer, S. H . , 237 Haugher, J . F., 103 Baum, K., 274 Baum, R. G., 65 Baumann, J., 505 Ilaurngarten, E., 266 Dauminger, E. R., 406, 418, 495,496, 497, 499 Ilavay, J.-C., 372 Ihviera, A., 115 Bayukov, 0. A.. 466 Bazhin, N. M., 74, 427 Ihi.ileva, 0. V., 372 Heach, D. L., I I lkachley. 0. T., jun., 83. 237 Bcngley, B., 263 Beard, C. D., 274 Hearden, A . J., 439 13earden, W. H., 21 Henttie, I. R., 16, 191, 194 Beatty, C. L., 109 Reaudet, R. A., 187 Beaulicu, W. B., 239 Becher, H. J., 199, 201, 295, 3 70 Heck, A. K . . 268 Beck, W., 37, 290, 348, 351, 367 Becker, C. A. L., 366 Becker, H. J., 28 Becker, J., 415 Bedrina, M. E., 31 I , 357 Bee, M. W., 349 Beebe, N. H. F., 163 Beer, D. C., 127, 234 Beers, Y., 184 Beg, M. A. A., 80 Begalieva, D. U., 290 Begum, N. A., 208 Begun, G. M., 226 Behrens, U., 344

509 Behrman, E. J., 304 Beilin, S. I., 287, 299 Beke, Gy., 222 Bekka, R. A., 242, 3 16 Bekturov. A . B.. 290 Belin, C., 273 Belitskii, I. A.. 212 Bell. E. E.. 304 Bellarna, J. M., 63, 136, 138, 241, 256 Bellarny, L. J., 190 Hellerby, J . M., 365, 444 Relluco. V.. 30. 313. 333 Belokov, A. T., 175 Belonogov, A. M., 1 1 3 Belonogova, 0. W., 440 Relousov, M . V., 213 Belousoba, F. V., 373 Belov, A. F., 463 Belov. A. G., 243 Belov, V. F., 420, 463 Belov, V. V., 133, 233 Relova, L. F.. 216 Belozerskii, G . N., 460 Ilel'ski, N. K., 393 Bel'skii, V. E., 153 Belyaev, L. M . , 466 Belyaev, V. A., 93 Delyaev, V. S., 453 Belyaeka, A. A., 201 Belyakov, V. A., 408, 413 Belyakov, Yu. M., 114 Ben-Rassat, A. H. I., 359 Benderskaya. L. P., 479 Bendorius, R., 210 Rendtsen, J . , 184 Benedetti, E.. 304 Benedict, J. J., 19 Benettin, M., 312, 392 Bennett, L. H., 505 Bennett, M. A., 79, 304 Bennett, R. L., 15 Bentley, F. F., 207 Bentrude, W. G . , 155, 262 Bercaw, J . E., 86, 346 Bercha, D. M.. 210 Rereman. R. D., 297 Berenblut, €3. J., 1-17 Berezin, V. I., 317 Berezina. V. F., 397 Berg, R. W., 215 Bergalieva, Z. Kh., 251 Berger, Ch., 67 Berger, J., 220 Derger, S.. 4 Bergesen, K., 155 Bergnian, R . G., 86, 316 Bergrnann, E. D., 154 Bergmann, G., 246 Bergter, L., 427 Berjot, M., 362 Berkowit7, A. E., 454 Berlin, A. A., 430 Berlin, K. D., 91 Berrnan, H. M., 157 Berrnan, S. T., 78, 257 Bernard, B. B.. 277 Bernard, D., 63 Bernard, L., 362 Rernhagen, W., 348 Bernier, P., 92 Bernstein, E. R., 276 Bernstein, H. J., 280, 362 Bernstein, L. S., 203

Bernstein, M. L., 202 Berry, F. J., 162, 484 Bertazzi, N., 244, 246, 254. 267, 316, 353, 394, 472, 475, 476, 477 Bertelli, E., 386 Bertini, I., 100 Bertoluzza, A., 238, 263, 390 Bertucci, C., 33 Bertyakova, L. V., 66, 77 Besecke, S., 100 Bestmann, H. J . , 150 Retts. C. E., 306 Beuerle, E., 157 Bevan, J. W., 189 Revan, W. I., 90, 144 Beveridge, S. J., 76 Beysel, G., 16, 307 Bezdenezhnpkh. G . V., 377 Bezrukov, I . Ya., 114 Bhaduri. S., 29. 492 Bhalla, M . S., 295, 394 Bhandari, A. M., 321 Rhandari, S. S., 464 Bharagava. S. C., 455 Hhatia. V. K., 318, 384 Bhattacharyya, R. G., 373 Bhide, V. G., 422 Bhutra, M. P., 318 Bianco, P., 238, 397 Bibin, V. N., 294 Bibolov, I. N., 456 Bickelhaupt, F., 85, 148 Bidzilya, V. A., 102 Bied-Charreton, C., 26 Biedermann, H . G., 324 Bienert, R., 250 Biersack, H., 15 B!ggi, G., 313 Bignall, J. C., 191 Bigorgne, M., 301, 310, 334, 337 Bikeev, Sh. S., 101 Billard, D., 209 Billard, L., 501 Binbrek, 0. S., 221 Binder, J . , 492 Binev, 1. A., 363 Binger. P., 130 Binnatov, K . G., 501 Biradar, N. S., 288, 31 I , 379 Birchall, T., 135, 241, 458, 470, 473, 478 Biryukov, 1. P., 147 Bisang, T., 70 Bi$hop, M. E., 140 Hishop, M. W., 368 Bishop, S. G.. 108 Bist, H. D., 197, 214 Bitter, W., 131, 141, 259 Bizot, K. F., 55, 352 Bjoerseth, A., 186 B j o r ~ y ,M., 155 Blaauw, C., 396 Black, A. M., 204 Black, J . D., 219, 339 Blackborow, J . R., 81 Blackwell, L., 304, 433 Rlauensteiii. P.. 356 Blain, M., 232 Blake, A. B., 381 Blake, D. M., 26, 309 Blaknev. G.. 76 B l a n d i 'C., 7 '

5 10

Author Index

Blaser, H. U., 45 Blasius, E., 293 Blasse, G., 212, 213, 263 Blayden, H. E., 194 Blick. K . E. 235 Bliefert, C., 271 Blinc, R., 104, 105, 110, 170, 171 Blinn, E. L., 291 Hlinova, V. A., 40 Blomberg, C., 85 Rloodworth, A. J., 40 Blum, N. A., 483 Blunt, J. W., 30 Blutau, Chr., 252 Bobkova, N. M., 288 Roccuzzi, F. C., 162 Hochkareva, V. A., 295, 296, 354, 376 Bochko, A. V.. 235 Bodea, M., 501 Boden, N., 104, 147 Hodewitz, H. W. H. J., 85 Bodner, G . M., 12, 13, 27, 34 BBhland, H., 359 Boehm, J. L., 352 Boekema, G., 457 Boese. R.. 292 Bogatyr’, D. G., 287 Rogatyr, N. I., 391 Bogdanov, G. A., 119, 291, 294.295. 372 Bogd&ov,’V. S., 77, 81, 130 Bogdanovid, B., 150 Bogey, M., 183 Bogner, L., 415, 440 Rogolovskii, N. V., 266 Bogomolov, V. N., 470 Bogonostsev, M. A., 114 Bohm, V., 222, 307 Bohn, H. G., 114 Boiko, G. N., 3, 124, 125, 133

IG G t , J . P., I I I IJokemeyer, H., 405, 413 13okii, G. B., 212 I3okii, N. G., 249 I3okov, V. A., 455, 469 I3olard, J., 201 I3oldish, S. I., 210, 319 Ijole, A., 258 I3oleskawski, M., 238 I3olga, 0. A., 80 1jolgar, T. S., 358 I3olkhova, L. A., 75 I lolourtschi, M. A., 303 I30112, c. L., 3 13012, J., 501 I3ombieri, G., 320. 362, 351 IJonardet, J. L., 123 I3onati, F., 362 I3onazzola. G. C.. 414 Bond, A., ‘19 Bondar, A. M., 108 Bondarenko, G. N., 287, 299, 333 Bondarenko, L. I., 69, 379 Bondarenko, V. S., 107, 161 Bonds, W. D., 287 Bone. S. A., 155 Bonedeo, H., 192 Bonera, G., 115 Honfoey, D. B., 36 Boniface, B., 200 ’

Bonner, 0. D., 213 Bonnet, B., 238 267, 273 Bonnet, M. C., 365 Bontschev, Z., 406 Bontschwa-Mladeno\ a, Z., 270 Bonville, P., 420 Boolchand, P., 483, 484, 489, 498, 492 Boorman, P. M., 205, 796 Booth. B. L., 18, 26, 27, 28 Bor, G., 343, 345, 347 Bora, T.. 403 Borch, G., 251. 268 Borcherds, P. H., 207 Bordignon, E., 365 Borello, E., 294 Borely, C., 499 Boreskov, G. K., 294 Borg, A., 81 Borg, 1. Y., 463 Borg, R. J., 463, 501 Borisenko, A. A.. 147, 151 Borisov, A. E., 140 Borisov, V. V., 303, 391 Borkett, N. F.. 58 Borodin, P. M.. 4, 78 Borokov, V. Yu., 121, 123, 124 Borovikov, Yu. Ya., 264 Borring, A.-L., 257 Borsa, F., 115 Borshch, A. N., 294 BorStnik, B., 193 Borzo, M., 39 Borzova, L. D., 312, 373 Bos, A., 250, 478 Bos, K. D., 143, 477 Boschi, T., 34, 56, 313, 351, 362 Bose, A. K., 8, 160 Bose, K . S., 396 Bosman, W., 309, 388 Bosnich, B., 58, 74, 306 Rosse, J., 41 I Bosworth, Y. M., 200 Botar, A., 293 Both, E., 410 Botha, V. P., 312 Botschwina, P., 195 Botto. I. L., 263 Bottrill, M . , 19 Bouanich. J. P., 193, 226 Boucher, D., 185 Boucher, L. J.. 100. 281, 300 Bouchez, R., 464 Boudart, M., 396. 450, 451 Roudjebel, B., 157 Boudjebel, H., 157, 160 Bouffard, V., 104 Bougeard, D., 230 Bougon, R.. 206. 274, 295 Bouissou, T., 263 Bouix, J., 198, 239 Bourgon, R., 73 Bournay, J . , 218 Bouquet, G.. 337 Bowden, G . J., 410, 501 Bowen, R. P., 68 Bowmaker, G. A.. 178. 315 Bowman, K . C., jun., 1 1 1 Boyd, A. S. F., 86, 305 Boyle, A. J. F., 423 Bozadzhiev, L. S., 461

Bozhko, V. P., 492 Bozhovskaya, N. V., 238 Braca, G., 304 Bradbury, J. H., 75 Bradley, C. H., 146 Bradley, E. B., 235 Bradley, G. F., 345 Bradley, G. M., 202 Brady, R., 306 Brainina, E. M., 44 Braitsch, D. M., 323 Brandan, D., 240 Brandao, D. E., 432 Brandl, A., 354 Brandon, J. K., 221 Brandstatter, E., 245 Brandt, N. B., 501 Brasme, B., 269 Brassington, J. G., 96 Braterman, P. S., 190, 339 Bratos, S., 228 Bratt, P. J., 235 Brattas, L., 483 Bratushko, Yu. I., 349 Brau, C. A., 274 Braun, R. W., 63, 319 Braun, S., 23 Braun, W., 187, 210 Braunstein, P., 283, 339 Bravard, D. C., 295 Brawer, S., 212 Bray, P. J., 104, 1 I7 Breakell, K. R., 233 Breckner, A., 147 Breed, L. W., 249 Breen, J. J., 84 Brega, V. D., 358, 359, 390 Bregadze, V. I., 83, 234 Breitinger, D., 210, 317 Breitmaier, E., 4, 84 Brekhunets. A. G., 66, 122 Bremond, J.-P., 137 Brent, W. N., 9 Bresadola, S., 306 Bressan, M., 305, 306, 366 Bressani, T., 414 Breunig, H. J., 337 Brewer, D. F., 123 Brewer, W. D., 501 Brice, V. T., 126, 232 Briggs, R. W., 69 Briguet, A., 136, 137 Brilkina, T. G., 154 Brill, T. B., 134, 168, 240 Brill, W. J., 441 Brinckman, F. E., 15 Brinkmann, D., 107 Brintzinger, H. B.. 338 Bristoti, A., 427, 432 Ihitnell, D., 297 Brittain, H. G., 7 Brnitevic, N., 291 Brockner, W., 267 Brodbeck, C., 193, 226 Brodersen, K., 283 Brodie, A. M., 178, 315 Brodzki, D., 332 Brijll, W., 432 Brook, A. G., 90, 249 Brooker, M. H., 207, 218 Brookes, A., 19 Brooks, J. S., 410, 501, 505 Broomhead, J. A., 305 Broussier, R., 23

A rithor Index

511

Brown, C. W., 191, 193, 194, 197, 268, 271 Brown, D., 285, 321 Rrown, D. B., 364 Brown, D. G., 98 Brown, E. V., 314 Brown, G. M., 368 Brown, H. C., 125, 130, 231 Brown, J. D., 276, 281 Brown, J. M., 26, 27, 102 Brown, J. R., 463 Brown, M. P., 235 Urown, R. J. C., 175. 179 Brown, S. D., 93, 268, 295, 383 Brown, T. L., 28, 167 Browning, J., 32 Hrownlee, G. S., 308 Hrownstein, M., 156 Brubaker, C. H., 287 nruce, M. I., 15, 26, 58, 327 Hriiser, W., 293 Urumfach, S. B., 194 Urunner, H., 10, 1 1 Hrunot, B., 428 Brusetti, R.,489 Rrusset, H., 219, 319 Fruyneel, W., 463 Rruzzone, M., 232 Bryan, H. A., 351 f3ryan, P. S., 186 Rryant, R. G., 29, 68, 69, 74, 76 Hryukhova, E. V., 172, 179 Uryushkova, N. V., 65 Ihzoska, B., 505 Ruback, M., 225 Bubnov, Yu. N., 81 Uuchachenko, A. L., 93 Ihcher, E., 498 Ijuchler, J. W., 292, 304, 360 Huckingham, A. D., 4, 132 Buckingham, D. A., 74, 86 Iluckley, P. D., I , 43 Buckwald, R. A., 452 Hudagovskii, S. S., 501 Hudenz, R., 271 Bider, W., 156, 157, 258, 259 Uudnik, R. A., 47 Buchi, R., 72 ljulck, J., 311. 367 Buelow, L., 199 Biirger, H., 8, 137, 243, 252, 257, 287, 353 Hues, W., 195, 240 Hui Huy, T., 73, 295 Bukala, S. S., 234 Bukhanova, A. E., 393, 396 Bukhtereva, M. A., 290 Rukin, A. S., 120 Bukina, D. A., 120 Bukovec, P., 239 Bukshpan, S., 486, 488 Bukshpan-Ash, D., 432 Bula. M. J.. 83 Bulgak, I. I,., 430 Bulka, G. R., 115 Bulkowski, J. E., 136, 241 Bulmer. J. T.. 223 Bulten,’E. J..’ 143. 477 Bulthuis, J., 2 Bulychev, B. M., 133, 233 Bunbury, D. St. P., 327, 410 ’

Bunnell, C. A., 15 Bunzel, H., 416 Bur-Bur, F.. 163. 271 Burdett, J. K., 340 Burg, A. B., 125, 137, 246 Burgada, R., 63, 155, 157, 160 Burgemeister, T., 1 1 Burger, K., 150, 268, 270, 400, 473, 474 Burgess. C.. 30, 309 Burghoff. U., 112 Burgos, E., 220 Burie, J., 185 Burke, J. M.. 360 Burkert. P. K., 179 Rurkhardt, W. D.. 152, 259 Burlitch, J. M., 302 Burmeister, J. L.. 307, 392 Burnell, C. J., 191 Burns, G.. 210 Burrows, E. L., 21 1 , 222 Burt, J. C., 48 Burton, J.. 493 Ruryak, N. I., 226, 286 Rurzo, E., 501 Rusch, R., 254 Busch, D. H., 354, 355, 431 Rusch, M. A.. 49. 344 Bucchow, K. H. T., 496, 502, 505 Busev, S. A.. 140 Buskes. H. A.. 496 Buslaev, Yu. A., 78, 144. 160, 291, 295, 296, 354, 376, 402 Buslaeva. M. N., 65, 69 Busova, Z., 406 Buss, W., 270 Russetto, L., 351 Busikre, P., 461, 479 Butcher, R. J.. 296, 397 Butler. I. S., 341, 342, 368 444 Butler, J. E., 222 Butler, K. D., 441. 473. 477 Butler. R. N.. 316 Butsko, S. S.,’39h Buttery, H. J., 222 Rnttone, 3.. 408 Rychkov, Yu. F., 502 Rykov. V. N., 501 Bykova. E. V., 307 Ryrne, J. W.. 45 Byroni, F , 456 Bystrov, D. S., 218 Bystrov, G. S., 122 Bywater, S., 6 Cabreva, A., 3 12 Cabrino, R., 313 Cadeville, M. C., 417 Cadiot. P.. 130 Cadman, P., 417 Cadogan, J. 1. G., 157 Caffery, M. L., 390 Caglio, G., 306 Cahen. J. M., 70 Caillet, P., 324, 338 Cain, G. J., 501 Cairns. M. A.. 28. 37. 331 Calhoun, H. P., 261 . Callahan, K. P., 89, 234 Callahan, R. W.. 349, 368 240 Callawav. J. 0.. CaIIigaro; L., 18 Calogero, S., 443

Calves, J. Y ., 29 I , 354 Caminati, W., 187 Cammock, R., 440, 441 Campbell, D. H., 81 Campbell, M. J. M., 287, 400 Camus, A,, 306, 331, 333, 396 Candeloro de Sanctis, S., 34 Canham, G. W. R., 277 Cannas, M., 387 Canterford, R. P 217, 220 Canziani, F., 3351 Capderroque, G., 232 capka , M., 242 Carberry, E., 90 Cardaci, G., 327 Cardin, A. D., 39 Careless, A . J., 187 Cares, W. R., 455 Carey, F. A., 194 Caric, S., 428 Carlson, T. A., 454 Carlsson, B., 418 Carmona-Guzman, E., 103 Caro, J., 122 Carre, J., 235 Carreira, L. A., 204 Carrcll, H . L., 157 Carrick, M. T., 216 Carroll, W. E., 129, 234 Carter, H. A., 145, 268, 174 Cartner, A., 346 Carton, D., 130 Carturan, G., 30, 3 13 Carty, A. J., 36, 37, 228, 313, 316, 386 Carty, P., 308 Cary, L. W., 14, 36, 88, 312 Casanova, J., 40 Casellato, U., 319, 320 Casey, A. J., 387 Casey, C. P., 15 Cash, D. N.. 308 Cashion, J. D., 494, 496, 497, 50 I Cassidy, P., 315 Cassoux, P., 186 Castan, P., 129 Castleton. K . H.. 183 C a tta lini, ’~. ,313, 320 Caulton, K. G., 29, 53, 55, 79. 152. 301 Cavi, M.’P., 3 1 2 Cavaleiko, A. M . V. S. V., 290 Cavell. R. G., 149, 152 Cazaux, L., 143 Cazzoli, G., 183, 187 Ceccaldi, M., 223 Ceccon, A., 11 Celap, M. B., 396 Cenini, S., 5 5 , 352, 403 Ceraso, J. M., 71 Cerf, C., 201 Ceriotti, A., 347 Cernik, M., 270 Cervellati, R., 183 Cetinkaya, B., 10, 313 Chachaty, C., 99 Chadaeva, N. A., 63, 155 Chadha. S. L.. 266 Chadwick, A. V., 109 Chaillet, M., 268 Chakravorti, M. C., 206, 276, 300

512 Chakravorty, A., 358 Chakravorty. D., 229, 461 Chakurov, Kh. G 461 Chamberlain J. M., 208 Chamberlain: N. F., 2 Chamberod, A., 501 Champeney, D. C., 415, 501 Champetier, R. J., 207 Champion, P. M., 407, 409, 439 Chan, M.-S., 74 Chan, P. K., 304, 473 Chand, R., 285 Chandra, G., 501 Chandra, K., 502 Chandrasekaran E. S., 287 €hang, C. C., 382 Chang, C.-H., 95 Chang, 1. J., 120 Channing, D. A., 451 Chantrell, S. J., 263 Chao, T. H., 242 Chao-shiuan Liu, 253 Chapline, G., 409 Chappert, J., 407, 442, 497, 505

Charetteur, E., 382 Charpin, P., 73, 295 Charuel, M., 196 Chatt, J., 14, 36, 97, 292, 293, 305, 346, 349, 354, 364, 368 Chatterjee, R. M., 225 Chau, J . Y. H., 373 Chaudhuri, €3. K., 118, 426 Chaudhuri, T. R., 295 Chaves, A., 209 Chaves, F. A. B., 433 Chebotarev, N . T., 300 Cheburina, L. A., 173 Chechernikov, V. I., 504 Chekalova, E. G.. 75, 81 Chekmarev, V. P., 115 Chen, K.-N., 21 Chen. S. C., 23 Cheng, C.-W., 32 Cheng, P.-T., 80 Chenskaya, T. B., 310 Cherches, Kh. A., 113 Cheremesina, I. M., 31 1 Cherepanov, V. M., 457 Cherlow. J. M., 193 Chernyshcv, A . I., 83, 102 Chernyshov, B. N., 73 Cherwinski, W. J., 35 Chetty, S. C., 467 Chew. K . F.. 5 C’hcyne, R. M., 485 Chereau, J. M., 109 Chia, L. S., 28, 177, 445 Chianelli, R.. 203, 289 C‘hiang, R.. 439 Chiavassa, E., 414 Chibirova, F. Kh., 481, 482 Chichaw\.. A. V.. 465 ChieIi, P . c., 316 Chien, C . L., 501 Chicrico, A., 106 Chihnra, t i . . 109 (’Iiikuma, M.. 97 Cliini. P., 5 5 . 347 C’hirhin, C i . K . , 83 ChirLov, A. K . , 114 Ch i~h o lm . M . H., 3, 31, 32. 46, 8 5 , 8 8 , 379

Author Index Chistokletov, V. N., 261 Chistyakov, I. G., 418 Chistyakov, V. A., 501 Chiswell, B., 359 Chjttenden, R. A., 157 Chrvers, T., 205 Chi-wen Cheng, 253 Cho, Z. H., 415 Choca, M., 205 Chodos. S. L.. 204 Chodosh, D. F., 47 Choisnet, J.. 251 Chojnacki, T. P., 307 Chokki. Y.. 65 Chopin; C.; 411 Chottard, G., 201 Chow, K. K., 393 Chow, S. T., 397 Chow, Y. W., 439 Christe, K. O., 147, 160. 163, 198, 200, 203, 206, 252, 273 Christensen, A., 159 Christensen, L. C., 228 Christoe, C. W., 215 Christopher, R. E., 259, 324 Christophides, A. G., 391 Christov, D., 406 Chrobokova, E., 270 Chu, C.-K., 16, 326 Chu, H., 78, 85 Chua, K. L., 100, 312 Chudnovskaya, G. P., 276 Chudy, J. C., 401 Chugunova, G. P., 41 1 Chukhovskii, F. N., 413 Chumaevskii, N. A., 316 Chung, H. L.. 234 Chung, I., 105 Chung, Y. L., 26 Chung-Yi Lee, R., 61 Churakov, V. G., 404 Churchill, M. R., 21. 47, 302 Chuvaev. V. F., 9, 14, 67, 112, 287, 295, 386 Chuvileva, G. G., 122 Chuvylkin, N. D., 130, 147 Chvalovsk9, V., 137. 140 Chwojnowski, A., 83 Ciani, G., 46, 347 Cihonski, J. l.., 193, 340, 343 Cirak, H . , 433 Cirak, J., 427, 456, 179, 505 Cirlin, E. H., 462 Ciureanu, M., 273 Claes, K., 493 Claessen, H. M., 297 Clague. A. D. H., 36 Clardy, J. C., 37, 390 Clare, P., 156 Clark, E. R., 272 Clark, G. R., 344 Clark, H. C., 31. 31. 56, 80, 789, 309, 310. 31 I , 334 Clark. M. G.. 492 Clark; P. E., 454. 450 Clark, P. W., 53, ,307, 332, 37 1 C l a r k , K. J., 49, 344 Cl:rk, R . J. € I . , 191, 200, 202, -04, ‘80 Clarhc, TI. A , . 1 7 . 3.33 Clarbc, 1’. L., I34 Cldrhc, It.. 209

Clase, H. J., 331 Clausen, C. A., tert., 491, 500 Claydon, M. F., 211 Clayton, W. R., 125 Clearfield, A., 385 Clegg, W., 317 Cleland, A. J., 331 Clerc, T., 2 Clerici, M. G., 25, 306 Cloyd, J. C., jun., 13, 147, 148, 285 Clugston, M. J., 92 Coates, G. E., 7 Cochoy, R. E., 23 Cochrane, R. W., 501 Coe, C. G., 100, 300 Coe, D. A., 229 Coelho, A. L., 355 Coetzee, J. H. J., 153 Coey, J. M. D., 407, 421, 464, 489, 494 Cogne, A., 150 Cohen, M. A., 28 Cohen, R. L., 495 Cohen, S. G., 440 Cohen, S. M., 20, 163, 327 Cole-Hamilton, D. J., 79, 388 Collin, R. J., 285 Collins, M., 129 Collins, R. L., 442, 490 Collman, J. P., 438 Collomb, A., 460 Colombini, G., 402 Colquhoun, I . J., 31 Colthup, N. R., 190 Colton, R.. 16, 301, 342 Coluccia, S., 294 Commenges, G., 83, 129 Commons, C. J., 16, 343 Condorelli, G., 320 Condrate, R . A., 217, 288 Conneely, J. A., 26, 27 Connolly, J. W. D., 416 Connor, J. A., 339, 381 Consiglio, G . , 85 Constantinescu, S., 501 Conti, F., 352 Conti, L. G., 122 Contreras, J. G., 198, 276 Conway, A. J., 339 Cook, K. L., 183 Cook, T. H . , 229 Cooke, C. G., 446 Cooke, D. F., 118, 169 Cooke. M., 53 Cookran, K. J., 75 Cooper, G. H., 157 Cooper, M. K., 32, 337 Cooper, P. J., 243, 253 Cooper, R . A., 43 Copper, P. J., 188 Coqblin, R., 500 Corbelli, G., 185 Corbett, J. D., 134, 176 Corigliano, F., 290 Cormier, A. D., 276, 281, 389 Cornell, D. A., 107 Cornilson. H. C., 217 Cornus, M., 63 Cornut, R.. 500 Cornut. J . C ., 196, 7 2 3 Cornwcll, A . R . , I I , 19, 6 2 , 345, 374, 436, 471, 473 Coronas, J. M., 31 I, 393

Author Index

513

Coskran, K. J., 366 Cosrna, C., 111 Costa, D. J., 153, 154 Costa, G., 26, 331 Costarnagna, J. A., 432 Costello, A. J. R., 159 Costes, J., 90 Costes, R. M., 319 Costin, A., 386 Cotterill, R. M. J., 505 Cotton, F. A., 43, 45, 48, 50, 51, 59, 283 Cotts, R. M., 66 Couch, D. A., 86 Coucouvanis, D., 387, 390 Coulson, C. A., 228 Coulthard, M. A., 494 Couret, C., 142 Courtois, D., 191 Coussement, R., 423, 440, 464, 489 Coutts. R. S. P.. 287 Couzi,’M., 213 Covington, A. K., 67, 222 Cowley, A. H., 61, 63, 150 Cox. A. W.. 255 Coy-YI1, R.; 463 Crabtree, R. H., 349 Craciunescu, D., 3 13 Cradock. S . 4 1 . 135. 137. 191. 240,241 ’ ’ Cradwick, P. D., 349 Craft, R. W., 400 Cragg, R. H., 235 Craia. P. J.. 10 Craighead, K. L., 29, 68, 69, 74 Cram, A. G., 224 Cramer, R. E., 68, 86, 102, 353 Cranshaw, T. E., 503 Crawford. S. S., 379 Crea, J., 80 Creasear, C. S., 276 Crecelius, G., 495, 497 Creel, R. B., 116 C’reighton, J. A., 276 Cremer. S. E., 148 Cresswell, P. J., 86 Cresswell, D. J., 123 Creswell, R. A., 186 Cristiani, F., 324 Critchlow, P. B., 52, 302 Croatto, U., 351 Cmciani. B., 313, 322 Cronin, D. L., 5 Crookes. J. V.. 315 Cros, G . , 90 Cross, R . J.. 58 Crumbliss, A. L., 359, 392 Csakvari. E.. 473 Cser. L,,’ 462 Cucinella, S., 232 Cullen, D. L., 47 C’ullen. W. R.. 14, 16, 17, 28, 34, 50, 79, 85, 177, 445, 478 Cullis. A. G., 480 Cunningham, D., 474 Cunningham, J . A.. 92 Cunninghame, R . G . , 346 ~ ~ ~ l i n u lR., t c ,222 < i i i ran, C., 385. 475 C‘tirtis, E. C., 352 C lirtis, N. I-., 356 ’

‘

Cushner, M., 150 Cutler, A., 20 Cyvin, B. N., 203, 357 Cyvin, S. J., 191, 198, 203, 240, 267, 292, 357 Czako-Nagy, Z., 473 Czjzek, G., 489 Czopnik, A., 496 Dabard, R., 23 Dabrowski, L., 455, 456 Da Costa, F. M., 490 Dkmmgen, U., 8, 287, 353 Dagg, I. R., 183 Dahl. A. R.. 90. 141. 142. 241, 246, 250 Dahl, L. F., 347, 445 Dahlhoff, W. V., 130 Daigle, D., 13, 340 Dakkouri. M.. 187 Dale, A. J., 62 Dale, B. W., 408 D’Alessio, E., 192, 220 Dal Farra, M., 11 Dalgleish, W. H., 174 Dalirnov, D. N., 153 Dalrymple, D. L., 160 Daly, F. P., 194, 271 Daly, J. J., 22 Daly, L. H., 190 Dalziel, J. A. W., 401 Dalziel, J. R.. 267 Damangeat, C., 493 Damle, S. D., 108 Dance, N. S., 268 Daneshrad. A., 142 Daniel, F. B., 304 Daniels. J. M., 41 1, 501 Danilewicz, J. C., 373 Danon, J., 428. 442, 465, 491 Danzer, W., 348 Dao, N. Q., 319 Dapporto, P., 18, 302 Darensbourg, D. J., 85, 332 Darensbourg. -. M. Y.. 13. 85. 340, 342 Dariel, M. P., 501, 502 Darragh, J. I . , 167 Darwish. A.. 394 Das, T. P., 416 Dasgupta, S. R., 307 Dash, B., 360 Dash, K. C., 392 Date. S. K.. 420 Dattagupta, S., 411, 412 Daub, J., 52 Daunt. J. G.. 123 Dautob. L. M. 461 Dautreppe, D.. 172, 175 Davrd, I-’. G., 434 Davidenko, N . K., 102, 381 Davidovich. R . L.,, 73.. 161. 920, 386,481 Davidson, D. W.. 105, 110 Davidson, G . , 327. 3 1 8 Duvidson, G . R., 499, 500 Davidson, J. L., 17, 19, 34. 364 Davies, B. W.. 244, 474 Davies, G., 373 Da\,ies. Ci. J.. 492 I>n\ies, J. E. D., 217 D‘rLit‘s, M. B., 224 DaLic.;. N . C., 417 ’

,

Davignon, L., 302, 393 Davis, A. R., 225, 316 Davis, D. G., 71, 78 Davis, L. C., 441 Davis, R., 22 Davis, R. B., 373 Davis, R. E., 21 Davis, R. F., 479 Davison, J. B., 138 Davydov, V. A., 202 Dawes, P. P., 479 Dawson, D. A., 138 Dawson, P., 215, 217, 221 Day, R. K., 410, 501 Day, R. O., 57, 333 Day, V. W., 57, 81, 320, 333, 348 Dayal, B., 488 Dazord, J.. 235 Dean, G. W., 501 Dean, P. A. W., 76, 283 de Beer, J. A., 446 de Bettignies, B., 225 de Bie, M. J. A., 142 De Boer, B. G., 21, 47, 301 De Boer, E., 43, 70 Debrunner, P., 439 Debruyne, D., 162 De Camp, W. H., 306 de Carvalho, L. K. F., 404 Dechter, J. J., 77 Decius, J. C., 215 Deeg, T., 169 Deeming, A. J., 86 de Filippo, D., 324, 387 De Fonzo, A. P., 21 I . 265 Deganello, G., 18, 34, 48, 56, 351, 362 De Gennes, P. G., 410 Degetto, S., 320 de Graaf, H. G., 148,424 De Groot, K., 501 Dehand, J., 283, 313, 339 De Haves. L. J.. 14 Dehe, G.,‘453, 455 Dehnicke, K., 230. 233, 234, 244. 254. 258. 267. 290. 353 de- Hosson, J. ‘Th. ’M., ’318, ,377

DAl’A., 100 Deiseroth, H.-J., 303 de Jaegere. G.. 366 Dekabyun, L. L., I13 De Ketelaere, R. F., 149 Dekhtyar, I. Ya.. 114, 501 Delbouille. A., 450 Delcroix, P., 464, 479, 503 De Leeuw, J., 274 Delgass, W. N., 495 de Liefde Meijer, H . J.. 7, 322 Delimskii, Yu. K., 227 Delise, P., 106 Dellacasa, G., 414 Delmas, M. A., 143 Delrnau, J., 136, 137 Delplanque, C i . , I 1 I Delpuech, J.-J., 77 De Lucia, F . C., 181, 183. 1 S4 Delyagin, N. N., 501 Demas, J. N., 30 Dcmco, D. L .. 7 , I 1 3 Dc Member, J . K . , 70 Demerscimn, H . , 337

514

Author Index

Demetriou, B., 336 Demuth, K., 246, 257, 265, 299. 343 Dening, D. C., 168 Denise, B., 87, 309, 332, 371 Denisenko. G. 1.. 122 Denisov, V. M., 83 Denisovitch, L. I., 329 Denney, D. B., 154 Denney, D. Z., 154 Denney, R. C., 190 Denning, J. H., 238 Denniston, M. L., 131, 161 Dent, S. P., 313, 404 Deplano, P., 324, 387 Deporcq-Stratmains, M., 202 Derbyshire, W., 5 Dereppe, J. M . , 108 Dernova, V. S., 200 Derr, H., 240 d e Sanctis, S. C., 351 Desbat, B., 198 Deschauvres, A., 251 Desclaux, J. P., 416 Deshayes, J., 464 De Siqueira, M. L., 416 Desjardins, C. D., 162 Deslauriers, R., 4 Desreux, J. F., 1 0 0 De Trobriand, A, 223 Deutch, B. I., 468 Deutsch, E., 30 Devanarayanan, S., 4 I 8 Devarajan, V., 212 Devaure, J., 226 Devillanova, F., 324 d e Villardi, G. C., 101 de Villepin, J.. 214, 217, 258 Deviller‘s, J., 63 Devin, C., 375, 378, 383 Devine. A. M . . 141. 144. 250 L>evlin,’l. P., 201, 2’4 De Voe, J. R., 478 De Voe, S. V., 149 Dcvort, J. P., 481 de Vos, D., 140 Devoto, G., 285 de Vries, J. L. K. F., 416 De Waard, H., 483, 489, 490 Dewan, J. C., 290 Dexheimer, E. M., 144, 241 Dey, K., 361 De Young, D. B., 417 Dezsi. I.. 408. 409. 420. 424. 428: 432, 433, 442 Dhamelincourt, M.-C., 201 Dhar, S. K., 246 Dhingra, M. M., 96, 99, 103 Diamandescu, L., 41 I , 501 Diamant, A., 495, 496, 497 Diamantis, A. A., 14, 348, 349 Dias, S. A., 26, 334 Diaz, A., 324, 393 di Bianca, F., 244, 246, 254, 472. 476 Dickinson, R. J., 446 Dickinson, W. L., 351 Dickman, B., 239 Dickson, B. L., 420 Dickson, D. P. E., 440, 441 Dickson, R. S., 27, 28, 54, 331, 345 Dieck, R. L., 261 ’

’

Diehl, P.. 1 Dietl, M., 264 Dietrich, K., 316 di Gioacchino, S., 25, 306 Dilbeck, C. A., 91 Dillon, K. B., 88 Dilworth, J. R., 97, 293, 295, 368 Diman, E. N., 251 Dimroth, K., 38, 62, I54 d’lncan, J., 191 Dines, M. B., 289 Dipans, I., 242 di Pasquale, S., 290 Di Piro, F., 122 Dirand, J., 295 Dirkse, T. P., 76 Disalvo, F. J., 467 Di Santi, F. J., 23 Di Sipio, L., 443 Diversi, P., 374 Dixon, J. F., 140, 336 Dixon, K. R., 36. 37, 313 Dixon, N. S., 492. 498 Dixon. T. A., 182 Dmitricheva, N. A., 239 Dmitriev, V. P., 206, 216 Dmitrieva, L. V., 114 Dmitrieva, T. M., 466, 469 Doadrio, A., 313 Dobbie, R. C., 89, 151, 156, 257 Dobbs, G . M . , 184 Dohraniyd, W., 215 Dobrzynski, E. D., 390 Dobson. A., 79, 301, 302, 369 Dobson. C . M., 102 Docken, K. K.. 180 Dockum, B., 304, 430 Doddrell. D., 40, 134 Doddrell, D. M.. 92, 96 Dodokin. A. P., 456 Dotz, K. H., 10, 323 Dokuchaeva, I. M . , 216 Dolan. P. J., 126 Dolgashova, N. V., 357 Dolgoplosk, B. A., 287, 290, 299 D’Olieslager. J., 366 Dollish, F. R., 207 Dolphin, D.. 292 Dombek, R . D., 9, 338 Domnina, E. S., 97, 143 Don, B., 446 Donaldson, J. D., 209, 266. 273, 470,’471. 473, 482 Donets, 1. G., 251 Donnav. J. D. H.. 207 Ilonnier, M., 137’ Ilonohue, P. C., 467 Il oonan, D. J., 57, 98 Il oran, C. J., 208 IDorko, E. A., 199 IIormond, A, 7 IDornfeld, El., 276 IDorokhov, Yu. G., 294 1Boronina, L. A., 288, 386 1Doskocilova, D., 103 IDostril, K., 270 IUouek, I., 474 1Doughertv, J. P., 718 Douglas, k. E., 30, 376 Douglas, P. G., 301 Dovgei, V. V., 290, 363

Downs, A. W., 26, 334 Dows, D. A., 215 Dowty, E., 462 Doyle, G., 373 Dozzi, G., 232 Drager, M., 144, 252. Drafall, L. E., 319 Drago, R. S., 100, 360, 435 Drake, J. E., 265 Dreeskamp, D., 39, 138 Drent, E., 211 Drentje, S. A., 483, 489 Drew, D., 85, 229, 342 Drew, M . G. B., 303 Drifford, M . , 198, 216 Drijver, J. W., 501 Drokin, A. I., 466 Drost, H . , 413 Druding, L. F., 307 Dubbers, D., I l l Dubiel, S. M . , 502 Dubinin, V. N., 449, 461 Dublon, G., 502 Du Bois, D. L., 148, 264 Dubois, J. E., 292 Dubois, J. M., 418 Dubois, R., 68, 102 Dubrova, E. G., 207 Dubrovskii, G. P., 2013 Dubrulle, A., 185 Duce, D. A., 327, 318 Ducourant, B., 267 Ducruix, A., 34 Dudek, M., 295 Dudnik, E. M., 112 Dudnikova, K. T., 0 5 Dudreva, R., 437 DutT. J. M . . 249 Duff, K. J.,.437 Duggan, D. M., 276, 301, X Y . 329. 352 Dulin; D. A., 294 Dumas, G. G., 220 Dumesic, J. A., 396, 450, 451 Dumont. G . , 489 du Mont. W.-W.. 141, 144. 246, 253 Dunaj-JurEo, M., 314 Duncan. I. A.. 142 Dunlap,’ B., 493, 499, 500 Dunmur, R. E., 150 Dunn, J. G., 301, 365 Dunsmuir, J. T. R., 219 Dunster, M. O., 60 Duo, R., 427 Duperray, M . - H . . 351 Duplan, J . C., 136, 137 du Preez. J. G. H.. 103, 296. 321, 382 Durbin, G. W.. 457 Durie. J. K.. 186. 187. 188. 2Oi: 204. 2j7. 243. 249, 253. 255; 256, 265 DuSek, B., 287, 379 Dushin. R. B.. 205., 263.. 276 Dutartre, R., 461 Dutasta, J. P., 91, 156 Dutt, N. K., 357, 382 Dutz, H., 104 Duvckaerts. Ci.. 321, 312. 336 Dvbrkin, M . I.,‘ 201’ . Dwek, R. A., 92 Dwight, A. E., 493, 501, 504 Dwnich, T. F., 84

A rr tho r Index Dwyer, M., 74 D’yachenko, Yu. J., 304,355 Dyakov, V. M., 173 Dyntkin, B. L., 41,242,316 Dyatlova, C. V., 436 Dyatlova, N. M., 72, 383,

394, 398

Dybowski, C. R., 113 Dye, J. L., 70,71 Dykes, E., 217 Dylis, D. D., 195 Dyrnanus, A., 182 Dyrnova, Z. N.,119 Dyson, J., 151,261 Dzevitskii, B. E., 423,462 Dzhakhva, N.G., 479 Dzharnalova, Z. O., 290,380 Dzharnarov, S. S., 235 Dzhuraev, N. D., 238 Dziomko, V. M.,382 Dzyuba, E. D., 288 Dzyubenko, N. G., 318 Dzyublik, A. Ya., 412

515 Einstein, F. W. B., 16 Eisch, J. J., 59 Eisenberg, R.,57 Eisenstadt, A., 21 Eisenstein, J. C., 463 Eissa, N.A., 463. 464,479 Eisukov, E. P., 502 Eivazov, E. A., 466 Ekdahl, T., 501 Elder, P. A., 54 El-Ezaby, M.S., 318,352 Elfring, W. H., 361 Elgad, U., 85,271 Eliezer, Z., 466,502 Elistrator, N.V., 458 Elizarova, G. L., 478 Ellenberger, M.,72 Ellerrnann, J., 255, 292, 304,

308,370, 371

Eroshok. R. G.. 396

Esparza; F:, 147 Espinosa, G. P., 456 Estes, E. D., 386 Ettore, R., 358 Etzrodt, G., 27,347 Eujen, R., 41,137,243,257 Evans, B. J., 396, 455, 483,

502

Evans, C. A., 76 Evans, D. F., 37, 101 Evans, E. L., 417 Evans, G. O., 343 Evans, I. f’., 24 Evans, J., 48,54,55 Evans, M.C. W., 440 Evans, W. J., 89,234 Evdokimov, M. D., 463 Everett, G. W., jun., 24, 72,

Ellestad, 0. H., 202 Ellis, D. E., 456 Ellis. G. E.. 66 Ellis; H. W:, 207 Ellis, J. E., 8,323,340 92 Eahorn, C., 26, 31, 142, 310, Ellis, P. D., 24, 39, 125, 126, Everhart, D. S., 58 313, 404 129 Eversteijn. P. L. A., 366 Eade, L. M., 307 El’natanov, Yu. I., 62 Evilia, R. F., 58 Endy, C. R., 52,345 El’ner, V. Ya., 505 Evsikov, V. V., 69,239 Early, D. D., 168 El Saffar, Z. M., 1 1 1 Evstaf’eva, 0. N.,270, 309, Easleal, A. J., 70 Elschenbroich, C., 370 386, 395 Eastland, G., jun., 317 Elsner, G., 317 Evstyukhina, 1. A., SO2 Eaton, D. R.,75 Ely, N. M.,103, 318,336 Evtushenko, N. P., 226, 286 Eaton, G. R., 44 Elzaro, R. A., 186 Ewing, J. J., 274 Eaton, S. S., 44 Erneis, C. A., 21 1 Ewings, P. F. R., 145,250,471 Ebert, A., 120 Emme, L. M., 295,383 Extine, M., 46,85,379 Ebert, M., 304 Ernons, H.-H., 67 Eysel, H. H., 193 Ebert, W., 120 Ernori. S., 116 Ezerskaya, T. P., 113 Ebiko, H., 408,450 Empsall, H. D., 25, 28, 32, Ezerskaya, N. A., 395 Ebisuzaki, V., 213 306, 334 Ezhov, A. I., 312, 352, 373, Ebner. J. R..283 Emsley, J. W.. 2, 16 382 Ebsworth, E. A. V., 41,135, Endell, R.,354 137,240,241 Endres, H., 398 Fabretti, A. C., 285 Eckardt, D., 405,413 Enemark, J. D., 53,352 Fabulyak, F. G., 124 Edelev. M.G.. 130 Enernark, J. H., 55 Fachinetti, G., 364 Edeklass. S. M., 458 Eng, G., 140,244 Fackler, J. P., jun., 286 Edgington, D., 462 Engel, R.,75 Fadeev. Yu. V.. 31 1. 404 Edlund, U., 93 Engelhardt, G., 10, 41, 144 Fagnano, C., 238 Edmonds. D. T.. 167 Engelsberg, M., 109 Fairhurst, M . T., 76 Edwards.’A. J.. 291. 354. 375 Englemann, T. R.,27 Falardeau, E. Jt., 147,15 I , 265 Edwards; D. A:, 16,‘301,’315,Engler, E. M.,162 Falconer. W. E.. 119. 193 336, 365 English, A. D., 9,33,53 Faleev, D. S., 562 Edwards, J., 10,103,321 Falk, M., 196,197,203 Ennan, A. A., 253 Edwards, J. D., 19 Faller, J. W., 48,53 Ensling, J., 444 Edwards, P. A., 134, 176 Faltynek, R.A., 8,323 Enterling, D., 141 Eeckhaut, Z., 132 Fan, A., 466 Epperlein, B. W., 43, 131 Efes. E. F., 210,304 Faniran, J. A., 375 Epps, L. A., 86 Efratv. A.. 341 Fannin, L. W., 79 Epstein, M.,101 Efremov, V. A., 287 Fantucci, P., 55 Erchak, N. P., 242 Eggers, D., 268,271 Farago, M. E., 86,384 Ererneako, V. V., 211 Eggers, D. F., 271 Faraone, F., 388 Erernin, E. R., 89 Eggersdorfer, M ., 268 Erernin, Yu. P., 121,379, 393 Farhangi, Y., 84 Egorochkin, A. N.,241 Farkas. E.. 75 Erernina, E. P., 273 Egorov, A. S.. 359,474 Erickson, L. E., 35 Farmer, V: C., 190,207 Egorov, V. D., 243 Ericsson, T., 417, 418, 468, Farnum, D. G., 3 Egorov, V. K., 465,466 502 Farona, M. F., 254,255,445, Egorov, Yu. P., 146,264 476 Erikssun, L., 415 Egorova, A. A., 368 Ermakov, A. E., 503 Farrar, T. C., 144 Ehlert, K.. 254,477 Ermakova, M. N.,249 Fasag, K. M.,14 Ehlrnann, A. J., 230 Ermatov, S. E., 241 Fately, W. G., 207 Ehntholt, D., 20 Faulds. G . R.. 348 Errnolaev, V. K., 112 Eibschiitz, M., 426,467,499 Ernst, H., 103 Faurskov Nielson, O., 433 Eicher, H., 438,440 Ernstbrunner, E. E., 346 Favre, R.,198 Eiletz, H., 151 Erofeev, L. N.,89, 113, 125 Fawcett, V., 217 Einig, H., 259 Eromalev, V. K., 161 Fay, R. C., 44,45,287 ’

‘

18

516 Fazakerley, G. V., 73, 285 Faznano, C., 263 Featherman, S. I., 62 Fedin, E. I., 12, 20, 22, 23, 39, 40, 61, 121, 128, 140, 154 Fedodeev, V. I., 121 Fedorin, V. L., 415 Fedorov, L. A., 12, 20, 39, 40, 41, 44, 81, 128 Fedorov, V. E., 466 Fedorovskii, Ya. A., 479 Fedro, A. J., 104, 504 Fee, W. W., 402 Fehlhammer, W. P., 313, 334 Feiccabrino, J. A., 243, 381, 475 Feigel, M., 150 Feldman, C., 483 Felkin, H,. 34 Felner, I., 406, 418, 495, 497 Feltham, R. D., 53, 55 Fender, B. E. F., 460 Fenaer. J.. 41 5 Fenske; D., 370 Fenske, R. F., 445 Fenton, D. E., 145, 250,471 Fenton. R. H.. 362 Ferguson, G.,’231, 306, 381, 386 Ferguson, J., 214 Ferauson. M. W.. 455 Ferguson; S. J., 3 Fernandez, V., 290 Ferraro, J. R., 205, 206, 207, 275 Feser, M., 261, 269 Feshchenko, N. G., 264 Feshin, V. P., 173 Fetter, K., 129, 232 Fiat. D.. 101 Fick, H.‘G., 290 Field, R., 180 Field, R. W., 183 Fields. R.. 20 Figueras, F., 479 Fild, M., 150, 151, 156 Filgueira, R. R., 185 Filho. W. W.. 178 Filin.’M. V., 458 Filippov, A. P., 73 Filippova, T. M., 130 Filoti, G., 454 Finch, M. A., 252 Fini, G., 247 Fink. J.. 489 Finkman, E., 2 1 1, 265 Finocchiaro, P., 44 Firestein, G., 325, 379 Firov, A. I., 486 Firsova, A. A., 461 Fischer, D., 141, 241, 245 Fischer, E. O., 10, 1 1 , 322, 364 Fischer, F., 21 I Fischer, G. W., 160 Fischer, J., 96 Fischer, J. C., 269 Fischer, P., 52, 133, 247 Fischer, R., 141 Fischer, R. M., 462 Fischler, I., 21, 343 Fish, R. H., 88 Fishman, A. I., 257

Author Ina Fitzpatrick, N. J., 132 Fitzsininions, B. W., 432 Fjeldly, T. A., 208 Flamini, A., 312 Flanagan, M. J., 187, 249 Fleish, J., 435 Fleming, C. A., 277 Flemming, V., 277 Fletcher, J. L., 1 1 Flewett, G. W., 273 Flick, W., 141 Flint, C. D., 204,285,293,294 Flood, T. C., 23 Florence, J.-C., 138 Floriani, C., 291, 364 Fluck, E., 157, 408, 444, 473 Flynn, B. R., 306 Flynn, C. M., jun., 30 Fochi, R., 162 Foct, J., 418, 501 Fokin, V. N., 125 Folcher, G.. 319 Foley, P., 61, 246, 472 Folland, R., 109, 147 Fomicheva, K. K., 295 Fomina, T. A., 309 Foner, S., 430 Fong, F. K., 79 Fontana, M., 209 Fontana, S., 364 Fonteneau, G., 319 Fookes, C. J. R., 159 Forchioni, A., 99 Ford, L. O., 102 Forel, M. T., 238, 239, 249, 390, 404 Forester, D. W., 497, 502 Formanek, H., 438 Formicka-Kozlowska, G., 41, 96 Fomina, T. A., 386 Forneris. R.. 202 Forni, E., 374 ForniCs, J., 312, 357, 393 Forrest, 1. W., 219 Forrest. J. W.. 109 Forsellini, E.,’ 320 Forsen, S., 3, 82 Forsythe, D. A., 226 Forti, P., 185 Fortunato, B., 247 Fotiev, A. A., 1 I4 Fouassier, M., 238, 239 Foucaud, A., 156, 157 Fourcade, R., 267 Fowles, G. W. A., 297 Fox, W. B., 273 Foyt, D., 408, 490 Fradin, F. Y., 92, 503 Fragala. I., 320 Frahm. J.. 68 Fraissard,’J. P., 124 Frait, Z., 100 Fraitova, D., 100 Fraknov. V.. 482 Franc, B., 262 Franck, E. U., 196, 225 Franck. R., 295 Frank, A., 1 I , 370 Frank. E.. 432, 462 Franke, P., 145 Franke, R., 38, 313, 316 Frankel, R. B., 304, 407, 419, 430, 432, 435

Frankiss, S. G., 194 Franklin, M., 28 Franks, M. L., 191, 280 Franz, J. A., 264 Franz, K. D., 13 Fraser, G. W., 163 Fraser, L. R., 381 Fraser, M. J., 474 Fratiello, A., 82, 133 Frauenfelder, H., 405 Frazer, G. W., 273 Fredette, M. C.. 374 Fredga, -A., 161 Fredin, L., 196, 228 Fredrickson. L. R.. 215 Freedman, T. B., 361 Freeman, A. G., 414 Freeman, A. J., 406, 407, 4 456 Freeman, R. R., 180 Freeman, W. H., 134, 168 Freeman, W. J., 85, 149, 1 153, 160 Freitag, W., 101 Frembs, D. W. R., 404 Freni, M., 46 Freymann, R., 128, 232 Fridman, A. Ya., 398 Fridman, Ya. D., 357 Friedt, J. M., 414, 428, 4 488, 499, 503 Friese, G. J., 207 Fripiat, J. J., 120, 122, 123 Frisse, M. E., 368 Fritz, G . , 131 Fritzer. H. P.. 215 Fritzsche, H.,’95 Frlec, B., 275 Froehlich, F., 113 Frraven. P.. 62 Frojndiich,’ D., 406, 418. 41 Froix, M. F., 109 Frolkov, Y. A., 175 Frolov, E. N., 407, 440 Frolov, V. I., 291 Frolov, V. M., 290 Frolova, 0. M., 462 Frolova, T. L., 503 Fruwert, J., 268 Frye, J. S., 96 Fuller, H.-J., 133 Fullgrabe, H.-J., 131, 142, 2 Fuentes, R., 25 Fuentes, R., jun., 75 Fuger, J., 321, 336 Fuhr. B. J.. 76 Fuhrhop, J.-H., 100 Fujimoto, S., 441 Fujioka, M., 449 Fujioka, N., 505 Fujita, F. E., 406, 417 Fujito, T., 103 Fujiwara, F., 132 Fukai, Y., 114 Fukushima, E., 113 Fukushima, K., 360 Full, R., 22, 130, 233 Fumagalli, A., 55 Funck, E., 212 Fung, K. W., 226,289 Funke, L. A., 87 Furman, K.,369 Furubayashi, R., 450 Furuike, C. K., 102

Author Index

517

Furukawa. Y.,174, 175, 176 Furuya, N.. 218 Fussenegger, R., 43 FUSU, I. L., 355 Gabelnick, S. D., 283 Gabes, W., 320 Gabriel, H., 411 Gabrielli, A., 21 Gabuda. S. P.. 107. 113. 116 Gadsden, J. A:, 190 ‘ Giibelein, H., 292 Gaechter, B. F., 222, 307, 322, 329 GBthje, D., 252 Gager, H. M., 408 G a p e , R. R., 438 Gaidamaka, A. P., 492 Gailey, K. D., 30 Gaines, D. F., 6, 126 Gainsford, G. J., 74, 86, 339 Gajendragad, M. R., 285, 400 Gal, A. W., 309, 388 Galaktionova, 0. V., 384 Galat, V. F., 121 Galbraith, A. R., 301 Gale, D. J., 142 Galich, P. N., 120 Galitsyn, Yu. G., 119 Gallagher, K. J., 396 Galla her, M. J., 159 Gallafer, T., 178 Gallo, A. A., 73 Gallus-Olender, J., 262 Galois, A., 301 Galyutina, E. F., 415 Gambino, O., 51 Gamble, F. R., 115 Game, C. H., 299 Gams, R. A., 77 Ganapathy, S., 103 Gancedo, J. R., 492 Gangas, N. H., 464 Ganguli, P., 96, 422 Ganin, V. V., 3 I7 Gans, P., 259, 359, 392 Gaoni, Y., 22 Garaj, J., 314 Garber. A. R.. 10. 126. 127,. 129, 232 Garbuzova, I. A., 302, 314, 333 Garcia Figueroa, E., 312 Gard, G. L., 93, 268, 295, 383 Gardiner, D. J., 225 Gardner. S. A.. 54. 332 Garg, A: N., 365, 434, 441 Garg, S. K., 105, 110 Garg, V. K., 427, 433, 434 Ganto. A. P.. 312 Garmash, V.‘Ya., 456 Garner, C. D., 159, 283, 296 378 Garnett, M., 385 Gamier, F., 292 Garrard, J. E., 301, 342 Garreau, M., 162 Garrone, E., 294 Garrou, P. E., 5 , 10 Garroway, A. N., 66 Garten, R. L., 461 Gasanov, A. I., 9, 14, 112 295 ~~,

;asanov, M. S., 208 :asanova, R. Yu., 249 Jasasnov, K. G., 128 ;ashimov, G. I., 466 ;asiunas, K., 112, 113 ;aspamini, F., 313 ;asser, O., 150 ;assmann, P. G., 332 3ast. E., 267 3atilova, S . G., 235 3audemer, A., 26 3aughan, A. P., jun., 218 3aushan. R. R., 281 3auK M.’, 12 ;sunder, R. G., 400 3autier. F.. 489 Sautheron,’R.. 8, 23 3avini. A., 210 3avrilenko. U. V., 233 3avrilova, L. A., 125, 253 3avrilyuk, M. I., 501 3avrilvuk. V. G.. 417 3avrynsheva, N.. I., 428 Say, I. D., 124 3ay, R. S., 276 3azarov. R. A.. 112 Seanangel, R. A., 125, 231, 390 Sebala, A., 103 Sebert. E.. 274 Seheeb. N’.. 308. 371 Gehlert; P.,’ 1 5 6 ~ Seisel, T., 213 Geiseler. G.. 268 Gelbaum, -L:, 75 Gelencser, P., 482 Gellatly, B. J., 296 Geller, R., 461 Geller, S., 456 Gence, G., 159 Generalov, 0. N., 464 Generalova, N. B., 395 Gennick, I., 197, 211 Gentil, L. A., 385 George, T. A., 348 Georges, D., 99 Georgiev, S., 450 Georgiew, G.. 270 Georgopapadakou, N., 30 Gerard, A., 412, 463 Gerbaux, M. M. X.. 196 Gerbeleu, N. V., 436 Gerber, J . N., 14 Gerbuz, V. V., 391 Gerchman, L. L., 136, 241, ?C?

LJL

Gerdau, E.. 405 Gerding, H., 320 Gergel-kis. I., 307. 355 Gergely, A., 75 Gerger, W., 172 Gerisch, K., 96 Germa. H.. 155 Germain, A., 226 German, A., 194 Geronov. 1. M., 450 Gerry, M. C. L., 177, 185 Gersonde, K., 440 Gertenbach, P. G., 70, 229 Gervais, D., 7 Gervais, F., 208, 209 Gerval, P 243 Gerwarthi’U. W., 81, 130 Gerzha, T. V., 372

;esland, J. Y.,209 ;evlitch, L. P., 428 jhali, E. L., 295 jhatak, S. K., 494 ;hilardi, C. A., 306 jhiotti, G., 294 ;hirvu, C., 3 13 3hosh, T. K., 230 3iacomelli, A., 35, 31 1, 377 jiacometti, G., 11 3iberman, E., 440 3ibb. T. C., 411, 424, 442, 457, 496 3ibbons, C., 287 3ibson. D. H.. 444 3ibson; J. A.; 63, 147, 150, 259, 262 3jdney, P. M., 374 helen. M.. 19. 84. 143 ;iering, W. P.’, 303 3ierisch, W., 505 3iesbrecht, E., 312, 403, 442 3iguere, P. A., 199 3ilak. A.. 147 3ilbert, B., 226, 289, 321, 336 3ilje, J. W., 63 sill, D. S., 306 Sillard, R. D., 373 sillespie, R. J., 199 sillies, G. C., 175 Sillman, H. D., 383 Sil’manov. A. N.. 76 Silyarov, V. A., I50 fimarc, B. M., 203 Singell, A. C., 327 Sinzberg, A. G . , 338 S!nzberg, S. I., 309, 386 Siordano, G., 347 fiordano, N., 294 Giordano, T. J., 335 Girard, B., 295 Girgis, A. Y., 304 Girling, R. B., 225 Giuffrida, S., 320 Given, R., 18 Gladkii, Yu. G., 74 Gladkowski, D., 127 Glassel, W., 151 Glasbera. B. R.. 84 Glasel, 5: A., 43 Glasser, F. P., 251 Glaunsinger, W. S., 225 GlaviE. P I 258 Glazkova, N. P., 97 Glebov, A. N., 73 Glebov. L. €3.. 251 Glebov; V. A.; 94 Glembotskii, V. A., 121 Glemser, O., 17, 160, 163, 261, 264, 269, 271, 400 Glentworth, P., 408 Glickson, J. D., 77 Glidewell, C., 142 Glockling, F., 310 Glonek, T., 70, 153, 159 Glover, G . H., 456 Glowiak, T., 293 Glozman, E. A., I15 Glubeva, N. G., 216 Glukhikh, V. I., 143 Glushkova, M. A., 368 Goble, D. F., 421 Goddard, R., 19, 22, 48 Godleski, S., 3

518 Godnevai, M. M., 288 Godovikov, S. K., 415 Godwin, G. L., 20 Goedken. V. L.. 97 Goel, R.‘G., 474 Goel, R. K., 198 Goerlich, E., 212, 496, 502 Goetz. G . J.. 198 Gotz, ‘J., 251 Gotze, H.-J., 246 Goetze, K., 237, 257 Goffart, J., 322, 336 Goaan. N. J.. 16. 326 Goggin, 1’. L’, 37’ Gogorishvili, P. V., 357 Goher, M. A. S., 314, 315 Gokhman. L. Z.. 294 Goldanski’i, V. I . , 405, 407, 408, 412, 413, 418, 430, 440, 442, 46 1, 505, Goldberg, I . B., 462 Goldberg, S. 2.. 57 Golding, B. T., 86 Gol’ding, 1. R., 314 Golding, R. M., 437 Goldstein, C., 488 Goldstein, J. H., 147 Goldstein, M., 254, 255, 286, 289, 3.16, 471 Goldwhite, H., 63, 147, 156, 259 Golenishchev-Kutuzov, V. A., 114 Golenwsky, G. M., 125, 235 Goll, w., 54 Golovach, 1. I., 210 Golovanova, G. F., 117 Golovchenko, J. A., 468 Golovin, Yu. M., 319, 390 Golovinova, E. V., 354 Golovko, T. F., 196 Golovkova, L. P., 102 Gol’shtein, S. B., 299 Goltzene, A., 421 Golub, A. M., 394, 400 Golubev, A. M.. 294, 295 Golubiushaya, L. M., 234 Golubnichaya, M. A., 307 Golubova, G. A., 212 Gornbler, W., 162, 163, 271 Gornez Lara, J., 312 Gornory, P., 473 GonGalves, H., 157, 160 Goncharov. G. N., 463 Gonser. U.. 405. 406, 407, 416, ’420,’ 421,. 418; 460; 502, 505 Gonzalez-Jiminez, F., 420, 499. 500 Good; B. W., 100 Good, M. L., 408, 446, 490, 49 1 Good, R., 79 Goodall, B. L., 15, 26 Goodfellow, R. J., 37 Goodisman, J., 98 Goodwin, H. A., 434 Gopalakrishnamurthy, H. S., 288 Gorbachev, V. V., 486 Gorbanev, A. I., 462 Gorbatov, I. A., 207 Gordeeva, G. A., 294 Gordienko, V. A., 454

Author Index Gordon, M. D., 62 Gordon, M. I., 116, 118 Gordy, W., 182 Gorelik, V. S., 213 Gorclikova, N. V., 463 Gorenstein, D. G., 159 Gorkov, V. P., 481 Gorohchenko, V. D., 413, 42 Gorokhov, V. N., 449 Gorokhova, T. I., 123 Gorokhovatskaya, N. V., 12 Gorshkov, V. V., 114 Gorter, C. J., 91 Gosgrove, J. G., 490 Gosling, P. D., 151, 156, 25 Gosselin. J. R., 465 Crosser. L. W., 27 Gottlieb, A. M., 503 Goubeau, J., 152, 259, 261 Gouch, S. R., 110 Could, N. J., 343 Could, H. O., 157 Could. T. H.. 502 Gouterman, M., 292 Govil, S., 291 Gowenlock, B. G., 230, 378 GovDiron. A.. 217 Graddon,’ D. ’P., 84 Graham, M . A., 340 Graham. M. J., 451 Graham, W. A. G., 12, 1~ 15, 339, 341, 343 Grakauskas, V., 274 Gramniakov, A. G., 113 Grande, S., 437 Grandjean, D., 23 Grandjean, F., 412, 463 Granot, J., 101, 486 Granoth, I , 154 Granovskii, E. V., 5 0 4 Grant, D. M., 94 Grant, M. E., 25 Grant, R. W., 406 Grasdalen, H., 102 Graus, V., 212 Graves, G. E.. 157 Gray, G. A., 4, 148 Gray, H . B., 74, 283, 344, 43 Gray, R. T., 88 Graybeal, J. D., 178 Graziani, M., 313 Graziani, R., 320 Greatrex, R., 446, 457, 490 Greaves, C., 460 Grechishkin, V. S., 173 Green, M.. 19, 20, 21. 22, 2f 28, 31, 32, 34, 56, 127, 125 234, 299, 345, 364 Green, M. L. H., 8, 287 Green, S., 182 Green, T. H., 58 Greenberg, M. S., 66 Greenblatt, M., 117 Greene. D. L., 100 Greenhalgh, D. A., 317 Greenlee, W., 445 Greenwood, N. N., 127, 121 190, 232, 235, 457, 468, 47; 486, 490, Gregson, A. K., 92, 96 GreguShova, M., 433 Grenier, J.-C., 458 Greskovich, C., 456 Greve, K. S., 83

Grevels, F.-W., 327 Grevtsev, A. M., 287, 386 Grey, I. E., 466 Grib, B. N., 218 Gribov, B. G., 83 Gribov, L. A., 267 Gridnev, V. N., 417 Griffin, C. F., I16 Grjffin, I. M., 40 Gr!ffin, M. G., 204 Griffin, P. A., 144, 250 Griffin, R. G., 118 Griftith, E. J., 70 Griffith, W. P., 277, 287, 363, 364 Griffiths, J. E., 193, 226 Griffiths, P. R., 190 Grignon, J., 90 Grigor’ev, A. I., 72, 230, 353, 375, 383, 393, 394 Grigor’ev, A. N., 172 Grigor’ev, M . S., 503 Grigoriev, V. P., 109 Grigorovich, Z. I., 273 Grill, A., 418 Grim, S. O., 13, 14, 148, 384 Grimes, N. W., 479 Grimes, R . N., 81, 127, 234 Grimmer, A. R., 112 Grimmer, D. P., 123 Gritsenko, A. P., 207 Grizik, A. A., 319, 390 Grobe, J., 16, 17, 147, 292, 299, 307, 343 Groenenboom, C. J., 7, 322 Groeneveld, W. L., 285, 366 Groffart, J., 321 Grornova, T. M., 210 Gronowitz, S., 22, 161, 162 Gros, Y., 466 Grosescu, K., 107 Gross, S., 93 Grosse, J., 156 Grosse-Bowing, W., 264 Grossmann, Ci., 146 Groves, J. L., 439 Grow, R. W., 218 Grubbs, R. H., 287 Grurnprecht, D., 496 Grundy, K. R., 330, 344, 388 Grupp, M., 111 Gruzin, P. L., 414, 449, 456, 501, 502 Gryaznov, M. K.,414, 456 Grynkewich, G. W., 49 Grzeskowiak, R., 316, 336 Grzybowski, J. M., 191, 192, 194 Gsell, R., 250, 471 Guarnieri, A., 184, 271 Guastini, C., 35, 377 Guay, M., 214 Gubaidullin, F. F., 76 Gubbens, P. C. M., 502, 505 Gubin, S. P., 22 Gudlin, D., 17 Gudov, V. I.. 415 Guenias, L., 230 Guerchais, J. E., 254, 266, 288. 289. 291. 354. 372. 375. ‘ ’ ‘ 376: 387i476; Ciuergerich, C. P., 365 Guerney, P. J., 32 Guerreiro, R., 7

Author Index Guest, M. F., 184 Giitlich, I>., 406, 427, 435, 444 Guggenberger, L. L., 45 Guggenheim, H. J., 499 Guibe, L., 176 Guillory, W. A., 202 Guimaraes, A. C., 91, 150 Gukasyan, S. E., 481 Gulbis, J., 72 Gullman, J., 468 Gullotti, M., 288 Gulya, A. P., 80, 97 Gulyaev, L. S., 120 Gumerov, F. M., 94 Gumnerova, L., 415, 473 Gumprecht, D., 505 Gunawardane, R. P., 251 Gundin, A. G., 111 Gundovin, N. V., 288 Gunsalus, I. C., 439 Gunsser, W., 420 Gunther, L., 412 Gunz, H. P., 296 Gupta, B. D., 40 Gupta, D. C., 503 Gupta, L. C., 108 Gupta, L. R., 504 Gupta, M. P., 111, 454 Gurarii, L. I., 160 Gurley, T. W., 158 Gurrieri, S.. 320 Gurtovoi, G. K., 457 Guryanova, E. N., 172 Gusakov, G. M., 83 Guseva, A. S., 130 Gustavsson, H., 71 Gustyakova, M. P., 144, 296, 376 Gutovskii, I. G., 503 Gysegem, P., 63, 156, 259 HIaaland, A., 186, 336 H!ass, A., 163, 271 H aas, B., 187 H‘aas, C. H., 242 H abeeb, J. J., 234, 400 H achey, J.-M., 295 H ackbusch, W., 29 H acke, N., 283 H ackelberg, O., 387 H ackeloer, H. J., 104 H ackett, P., 446 H addock, S. R., 37 H adjikostas, C. C., 391 H adjiliadis. N., 88, 312 H adjiminolis, S., 266, 471 H adni, A.. 196 H aeberlen. U.. 107. 112 Hsgele, G., 138 . Haggstrom, L., 410, 417, 418, 468. 502 H aen,‘ P., 421 aeuselcr, H., 208, 210 H H afner, S. S., 406, 462 H agelee, L. A., 130 H agemann, H., 245 H agen, G. P., 340 H ager, L. P., 439 H aggenmuller, P., 458 H agihara, N., 34, 334 H aiduc, I., 312 H aines, A. H., 72, 142 €iaines, R. J., 446 H ajek, M., 92

519 Hakuta, K., 193 Iialadjian, J., 238. 379 Halbert, 1’.K., 438 Hall. D. 0.. 440. 441 Hall, G . R.’, 352’ Hall, J. R., 210. 397, 398 Hall, L. D., 4, 34, 79 Hall. L. W.. 125. 129 Hall, M. B.; 445 Hall, R. J. B., 217 Halliwell, R. E., 175 Hallpop, P., 2 Halstenberg, M., 141 Ham, F. S., 407 Hamaguchi, H.. 205, 280 Hamilton. W. C.. 157 Hammerschmidt.’R. F., 15 Hanafi, 2. M., 263 Hanai, K., 269 Hance, R. L., 277 Handke, M., 212 Handke, R., 261 Handy, L. B., 15 Hangartner, M.. 356 Hanke, H. E., 252 Hanke, W., 250 Hanlan, L., 280, 345 Hanna, S. S., 483, 484, 492, 498 Hanprasopwattana, P., 373 Hansen, H.-D., 234 Hanslik, T., 133 Hanson, B. E., 95 Hanson, L. K., 292 Hanson, R. C., 208 Hanuza, J., 220 Hara, K.-I., 116 Hara, Y.,303 Harada, I., 205, 280 Harbach, F., 211 Hardy, W. N., 220 Hare, J., 438 Har reave M. M., 215, 217 Harfe, E.: 359 Harland, L., 222 Harley, R. T., 318 Harley, S. F., 168 Harmon, C. A., 20, 21 Harmon, K. M., 197, 211 Harrell, J. W., jun., 110 Harris, D. C., 74, 283, 344 Harris, D. H., 139, 283 Harris, D. O., 183 Harris, F. E., 416, 426, 432, 438, 442, 460 Harris, I. R., 503 Harris, R., 501 Harris, R. K., 135, 137, 142, 150, 151, 156, 160 Harris, R. O., 344, 388 Harris, S. J., 185 Harrison. D. J.. 194 Harrison; M. R., 102 Harrison, P. G., 11, 19, 62, 145, 250, 304, 345, 374, 433, 446. 471. 412. 475. 478 Harrod, J.’ F., 8 Harrowfield, J., McB., 386 Hart, D. W., 7 Hartley, F. R., 30, 309 Hartman, J. S., 82, 83, 133 qartmann-Boutron, F., 41 1, 500 iartshorn, A. J., 323

Hartwell, G. E., 10, 53, 307, 332, 371 Iiasebe, T., 109 Haserrawa. R.. 501 €IashTmoto, K., 78, 8 5 , 266, 378, 383 Hasiguti, K. K.,468 Hassairi. M.. 157 Hasselbach, K. M., 427, 435 Hastie, J. W., 197 Haszeldine, R. N., 18, 20, 26, 27, 28, 90, 138, 141, 144, 145, 250, 306 Hatano, T., 502 Hatfield, W. E., 314 Hathaway, C. E., 215 Hatzenbuhler, D. A., 194 Hauge, R. H., 195, 197 Hauk, J., 213, 300 Haupt, H.-J., 283, 342 Haupt, W., 122 Hawser, K. H., 3 Hawke, R. S., 195 Hawkes, G. E., 42, 59, 146 Hawley, G., 291 Hawthorne, M. F., 89, 126, 127, 128, 129, 232, 234, 238 Hay, R. W., 374 Hayamizu, K., 95 Hayashi, M., 188, 463 Hayashj, N., 450 Hayash!, S., 207, 273 Hayashi, T.. 261 Hayes, D. J., 246 Hayes, W., 318 Haymore, B. L., 24, 301, 349, 350. 369 Hayward, H. P., 196 Hazel, F., 396 Hazony, Y., 407 Head, R. A., 25 Healy, M. A., 5 , 158 Heath, G. A., 14, 348 Heaton, B. T., 38, 5 5 Heck. L.. 357 Hedges, R. E. M., 464 Hegedus, L. S., 31 I Heicklen, J., 202, 268 Heidemann, A., 492 Heil, B., 19 Heil, C. A., 90, 241 Heiman. J. R.. 60. 390 Heimari; N., 503 ’ Heimau, D., 209 Heimburger, R., 267 Heinrich, S., 257 Heitians. P.. 1 I I Hei&ch,‘C. ‘W., 38 Held, W., 10 Hellams, K. L., 188 Helland. C.. 154 Heller-Kallai, L., 212 Helminger, P., 183, 184 Helsen, J. A., 464 Hemmer, H., 334 Hemmerich, P., 72, 73, 95 Hemmings, R. T., 265 Hcndra, P. J., 190 Nendricker, D. G., 301 Hendricks, €3. M. I)., 43 Hendrickson, A. R., 30 Hendrickson, D. N., 302, 309, 329, 342, 352, 449 Hendrickson, J. R., 108

520

Author Index

I4endriksen, L., 64 Idengge, E., 241, 244 1Aenneke, H. W., 111, 120 1hennig, H. J., 117, 123 1qeno!d, K. L., 59 1denrichs, P. M., 93 1Henriks, B. M. P., 70 1Henriksen, I., 268 IHenriksen, L., 251 1Henry, H. 2.. 73 Hentges, S. G., 340 Herak, J. N.. 118 Herber, R. H., 250, 353, 407, 474. 475. 479 Herberhold. M.. 46. 190,. 326. 348, 372 Herberich, G. E., 28 Herbstein, F. H., 221 Herlt. A. J.. 86 Herman, M.. A., 262 Herman, R. G., 385 Hefmhnek, S., 127, 128, 129, 133. 232 H erring, F. G., 57 H errmann, D., 265 Herrmann, E., 84 H errmann, W. A., 15, 16 H ersh, K. A., 61 H ertz, H. G., 43 H erzog, F., 62, 258 H erzog, J.-F., 238 H esse, J., 503 H ester, R. E., 225 Hetfleji, J., 242, 249, 306 Heuschmann, M., 63 H eusler, H., 313 H ewson. M. J . C.. 150 Hexeni,‘J. G., 93. Heyer, G., 292 Heyman, K. M. F., 503 Hevns. A. M.. 266 Hiiu , Y . S., 296 Hickernell, D. C., 123 Hickey, J. P., 50 Hickman. R. J., 102 Hidai, M’., 14, 348 Higasi, K., 201 Higbie, F. A., 332 Higgy, E. S. M., 415 Hightower, J. W., 455 Hildenbrand, K., 21, 39, 138, 343 Hill, M . N. S., 56 Hill, W. E., 89 Hillel, R., 198 Hillier, 1. H., 182 Hills, M. E., 214 Hilton. A. R.. 246 Hilton; B. D.,- 76 Hilton, J., 1 Hinchcliffe. A. J.. 191 Hinman, D. D., ‘109 Hinton, J. F., 69 Hintsche, R., 24, 96 Hirai, H., 78 Hirayama, M., 101 Hirayama, Y., 35, 400 Hirsch, A. A., 452 Hirsekorn, F. J., 57, 333 Hirst, L. L., 406, 503 Hiruma, H., 210 Hisatake, K., 449, 505 Hisatome, M., 330 Hisatsune, 1. C., 202, 268 I

_

,

~

-iitchcock, P. B.. 10, 313, 339 ditchman. M. A.. 315 ditomi, T:, 140 ’ Ho, B. Y. K., 243, 374 do, E. Y., 449 -lo, K. S., 30 40, Y. K., 473 .lo, V. J., 74 tlobson, M . C., 408 Hoch, G., 372 Yoch, M. J. R., 116, 118 lochheinier, H. D., 208 .locking, W. H., 185 docks, L., 321, 336 Hodges, K. C., 10, 324 Hodges, K. D., 313 Hodgson, D. J . , 386 Hoebbel, D., 144. 145, 251 Hobold, W., 8 Hofer, R., 261, 264, 269 Hofler, F., 244, 245, 253 Hofler, M., 241, 394 Hoel, E. L., 126, 128, 234 Hofer, R., 163 Hoffbauer, M., 277 Hoffman, M . Z., 369 Hoffman, P. R., 53, 152. 301 Hoffman, R. W., 503 Hoffmann, E. G., 7, 323 Hofstotter, H., 237 Hogan, R. J., 65 Hogenkamp, H. P. C., 25 Hogg, C . S., 463, 464 Hohenemser, C., 408, 503 Hohmann, F., 364 Holah, D. G., 306, 387 Hohorst, F. A., 206, 274 Holba, K., 456 Hollander, F. J., 387 Hollis, D. I]., 95 Hollowav. J. H.. 15. 163. 199.’ 226, 275, 277,.296; 3 15‘ Holm, R. H., 407, 435 Holste, G., 283 Holtzbere. F.. 494 HolzapfeT,’ W.’ B., 195, 408 Holzer, W., 193 Honda, H., 378 Hong, S. R., 467 Hoogzand, C., 19 Hopkins, A. G., 191, 193, 194 Hoppe, H.-R., 250 Hoppe, R., 493 Horak, M., 190 Hordan, H., 292 Hori, K., 308 Hori, T., 455 Horn, H. G., 119 Hornfeldt, A. B., 161, 162 Hornstein, F., 412, 503 Horstschafer, H.-J., 130 Horwood, J. L., 465 Hoskins, B. F., 343 Hoselton, M. A., 99, 100, 360, 43 5 Hosmane, N. S., 41, 135, 241 Hosoda, H., 142 Hosokawn, K., 174 Hossain. S. F.. 162 Hosseini, H. E., 80 Hou, F. L., 17, 85 Houk, L. W., 157 House, D. A., 30, 307

Housley, R. M., 456, 462 Hovdan, H., 267 Howard. C. J.. 184 Howard; J. A.’ K., 20, 31, 32, 56, 127, 364 Howard, J. W., jun., 39 Yoward, W. F., jun., 192, 193 280 tlowarth, 0. W., 5 , 86 Howe, A. T., 250, 396, 478 Howell, B. A., 1 I Howell, J. A. S., 49, 52, 79 Howie, R. A., 217, 476 Hoxmeier, R., I5 Hoy, G. R., 412 Hoyer, E., 443 Hrichova, R., 457, 479 Hrung, C. P., 47 Hrynkiewicz, H., 496 Hsi, E., 76 Hsieh, A. T. T., 320 HSU, C.-Y., 310 Hsu, Y . F., 154 Huang, C., 196, 217, 476 Huang, Y . - Y . , 461 Hubble, F. F., tert., 115 Huber, F., 342 Huber, H., 342, 345, 347 Hubert, J., 88, 313, 335 Hubert-Pfalzgraf, L. G., 291, 383 Huckaby, D. A., 230 Hudgens, B. A., 237 Hudson, M. F., 42 Hufner, S., 496, 505 Huff, R. B., 391 Huff, L., 147 Huffman, G . P., 462 Huffman, J., 127, 232 Huflnian, J. C., 129 Huggins, F. E., 464 Hughes, A. N., 306 Hughes, B., 159, 378 Hughes, J., 285 Hughes, M. N., 385 Hughes, 0. H., 208 Hughes, R. J., 289 Hughes, R. P., 19, 20, 22 Hui, B. C., 306 Huis. R., 90 Huiskamp, W. J., 496 Huler, E., 220 Hull, G. W., 467 Humphries, A. P., 22, 48 Huneke, J . T., 353 Hunnius, W.-D., 294 Hunter, D . L., 45, 48, 50, 51 59 Hunter, F. D., 212 Hunter, G., 46, 63 Huong, P. V., 198 Huray, P G., 493 Husa, D. L., 123 Husebye, S., 485 Hussiun. A. L.. 479 Hutchinson, B.; 277 Hutter, F., 179 Huttner, G., 11, 16, 256, 370 Hutton. W. C.. 83. 147 Huvenne, J. P.’, 200 Huynh, B. H., 439 Hwang, T. Y.,109 Hyatt, H. A., 193 Hyde, E. M., 28, 306

Author Index lannarella, L., 491 lannuzzi, M. M., 290 Ibanez, F., 233 Ibbott, D. G., 76, 283 Ibers, J. A., 24, 80, 301, 349, 350, 369 Ibrahirn, E. M. H., 263 Ichida, S., 330, 479 Idogaki, M., 471 Idrisov, T. Ch., 376 igi, K., 30 Ignat’ev, I. S., 190 Ignat’ev, Yu. A., 4 lida, S., 453 lijima, K., 203 Ikeda, R., 167, 176 Ikhenov, D. A., 177 Ikonnikov, V. P., 466 Ikorskii, V. N., 116 Ilie, N., 7 Iliew, N., 496 Il’in, E. G., 78, 160, 177 ll’in, M. A., 208, 243 Ilmaier, B., 291 Il’yasova, A. K., 290 Ilyushin, A. S., 505 Imbert, P., 415, 420, 499, 500

Immirzi, A., 30, 351, 374 Imoto, S., 103, 399 Inagaki, F., 102 Indelli, A., 35, 377 Infante. A. J.. 128 Inglis, T., 27, 283 Ingold, K. U., 130 Ingrosso, G., 374 In’kova, E. N., 320, 399 Inlow, R. O., 383 Inokuchi, H., 440 Inoue, H., 277 Inoue, M., 116 Inzett, Gy., 222 loffe, M. S., 478 lotre, P. A., 464, 465, 479 lolins, E., 413, 503 lonin, B. I., 146 lonov, S. P., 408, 481, 486 lonova. G. V., 408, 481 Iqbal, Z., 215 Ireland. P. S., 167 Irish, D. E., 223, 224, 316 Irkaev, S. M., 483 Irmer, R., 223 Irzikevicius, A., 210 Isaacs, E. E., 12, 14, 339, 341 Isabirye, D. A., 304 Isaev-lvanov, V. V., 421 Isaeva, L. S., 310 Isakov, L. M., 414 Isbrandt, L., 19 Ishchenko, 0. S., 244 Ishibitsu, K., 144 Ishida. Y.. 503. 505 Ishii, Y . , 312 ‘ Ishimori, I., 369 Ishimori, T., 277, 370 Ishino. M.. 74 Ishmaeva, E. A., 261 Isida, T., 140 Isied, S. S., 365 Isihara, H., 171 Iske, S. D. A., 348 Ismail, Z. K., 195

521 Ismailzade, 1. G., 458 Isobe, K., 300 Isobe, T., 98 Isozumi, Y., 414 Issleib, K., 148, 261 Istru, L. N., 358 Isuyama, R., 381 Itkina, L. S., 65 Ito, A., 422, 423 Ito, T., 97, 107, 112, 305, 376 Itoh, K., 312 Ittel, S. D., 53, 80, 350 Ivan, E., 371 Ivanitskii, V. P., 462, 463, 466 Ivanov, A. S., 409, 413 Ivanov, B. E., 153 Ivanov, 0. A., 503 Ivanov, V. A., 83 Ivanov, V. V., 116, 120 Ivanova, L. I., 379 Ivanova, N. N., 373 Ivanova, N. M., 216 Ivanova, N. V., 303. 369 Ivanova. 0. M.. 177 Ivanov-Emin, B. N., 312, 373, 382, 400 Ivanvushkin. E. M.. 501 Ivasfichenko: A. V.: 382 Ivkina, N. A., 449, 461 Ivlev, Yu. N., 143 Ivoilov, N. G., 501 Iwaizumi, M., 98 Iwatani, K., 235 Iwatate, K., 307 Iwayanagi, T., 33, 310 lyengar, P. K., 455, 504 Iyengar, R. R., 396 lyer, H. P., 376 Izumi, F., 285 Izydore, R. A., 132 Jablonski, C. R., 56, 31 1 Jaccarino, V., I15 Jach, J., 433 Jack, T. R., 58, 80 377 Jackowski, K., 98 Jackson, G. E., 73 Jackson, W. G., 19,47, 52, 58, 74. 86. 306. 402 Jackson,‘W. k., 1 1 Jacob, R. A., 252 Jacobs, I. S., 454, 456 Jacobson, A. R., 180 Jacobson, S. E., 36,37,228,313 Jacobus, J., 102 Jacox, M. E., 199 Jadhao, V. G., 422 Jaecker, J. A., 301 Jackh, C., 131. 270 Jagner, S., 363 Jain, Y. S., 214 Jain, S., 403 Jakobsen, H. J., 136 Jamerson, J. D., 59 James, B. R., 304, 305, 309 James, D. W., 216, 223 James, R. St., 415 James, S. M., 344 James, T. L., 2 Jameson, A. K., 163 Jameson, C. J., 163 Jancke, H., 144 Jancso, L., 222 Janda, K. C., 185

Jander, J., 265 Janickis, V., 271 Janjk, J. A., 31 I, 356 Janik, J. M., 3 1 1, 356 Jannach, R., 244, 253 Janoschek, R., 223 Janot, Ch., 464, 479, 503, 504 Janssen, E., 141 Janssens, G., 108 Janz, G. J., 225 Janzen, A. F., 147 Jaouen, G., 12, 338 Jarke, F. H., 159 JaroS, M., 263 Jarvis, J. A. J., 332 Jaworiwsky, I . S., 59 Jaworski, K., 238 Jeandey, C., 491, 503 Jeanne, C., 276 Jeffrey, K. R , 118, 169 Jehanno, G., 415, 419, 420 Jelus, R . L., 240 Jena, P., 483 Jennette, K. W., 76 Jennings, H . J., 4 Jennings, W. B., 3, 144, 157 Jensen, K. A., 64 Jentzsch, R., 160 Jerome, D., 106 Jerome, L., 1 1 1 Jerschkewitz, H.-G., 250 Jesser, R., 417 Jesson, J. P., 9, 13, 53, 384 Jessop, K. J., 437 Jeiows k a-Trze bi a t ows ka , B ., 41, 96, 220 Jha, S., 483 Jsrgensen, P., 163 Joesten, M . D., 383 Johannesen, F. H., 303, 344 Johannesen, R. B., 15, 159 Johannsen, G., 13 Johansson, D. A., 341 John, K. P., 157 Johns, W. S., 88 Johnson, A., 3 13 Johnson, B., 95 Johnson. R . F. G.. 19. 22, 35. 47, 48, 52, 54,.55,’56; 86; 345, 369 Johnson, B. V., 48, 53 Johnson. C. E.. 409. 406. 440. 441, 457 Johnson, D. A., 393 Johnson, D. F., 74 Johnson, D. W., 180 Johnson, F. A., 89 Johnson, G. H., 209 Johnson, H. D., jun., 59 Johnson, I., 22, 161, 162 Johnson, J., 90 Johnson, J. R., 74, 276, 302 Johnson, P. R., 315 Johnson, R. C., 351 Johnson, R. N., 79, 304 Johnson, S. H., 27 Jokisaari, J., 135 Jolicoeur. C.. 92 Jolley, K: W.’, 1, 43 Jonas, K., 56 Jones, C. H. W., 485,488 Jones. D. H.. 304. 433 Jones; G. C.’H., 25, 493 Jones, G. P., 3 ,

I

,

522

Author Index

Jones, 1,. H., 219, 276 Jones, M. T., jun., 38 Jones, P., 68, 74 Jones, R. D., 451 Jones, R. G., 66 Jones, W. E., 1 I 7 Jordan, R. R., 68 Jordan, K. W., 231 Josephson, W. D., 493 Josson, C., 202 Jost, R., 274 Joubert, P., 206 Jouve, P., 191 Joy, G., 218 Juchnovski, 1. N., 363 Julliard, J., 209 Jumper, C. F., 223 Jungk, E., 234, 379 Juranid, N., 123 Jurkowitz, D., 276 Jutzi, P., 62, 258, 313 Kabachnik, M . I., 150 Kachi, S., 421 Kacirek, H., 122 Kaczmarczyk, A., I29 Kadaba, P. K., 110, 170, 171 Kadenarsi, B. M., 505 Kadlecovh, H., 238 Kadooka, M. M., 401 Kadowaki. T.. 107. 122 Kaerger, J., 122 Kaesz, H. D., 15, 18, 74, 302, 325. 379 Kagan, J., 20, 327 Kagan, Yu. M., 405 Kahn, O., 324 Kaidalova, T. A., 290 Kaindl, G., 492 Kainosho, M., 101, 102 Kaipov, D. K., 415 Kaiser, S. W., 28 Kajiwara, M., 136, 156 Kakiuchi, Y., 43 Kalamkarov, G. R., 440 Kalasinsky, V. F., 186, 187, 237, 249 Kalb, A. J., 440 Kalbacher, B. J., 297 Kalbfus, W., 10 Kalck, P., 388 Kalder, H. J., 10 Kaldygozov, E., 251 Kalen, K., 23 Kalina, D. G., 340 Kalinichenko, A. M., 1 I I , 113 Kalinichenko, I. N., 381 Kalinin, A. E., 150 Kalinin, V. N., 128 Kalinina, A. M., 251 Kalinnikov, V. T., 291, 376, 402 Kalir. A.. 154 Kalisvaart. W. I., 90 Kallweit. R., 7, 323 Kalvius, G. M.,407, 408, 423, 432. 440. 493. 495. 505 Kalyarnin,'A. V., 434, 461 Kamcntsev, Y.S., 171 Kaminsky, W., 44 Kamishina, Y., 169 Kamyshev, V. A,, 213 Karnzin, A. S., 455 Kana'an, A. S., 195 '

Kanamori, € I . , 207 Kanas, A., 295 Kanashiro, M., 493 Kane-Maguire, L., 305 Kanert, O., 104 Kaneshima, T., 53 Kaneto, H., 72 Kankeleit, E., 405, 409, 413 Kano, Y., 354 Kanter, H., 38 Kao, R. R., 59 Kapacauskas, I., 112, I I3 Kapila, V. P., 384 Kapkan, L. M., 77 Kaplan, J. I., 104 Kaplyanskii, A. A., 221 Kapoor, P. N.. 291, 323 Kaptein, R., 90 Kar, D., 159 Karaianev, S., 192 Karakishev, S. D., 501, 503 Karamyan, A . A.. 209 Karasev, V. E., 320, 377, 378 Karaskin, Yu. N.. 233 Karayannis, N. M., 3 1 1 , 383, 384, 403 Karczewska, I., 69 Karelin, A. I., 194, 273 Karetnikov, G. S., 372 Karimov, Yu. S., 417 Karlsson, E., 418, 502 Karlysheva, K. F., 8, 288, 375 Karmanov, V. I., 266 Karnaukhov, A. S., 380 Karnezos. N.. 479 Karpenko, N.' V., 43 Karsch, H. H., 18, 25, 28, 53, 307. 371 Karyagin, S. V., 412, 413 Karyakin, A. V., 196 Kasatochkin, V. I., 417 Kasaya, M., 1 I5 Kaschube, M., 61 Kash, R. M., 490 Kashcheev, V. N., 41 1 Kashman, Y., 153 Kashpruk. 0. A., 124 Katada. M., 479 Katayama, A., 66 Katiyar, R. A., 209 Kato, K., 285 Kato, M., 503, 505 Katolichenko, V. I., 264 Katsnel'son, A. A., 501 Katz, J.-J., 7, 125, 231 Kauffman, K., 396 Kaufmann, J., 14. 263 Kaur, M., 384 Kavan. L.. 304 Kavathekar, B. J., 32 Kavun, V. Ya., 73 Kawaguchi, S., 300, 310 Kawakami. K.. 53, 54 Kawaki, H., 101, 102 Kawamori, A., 100 Kawarnoto, H., 285 Kawamura, K., 226 Kawamura, T., 218 Kawano, K., 29 Kawasaki, Y., 78, 85. 134, 141. 244. 266. 378. 3 8 3 Kazakov, M., 417, 464 Kazama, S., 114 Kazanskii, L. P., 9, 295

Kazanskii, V. B., 121, 123, 124 Kazankov, M. V., 400 Kazuaki, I., 212 Keat, R., 58, 151, 174 Keating, T., 56 Kecki, Z., 67, 69, 97, 98 Kedern, D., 106 Kedrova, N. S., 316 Kedryavtseva, L. V., 140 Keene, T., 90 Keiderling, T. A., 276 Keisch, B., 407 Keister, J. B., 47, 52, 302 Keiter. R. L., 14 Kelland, J. W., 19 Keller, H. J., 3, 367, 398, 453 Keller. H. U.. 107 Keller; J., 213 Keller, N., 319 Keller, P. C., 89 Kellett, S. C., 20 Kelling, H., 141 Kello, E., 314 Kelm, H., 386 Kelsey, R. J., 38 Kemmitt, R. D. W., 27, 333 Kemmler-Sack, S., 319 Kem ny H.-P 46, 370 K e n g i c i , J., ik2 Kennedy, J. D., 31, 136, 139, 142 Kennedy, R. C., 204 Kennelly, W. J., 45, 231 Kepert, D. L., 257, 290 Keresztury, G., 251 Kergoat, R., 291, 372 Kerridge, D. H., 290 Kessenikh, A. V., 130 Kessler, Yu. M.,65 Keszthelyi. L., 464 Kettle, S. F. A., 211, 215, 222, 349 Keubler, M., 352 Keulks, G. W., 461 Keune, W., 420, 465, 502, 503 Kevdin, 0. P., 418 Kew, D. J., 200 Khabibullin, B. M.,114 Khaddar. M. R.. 77 Khalezov, A. A.; 213 Khalil, G.-E., 292 Khalil, M. I., 5 Khaloimov, A. I., 196 Khammouma, S., 450, 451 Khan, M. M. T., 305, 431 Khan, S. A., 285, 311, 312 Khanakova, L. G., 317 Khandelwal, D. P., 197 Kharitonov, N . P., 142, 249 Kharitonov, Yu. Ya., 231, 233, 239, 285, 307, 313, 317, 358, 359, 380, 381, 386, 390, 395, 398 Kharrasova, F. M., 261 Khashkhozhev, Z. M., 208 Khat'sko, E. N., 294 Khemdoudi, J.. 263 Khetrapal, C. L., 1 Khirnich, T. A . , 463 Khimich, Yu. P., 460 Khlebodarov, V. G., 290 Khlystov, A. S.. 461 Khodos, 1. I., 106

A uthoY Index Khodosov, E. F., 106, 114 Khodzhaev, 0. F., 290 Klioi, L. D., 108 Khokhlova, L. I., 375 Khokhryakov, K. A., 311 Khomyak, T. P., 1 1 1 Khorshev, S. Ya., 241 Khotsyanova, T. L., 172, 174 Khozhaev, 0. F., 380 Khozhainov, Yu. M., 270 Khozhainova, T. I., 263 Khraniov, A. S., 476 Khrapov, V. V., 124 Khripun, M. K., 64 Khrustaleva, S. V., 288 Khudobin, Yu. I., 142, 249 Khulbe, K. C . , 292 Khullar, I . P., 388, 400 Khutsishvili, G. R., I13 Kicas, P., 1 I3 Kidani, Y.. 285 Kidd, D. R., 28 Kidd, R. G., 159 Kiefer, W., 192 Kielbasinski, P., 160 Kielman, H. S., 84, 158 Kiernan, P. M., 364 Kieselack, P., 154 KiKen, A. A., 81, 88 Kigawa, M., 449 Kihara-Morishita, H., 292 Kilner, M., 283, 333, 346 Kim, B., 399 Kim, C. S., 466 Kim, J. 3.. 203 Kim; K . S., 117 Kimball, C. W., 493, 502, 503, 504 Kimber,B. J., 135,136,137,142 Kimel’fel’d, Ya. M., 192, 273, 307 Kimura, K., 440 Kinas, R., 159 Kinberger, K., 231 Kincaid, J., 230, 277 Kindurys, A., 210 King, A. R., 115 King, R. B., 10, 13, 20, 21, 147, 148, 257, 285, 323, 324, 325 King, R. W., 125 King. W. B.. 316 Kinoshita, T., 450 Kinrade, J., 462 Kipker, K.. 151, 152, 264 Kirby, R. G., 263 Kirchmeier, R. L., 148, 156, 252,269 Kirchner. R. F.. 438 Kireev, V. V., I56 Kirichok, P. P., 456 Kirillov, S. A., 227 Kirk, A. D., 293 Kir’yanov, A. P., 505 Kisch, H., 23, 328, 391 Kiselev, V. F., 105, 117, 288 Klsin, A. V., 61 Kistruga, L. Ya., 359 Kitagawa, M., 360 Kitagawa, T., 360 Kitazima, S., 378 Kitching, W., 40, 134 Kivrina, N. K., 418 Kjekshus, A., 482

Klaboe, P.,251, 268 Klein, B., 357 Klein, C.. 461 Klein, H.-F., 18, 25, 28, 53, 307, 371 Klein, U. F., 407 Kleinberger, R., 428 Kleine, W., 1 1 Klement, R., 385 Klemperer, W., 180, 185 Klemperer, W. G., 9, 64 Klenus, V. G., 213 Kleps, R . A., 70 K l e s ~ e r .E.. 3 Klevkova, R. F., 294 Klimov, V. D., 194, 275 Klingebiel, U., 141. 241, 245 Klinkova. V. V.. 316 Kiioze, S:, 30 ’ Kloosterboer, J. G., 76 Klopsch, A., 230, 233 Klosowski, J., 386 Kloth, B., 159, 264 Klotzbucher, W., 350, 373 Kluchnikov, V. M., 379 Kliipfel, H.-J., 196 Kluemel. H. J.. 273 Klug; ’W.’, 163, 271 Kluger, R., 72 Klushin, N . A., 470 Klushina. T. V.. 270 Klygin, A. E., 379 Klyucharev, V. A., 492 Kmiec, R., 496, 502 Knappwost, A., 420 Knauss. D. C., 104 Knehr, H., 187 Knidiri, M., 219, 319 Knisuel. R . R.. 85. 113 Knoble,‘ D. W:, 493 Knop, O., 196, 197, 203, 217, 476 Knox. S. A. R.. 18. 19. 22. 48. 74, ‘302 Knubovets, R. G., 113 Knudsen, J. M., 223, 304,4 33 Knunvants. I. L... 242., 316 KO, D., 147 Kobayashj, T., 421 Kobayashi, Y., 91 Koberssi, M. A., 503 Kober. F.. 263 Kobyakov; A. K., 93 Kobycheva, S. A.. 288 Koch, D., 151, 152, 159, 264 Koch. F.. 1 1 1 Koch; S.,’ 435 Kochetkova, N. S., 23 Kochi, J . K., 87 Kochnev, I. N., 196 Kodama, G., 89, 125, 126 Kobler, U., 495 Kohler. F. H.., 10., 22.. 92. 97. 133, ‘1 49 Kohler, H., 157, 400, 474 Kohler, K., 317 Koehler. P.. 253 Koehler; W. H., 225 Konig, K., 434 Koenig, M., 159 Koenig, M. F., 324 Koenig. S. H., 101 Koniger, F., 200, 206, 276 Koniger-Ahlborn, E., 276,296

523 Koepke, J. W., 18, 74, 302 Kocrner von Gustorf, E., 21, 327, 343 Kiistcr, R., 130 Koettgcn, D., 261 Koezuka, H., 312 Kofman, V. L., 290 Kogan, V. A., 359, 474 Koglin, E., 191 Kohlschiitter, U., 112 Kohout, V., 379 Koike, H., 285 Koizumi, M., 450 Kojima, M., 29 Koketsu, J., 261 Kokot, E., 376 Kokunov, Yu. V., 144, 295, 296. 354. 376 Kolb,.J. R:, 44, 103, 231 Kolchanova, N. M., 421 Kolesnikov, I . M., 463 Kolesova, V. A., 22Y, 251 Kolin, V. V., 205, 276 Kolinski, K. A,. 361 Kolitsch, W., 203, 321, 352 Kolk, B., 480 Kolli, I. D., 235, 294 Kollman, V. H., 43 Kollmann, G., 244 Kolmakova. E. I.. 133 Kolobova, ’N. El, 17Y, 299, 325, 338 Kolodziejski, W., 67 Kolokol’tsov. V. B.. 67 Kolosovskaya, E. A., 120 Kolpakov, A. V., 409,413,503 Kolpakov, N . S., 414 Kol’tsov, A. I., 83 Komissarova, L. N., 172, 287, 288, 377, 386 Komiyama, M., 78 Konarev, M. I., 300 Kondilenko, I. I., 216, 218 Kondo, Y., 204 Kondratenko, N . V., 41 Kondratenkov, G. P.,78 Kondratov, 0. I . , 196 Koningstein, J. A.. 307, 322, 329 Kononov, A. M., 245 Konovalov, E. V., 41 Konovalov, L. V., 283 Konovalov, Ya. D., 324 Konrad, P., 237 Koola, J. D., 244, 404 Koon, N. C.. 505 Koop, H., 156 Kopcewicz, M., 427, 442, 503 K o ~ v l o v .V. M., 83 Korda, V., 102 Korecki, J., 502 Korecz, L., 270, 400, 474 Korenstein, R., 263 Koridze, A. A., 22, 446 Korn, C., 113 Korneev, E. V., 420, 463 Kornilov, M. Yu., 102 Korolev, V. V., 74, 427 Korol’kov, V. V., 299 Korotchenko, N. A., 294, 295, 3 72 Korotkov, P. A., 216, 218 Korovin, S. S., 379, 384 Korovushkin, V. V., 420, 463

5 24 Korybut-Daskiewicz, B., 361 Koshel’, A. V., 288, 375 Koshizaka, N., 210 Koshkin, L. l., 453 Koster, J. B., 150 Kosterina, 1. K., 501 Kostikas, A., 415, 425, 437, 464 Kostiii, V. I., 386 Kostromina, N. A., 3, 8, 72 Kostsov, A. M., 420 Kostyanovskii, R. G., 62 Kosuge, K., 421 Kotel’nikov, V. P.. 31 1 Kotenko, 0. M., 216 Koth, D., 179 Kothekar, V., 438 Kotlicki, A., 427. 442, 503 Kotov, A. V., 333 Kotova, G. N., 461 Kotova, L. S., 23, 329 Kotowycz, G., 95 Kotrelev, K. V., 245 Kouinis, J., 301 Kovachev, D. I., 308, 372 Kovalev, 1. F., 200. 249 Kovalev, U. F., 243 Kovalev, V. V., 291, 402 Kovaleva, L. T., 212 Kovaleva, S. K.. 503 Kovar, R. A., 231, 240 Kovba, V. V., 202 Kovobanova, N. L., 251 Kovrikov, A. B., 206, 276, 277 Kovtum, H: M., 503 Kowalewski, J., 4 Kowalik, T., 41, 96 Kozima, S., 140 Kozlov, E. S., 174 Kozlova, L. l., 294, 372 Kozlova, N. V., 200, 249 Kozlova, V. A., 479 Kozlowski, H., 41, 96 Koz’mina, M. L., 263 Kozulin, A. T., 266 Kozyrev, B. M., 94 Kozyrkin, B. l . , 83 Krabbes, G., 146 Kraemer, R., 157 Krainik, N. N., 171 Kramer, C. E., 373 Kramer, G. W., 130 Kramer, L., 157 Kramer, P. A., 88, 313 Kramolowsky, R., 335, 367, 387 Krane, J., 40 Krasnushkin, A. V., 120 Krasser, W., 191 Kraunich, H.-J., 270 Krauss, H. L., 367 Krausz, P., 292 Kravchenko, A. N., 313, 398 Kravchenko, E. A., 119, 177 Kravchenko, L. Kh., 263 Kravchenko, 0. V., 239 Kravchenko, V. V., 303 Kravtsov, D. N., 81, 154 Kreber, E., 416, 460 Krebs, B., 252 Kreevoy, M. M., 89 Kreiner, W. A. 187 Kreissl, F. R., 10, 1 1 Kreiter, C. G., 10, 46, 48, 32:

Author Index Cress, J., 230, 378 Creutzer, 1’. H . , 351 Crieger, J. K., 64 (riegsmann, H., 253 ., 358, 359 Stasyuk, I. V.. 217 Statelova, A. T., 308. 372 Statler, J: A., 14 Stec, W. J., 150, 154, 157, 159 Steele, 13. R., 31, 310 Steenhoek, L., 83 Stefanovich, V. A., 210 Steger, E.. 250, 386 Steger. H . F., 431 Stegmann, H . H . , 84 Steiger, Th., 268 Stein, G. E., 434 Stein, L.. 274 Stein, P., 360 Steinbach, W., 181 Steinback, E., 228 Steinbeisser, H., 271 Steinberger, H., 142, 264 Steiner, P., 496, 505 Steinfeld, J. I., 184 Steinfink. H., 466 Steinkilbcrg, W., 17 Stelzer, 0.. 13, 14, 1 3 1 Steniplle, W., 7, 323 Stepanenko, 0.N., 396 Stepanenko, V. I.. 415 Stepanov, I. A., 261 Stepanova, L. I., 428 Stepanova, V. A., 81 SteDhenson. T. A.. 25.. 79., 86. 305, 388 Stepin, B. D.. 381 Stern, M., 389 Stetsenko. A. I.. 75. 357 Stetsenko; M . E., 466 Stetsenko, T. S., 212, 294 Steudcl, R., 271 Stevens, D. C., 324 Stevens, J. G., 406, 408 Stevens, V. E., 406 Stevenson, J. R.. 207 Stewart, J . M., 14 Stewart, R. C., 5, 310 Stewart, R . P., jun., 19 Stibbs P. 82 133 Stibr. 'R..'I2?. 232 Stikham, H. D., 316 Stillinger, F. H., 222 Stobart, S. R., 247, 345 Stocco. G . C.. 244. 246. 254. 316. 394, 472, 476 Stockis. A., 49 Stoeckli-Evans, H., 200 Stoeckmann, H. J., 1 1 1 Stohr, J., 497, 499 Stofko, J. J., jun., 27 Stohler, F., 370 Stoklosa. H . J.. 314 Stolarczyk, U., 353 Stoll, H., 261 Stolpovskaya. V. N., 217 Stone, F. G. A., 15, 19, 22, 26, 31, 32, 34, 48, 56, 127, 129, 234, 299. 345, 364 Stone, J., 251 Stone, J. A., 354, 431, 500 '

Stone, N. J., 4 Stone, W. E. E., 104, 120 Stopschinski, W.. 274 Storhott; B. N., 128 Storr, A., 57, 233 Story, H. S., 105 Stothers, J. 13.. 31, 32 Stover, C. S., 82 Stoyanov, E. S., 267 Strack, H., 46 Strakhov, N . B., 113 Strange, J. H., 109 Stranks, D. R., 77 Stransky, K., 249 Strathdee, G., 18 Straub, D. K., 434 Straughan, B. P., 156, 257, 317 Strauss, H. L., 202 Streefkerk, D. G., 142 Strehlow, H., 68 Strekas, T. C., 281, 372 Strelenko, Yu. A., 61 Stringer, A. J., 32, 334 Strizhkova, I. G., 359 Strobel, G. J., 75 Strommen, D. P., 317 Strouf, O., 238 Strouse, C. E., 89, 234 Struchkov, Yu. T., 150, 249, 41 7 Stucky, G. D., 65 Stuber, S., 46 Stuhler, H.-O., 54 Stunzi. H.. 356 Stufkens, D. J., 25, 33, 306, 311, 350 Strugova, L. I., 505 Stukan. R. A.. 408. 414. 417. 418, 430,,436, 440, 442, 446 Stumbreviciute, Z., 39, 40, 41 Stupel, M . M., 505 Stutz, C. I., 168 Su, S. R., 403 Subayhiev, V. K., 238 Subramanian, M. S., 103 Subramanian, Y., 462 Sudol. T.. 157 Sudzhben; D., 312, 373 Suss, G., 372 Suetaka, W., 450 Suaitani. Y.. 285 Sugiura,' M.; 160 Sugiura, Y., 35, 400 Suglobov, D. N., 296, 376 Sukhikh, A. I . , 300 Sukhoverkhov, V. F., 423 Suknev, V. S., 251 Suleimanov. S. P.. I I2 Sullivan, B.'P., 129, 234 Sullivan, J. C., 386 Sultanov, G . D., 458 Summers, S. E., 102 Sun, T. S., 220 Sunder, S., 280, 362 Sundermeyer, W., 131, 270 Sundmeyer, L., 270 Surana, S. S. la.,318 Surkov, B. A , , 23, 302 Sushchinskii, M. M., 213 SuSiE,, M., 123 SutclitTe, L. H., 1 Suter, R., 503 Sutherland, K. G., 23

Author Index Sutor, P. A., 144 Suvorova, K. M., 376 Suwalski, J., 455, 456 Suzdalev, I. P., 408, 418, 430, 450, 453, 461, 505 Suzuki, E. M., 268 Suzuki, H., 288 Suzuki, M., 184 Suzuki, T., 441 Suzuki, Y., 433 Svanidze, 0. P., 357 Sventitskii, E. N., 68, 153 Svergum, V. I., 287 Svilarich-Soenen, M., 156 Svitych, R. B., 93 Swallow, G. A., 451 Swanenburg, T. J. R., 104 Swanson, R. I., 219, 276, 283 Swartzendruber, L. J., 483, 502 Sweger, D., 497, 502 Swile, G. A., 397, 398 Swyke, C., 63, 156, 259 Syassen, K., 195 Svch. A. M.. 213. 287. 391 Sychkova, L: D.,’40 ’ Symes, K. C., 72 Synions, M. C. R., 223 Svritskava. Z. M.. 108 Syrtsova, G. P., 358 Syrtsova, Zh. S., 83 Szabo, A., 360 Szafraniec, L. L., 154 Szczecinski. P.. 70 Sze, Y. K., 3 1 6 Szcfcr. M., 427, 503 Szytula. A., 502 Tabacik, V., 203 Tachikawa, M., 52 Tacke, R., 242 Tacon, J., 285 Taft, C. A., 465 Taillandier, E., 247 Tajtelbaum, D. J., 324 Takacs, L., 417 Takada, T., 421,422,469, 505 Takafuchi, M., 414 Takagi, I., 29 Takahashi, A., 69 Takahashi, H., 201 Takahashi, S., 34, 102, 334, 398 Takamura, T., 292 Takano, M., 421, 469 Takashima, Y., 304, 431 Takats, J., 8, 48, 289 Takayanagi, H., 31 I Takeda, M., 422, 486 Takeda, Y., 469 Takeda, Y.-I., 64 Takenaka, T., 273 Takeno, S., 273 Takeuchi, K., 54 Takeuchi, M., 101 Takezhanova, D. F., 290 Takiguchi, T., 288 Takizawa, T., 336 Takusaka, T., 235 Talalakin. G. N., 421 Talalkar, P. V., 385 Taldenko, Yu. D., 349 Tallerchik, B. A., 420 Tamaev, S. T., 483

539 Tan, H.-W., 155, 262 Tanaka, H., 35, 400 Tanaka, K., 8 I , 299, 3 12 Tanaka, N., 376 Tanaka. T., 53, 54, 64, 81, 83, 97, 183 Tanc, J., 211 Tandon, J. P., 363, 382, 399 Tandon. S. K.. 254 Tandon; S. P.,’318, 321 Taneja, S. P., 502 Tanemoto, K., 226, 301 Tang, S., 59 Tang, S. P. W., 281 Tang, S.-Y., 268 Tang Wong, K. L., 338 Tanh, N. V., 226 Tanswell, P., 102 Tantot, G., 274 Taragin, M. F., 463 Taranukha, 0. M., 120 Tarasevich, A. S., 146 Tarasov, V. I . , 421 Tarasov, V. P., 133 Tarasova, A. I., 237, 393 Tarina, D., 41 1, 423 Tarli, F., 400 Tashtanova, M., 210 Tasumi. M..,102, , 398 Talsimirskii, K . B., 381 Tatsumi. T.. 14. 348 Taube. H., 201,’349, 365 Tauc, J., 265 Tauszik, G. R., 26 Tavares-Forneris. Y.. 202 Tayim, H. A., 309, j13, 332, 394

Taylor, G. A., 60, 138 Tavlor. K. R.. 8 Tailor: N. J.. 37. 228. 3 13. 3 16 Taylor; P., 15, 162, 275 Taylor, P. C., 103 Taylor, R. C., 186 Tavlor. S. H.. 19. 26. 28 Taylor; W., 217’ ‘ Tazeeva, N. K., 63, 155 Tchir, P. 0..199, 200 Tegenfeldt, J., 110, I 1 3 Teichman, R. A., 193 Teichmann, H., 154 Teichner, S. J., 358 Tejada, J., 438 Telkova, I. B., 156 Temme, G. H., tert., 30 Temperini, M . L. A., 201 Templeman, G. J., 6 Temussi, P. A., 75 Temyachev, I. D., 91 Tenhover, M., 483 Tennent, N. H., 403 Tensmeyer, L. G., 72 Teo, B. K., 445 Terry, J. H., 140, 244 Teslenko, S. P., 420 Teterin, E. G., 227, 289, 386 Tevault, D. E., 194, 281 Tevzadze, M. N., 285, 317, 380. 381 Thabct, S. K., 394 Thackeray. J . R., 387 Thapdeus, P., 187 Thain, J. M., 222 Thakkar, A. I-.,72 Thanh, N . V., 193

Thanebinkarn. S.. 1 1 Thaier, J. S., 394: 484 The, K . I., 149, 152 Theophanides, T., 88, 3 12, 313. 335. 362 Theuwissen, R., 440 Theveneau, H., 117 Thewalt, U., 287 Thich. P. B.. 295 Thiel,’R. C . ; 496 Thiele, G., 317 Thiele, K.-H., 8, 293 Thierling, M., 255, 304 Thirase. G.. I17 Thomas, €3.; 156 Thomas, B. S., 127, 235 Thomas, J. M., 449 Thomas, M. F., 457 Thomas, P., 386 Thomas, R. K., 196 Thompson, C. L., 440 Thompson, D. A., 128, 234 Thompson, D. J., 19 Thompson, J. C., 390 Thompson, J. R., 505 Thompson, P. J., 88 Thompson, R. C., 385 Thomson, A. L., 123 Thomson, J., 87 Thomson, J. O., 493, 505 Thornton, D. A., 277, 315 Thornton, D. D., 463 Thornton, E. W., 478 Thornton, J. M., 102 Thorpe, M . F., 232 Thorpe, R. V., 224, 316 Thouvenot, R., 295 Thym, S., 193 Tiemann. E.. 182 Tiezzi, El, 94, 95, 96 Tikhonina, N. A., 150 Timms, P. L., 22, 34, 83, 333 Timofeeva. G. I.. 150 Timoshchenko, 6. T., 196 Tinhof, W., 130 Tinyakova, E. I., 287 Tipping, A. E., 90, 1 38, 141, 144, 145, 250 Tipsword, R. F., 168 Tirouflet, J., 7, 8 Titov. L. V.. 89. 125 Titova, K. V., 133 Tiwar, S. K., 403 Tiwari, P., 254, 471 Tkachenko, I., 334, 388 Tkachuck, R. D., 25 Tobias, R., S., 76, 225, 229, 310, 313, 363 Todd, L. J., 5, 10, 50, 54, 127, 128, 129, 232 Tragersen, S., 159 Torring, T., 182 Tofield, B. C., 460 Tok, G. C., 255 Tokareva, S. A., 194 Tolman, C. A., 384 Tolgyessy, T., 408 Tolley, M. S., 157 Tolls, E., 151, 159, 264 Tolman, C. A., 13, 32, 33 Tolstaya, T. P., 299 Tolstoi, M. N., 251 Tom, G. M., 365 Toma, C., 371

540 Toma, H. E., 24, 442 Toma, S., 22 Tomala, K., 496, 502 Tomandl, G., 408 Tomarchlo. C.. 353. 475 Tom Dieck, H., 13, 20, 46, 327, 339, 364 Tomilov, S. B., 434, 463 Tominaga, T., 116, 408, 422, 423 Tomkins, I. B., 79, 304 Tomkinson, J., 233 Tomov, T., 450 Tondello, E., 319 Tong, D. A., 174 Tong, J. P. K., 74 Toniolo, L., 34, 48, 56, 351, 362 Topart, J., 143 Topchieva, K. V., 212 Topka, T. M., 140, 336 Toporkova, E. B., 83 Topouzhkanian. A., 191 Tomoe. H.. 396. 450. 451 Toichenkova, E: A,, '294, 295 Tori, K., 92 Toriyama, T., 449 Tornero. J.. 463 Torrance, 6. P., 325 Torres-Filho, A., 291 Torrie, B. H., 209 Tosi, G., 285, 304, 309, 316, 386 Tosi, M. P., 223 Tossidis, I., 390 Tosteson, D. C., 71 Totani, T., 235 Tourangeau, M. C., 76 Toutin, J., 263, 270 Towl, A. D . C., 55 Townsend, C. A., 30 Townsend, M. G., 465 Toya, T., 122 Tracey, A. S., 1 Traficante, D. D., 64 Trahanovsky, W. S., I I Tramontano, A., 9 Tran Dinh Son, 72 Tranquille, M., 390 Trautwein, A., 409, 416, 426, 432, 438, 442, 460 Traverso, O., 319 Travkin, V. F., 303 Trekoval, J., 322 Tremblay, R. J., 465 Trend, J . E., 162 Treppendahl, S., 162 Tribo. M.. 127 Trichet, L:, 106 Tricker, M . J., 414, 417, 449, 470 Trigwell, K. R., 257 Tripathi, S. C., 338 Triplett, B. B., 483, 484, 492, 498 Trippett, S., 146, 155 Tromel, M., 312 Trofimov, G. L., 116 Trogler, W. C . , 4, 30, 86, 95, 309, 310 Trogu, E. F., 324, 387 'Troilo, G., 365 Trojanowski, J., 92 Trommsdorff, K.-U., 265

Author rrontelj, Z., 109, 110, 170, 171 'rooster, J. M., 416, 424, 493 'rotter, J., 233, 304, 403 'rukhtanov, V. A., 440, 469 -rumble, W. R., 204, 215, 221 'ruter. M. R.. 378 rsai, K.-H., 140, 336 rsay, Y.-H., 22 rsemekhman, L. Sh., 464,465 rsetlina. E. 0.. 244. 251 rsin, T.'B., 304, 43i, 478 rsintsadze, G . V., 285, 317, 354, 358, 380. 381 rsipis, C. A., 391 rsitsishvili. V. G.. 121. 143 rsivadze, A. Yu., 285,317, 354 380, 381 rsuboi. M.. 190 rsurin,' V. A., 505 rsushima, T., 210 rsutsui, M., 47, 103, 318, 336 rsvetkova, E. V., 210 rsyashohenko, Yu., P., 218 rsyganov, A. D., 457, 461, 479 Tuchagues, J.-P., 129 ruck, D. G., 198, 234, 276, 400 Tucker, J. N., 101 Tucker, J . W., 115 Tucker, N. I., 18, 28 Tucker, P. A.. 27, 333 Tunstall, D. P., 2, 117 Tuohi, J. E., 109 Turaev, E. Yu.. 42 I , 470 Turbini, L. J., 125, 131, 235 Turnbull, K. R., 74 Turner, B. E., 182 Turner, G. K., 34, 37 Turner, J. J., 281, 338, 340, 34 1 Turner, K., 323 Turner, R. F., 340 Turney, T . W., 34, 333 Turov, A. V., 102 Turrell, G., 193, 207 Turta, K. I., 430, 436 Tweddle, N. J., 157 Tykachinskii, I . D., 479 Tzalmona, A., 112 Tzschach, A., 137, 241 Uchida, Y., 14, 348 Ucko, D. A., 76 Udovenko, V. V., 396 Udupa, M. R., 285, 3 1 5 Uebel, R., 157 Uehara, H., 193 Uehiro, T., 148 Uemura. E.. 72 Uemura; S.; 316 Ugi, I., 157 Ugo, R., 352 Uguagliati, P., 18 Uhl, A., 67 Uhlemann, E., 41 Uhrich, D. L., 254, 418, 468, 476 Ujihara, V., 433 Ukhanov, Yu. I., 208, 245, 304 Uller, W., 292 Ulman, J., 126

Index

Jmeyama, S., 503, 505 Jminskii, A. A., 274 Jmreiko, D . S., 206, 276, 277 Underhill, M., 345 Unger, E., 13, 14, 131 Ungerrnann, C. B., 79 Ungvary, F., 346 Uno, T., 245, 269 Unsworth, W. D,, 289 Upfield, J. A., 21 I Urland, W., 4 Urry, G., 245 Ursu, I., 7 Urushiyama, A., 204 Ushakov, N. V., 109 Ushakova, L. A., 105 Ushioda, S., 209 Uskov, V. A., 421 Uskova, S. L., 400 Uson, R., 233, 300, 312, 336, 357, 393 Ustynyuk, Yu. A,, 60 Uspenskii, M. N., 414, 456 Utebaev. U.. 140 Utida, T., 216 Utkina, 0. N., 227 Uttley, M. F., 79, 301 Uvarov. A. V.. 123 Uznanski, B., '157 Vaisburd, S. E., 464, 465 Vaishnava, 1'. I)., 318, 321 Vakhrameev, A. M., 119 Vakratsas, Th., 151, 152, 264 Valcu, N. 7 Valensin, G., 94, 95 Valic, M. I., 114 Valiev, K h . Kh., 483 Valueva, Z. P., 299, 338 van Raar, J. F., 25, 306, 350 Van Canteren, M., 274 Vanchikova, E. V., 15 Van Dam, E. M., 9 Vande Griend, L. J., 160 van den Berg, G. C., 283, 346 Van den Bergen, A. M., 26 van den Berghe, E. V., 135 Van den Eynde, I . , 19 Van Den Heuvel, C i . 1'. M., 263 van der Gen, A., 140 van der Kelen. G. P.. 132. 149, 257 Van der Klin, J. J., 71 van der Kooi, H. O., 140 Van der Kraan. A. M.. 505 van der Linden; J. G. M.,297 van der Ploeg, A. F. J . M., 309, 388 Van der Touw, F., 71 Van Der Veken, B. J., 262 Vander Voet, A., 191 Van der Woude, F., 396, 407, 457, 501, 503 Van d e Vondel, D. F., 135 Van Deyck, M., 464 van Diepen, A. M., 456, 466 van Dongen, J . P. C. M., 87 van Doorn, J. A., 32 Van Doorne, W., 68, 76 Van Duyneveldt, A. J., 91 Van Dyke, C. I{., 136, 241, 245, 252 Van Geet, A. L., 6

Author Index Van Gerven, L., 108 Van Hecke, P., 108 van Leeuwen, P. W. N . M., 90 Van Meerssche, M.,108 Van Loef, J. J . , 502 Van Oven, H. O., 7, 322 Van Paasschen, J. M., 125, 23 1 Van Rossum, M., 423, 464, 489 Van Steenwijk, F. J., 496 van Thinh, N., 38 Van Uitcrt, L. G., 499 Van Vliet, P. I., 28, 315, 352 van Vuuren, C. P. J . , 382 van Wazer, J . R., 90, 152, 153, 158, 159, 258 Van Winkle. J. L.. 301 Vara, J. M.; 427, ’463 Viradi, G., 346 Vardapctyan, R. P., 410, 483 Varfolomeev. M. B.. 482 Vargas, H . , i72, I75 Varhelyi, C., 307, 355 Varma, J., 464 Varma, R., 187 Varnek, V. A., 474, 478, 505 Varret, F., 415, 419, 420, 424, 499. Varwig, J., 27 1 Vasilescu, A., 79 Vasil’ev, L. N., 470 Vasil’ev, N. G., 124 Vasil’ev, V. G., 227 Vas/l’eva, N . P., 400 Vasilevskii, 1. V., 303 Vasil’kovskii, V. A., 503 Vaska. L., 306 Vast, P., 202 Vauahan. R. W.. 113 Vaxelti, E. L., 202 Vaziri, C., 138 Vdovin. V. M.. 249. 287 ’ Veillet,‘P., 108’ Velazco, J. E., 274 Velichko, A. V., 300 Venanzi, L. M.,33 Venkatesh, C. G., 195 Venkateswarlu, C., 376 Venkateswarlu. P., 214 Veracini, C. A., 33 Verani, G., 324 Verdonck, L., 257 Verenikina, S. G . , 130 Vereshchagina, A. P., 114 Vergagno, P. A., 404 Vergamini, P. J., 25 Verkade, J. G., 37, 151, 160. 259 Verlau, E. M., 213 Verma, A. L., 362 Verma, R. D., 193 Vermel, E. E., 79 Verner, 13. F., 465 Venevtsev, Yu. N., 469 Versaud, P.-C., 356 Verstuyft, A. W., 36, 80, 31; Vertes, A., 410, 441, 473, 48: Vesanen, 0. A., 110 Vesna, V. A., 496, 497 Vestin, R., 81 Vetrov, A. A., 196 Vetrov, 0. D., 113

54 1 Jiaene, L., 366 Jiard, B., 378, 383 v’iccaro, P. J.. 427. 432 Jicente,‘ J., 336 Jicentini, G., 381,384,385,404 Jidal. M.. 184 ijdali, M:, 312. 319, 320, 392 Jidulich, G., 133 diegcrs, M. P. A., 493 diennot. J. P., 220 digato, P. A., 319, 320 iigee. G . S., 81 diinikka, E. K., 416 v‘ijay. R. G., 382 r‘ijayaraghavan, R., I08 iilla, A. C., 35, 377 filla, J . F., 316 final, R. S., 373 fincent, D. H., 502 r‘incent, E. J., 4 Vincent, H., 265, 466 Vincze, I., 417, 505 Vinogradova, I. S., 1 1 1 Vinogradova, L. E., 234 Vinokurov. V. M., 115 Vinter, J. G., 8 Virlet, J., 99, 106, 110, 176 Vishnevskava. G . P.. 94 Vishnevskii: V. B., 251 Vishnyakov, Yu., S., 457 Visser, J. P., 81, 87 Viswanathan, K., 209 Vitagliano, A., 75 Viticoli, S., 400 Vlasova, E. V., 212 Vlingenthart, J . F. G., 142 Voelter, W., 75, 76 Vonel. H.. 424 VogeI, P. L., 1 6 Vogl, G., 407, 505 Vogl, w . , so5 Vogrin, F. J., 64 Voigt, R. F., 305 Voitkovskii, Yu. B., 458, 464 Voitlgnder. J.. 6. 118 Vojtech, O., 201’ Vold, R. L., 14 Vol’fkovich, S. I., 263 Volger, H. C., 301 Volgin, Yu. N., 208, 210, 245, 304 Vol’kenau, N. A., 23, 329 Volkov, A. F., 172, 480 Volkov, A. I., 288 Volkov, S. V., 226. 286 Volkov, V. L., 114 Volland, U., SO5 Vollenbroek, F. A., 309, 388 Vollhardt, K. P. C., 86, 346 Vollmann, W., 41 1 Vollmer, H.-J., 44 Vol’nov, I. I., 194 Volodin, A. A.. 156 Vol’pin, M. E., 417 Volponi, L., 285 Von Bardeleben, H. J., 421 von der Ohe, W., 204, 218, 321 Vongehr, M., 135 Von Lehmann, T., 23, 449 Von Meerwall, E., 445 Vonnahme, B. L., 444 von Philipsborn, W., 3 von Werner, K., 334 von Zdrojewski, W. V., 505 ’

dorob’ev, A. P., 218 Joronezheva, N. I., 72, 375, 394 v’oronkov, M. G., 142, 143, 173, 200, 243, 244, 249, 251 doronov, V. K., 97, 143 ioronovich, A. N., 64 Joronskaya, G. N., 384 ioss, J., 83, 335 dotava, W. E., 288 dotyakov, S. L., 41 dovelle, F., 220 v‘oznyuk, P. O., 449, 461 irabel, V., 314 iriesenga, J . R., 98 irieze. K.. 25. 28. 33. 57. 306. 311?s350, 352 ’ ’ ’ r‘uEeliC, D., 123 r‘ujatovic, S. S., 208 dvdrina. T. K.. 287 f’yunnik, I . M:, 417 ’

Waage Jensen, P., 220 Wachter, J., 1 1 Wachter, W. A., 320 Wada, K., 273 Wada, M., 32, 311 Wada, W., 251 Waddan, D. Y.,366 Waddington, D., 223 Waddington, T. C., 88, 233 Wtippling, R., 417, 418, 468, 493, 502 Wagner, B. E., 85, 93 Wagner, D.-L., 160, 264 Wagner, F. E., 491, 493 Wagner, H., 160, 264 Wagner, J. K.,301, 342 Wagner, U., 4Y 1 Wanner. W.. 497 W a h , A. c.;74 Wailes, P. C., 287 Waite, D. W., 127, 235 Wakabavashi. T.. 32 WakatsGki, K.,83 Wakatsuki, Y., 330 Wakerley, M. W., 319 Waki, S., 421 Waldvogle, G . G., 231 Walker, A., 308 Walker, F. A., 95 Walker, I. M.,102 Walker, J. C., 501 Walker, J. M., 124 Walker, M. L., 24, 158, 343 Walker, N., 108 Walker, R., 36, 292, 313, 364 Walker, W. R., 76 Wall, I., 319 Wallace, F. A., 76 Wallace. W. E.. 505 Wallart,. F., 200 Wallbridge, M. G. H., 34, 367 Walls. C.. 188 Walrafen,’ G. E., 251 Walsh, P. T., 496 Walter, A., 122 Walter, E., 152, 259, 261 Walter, W., 61, 83 Walton, D. R. M., 142 Walton, R. A., 283, 301 Wan, E., 89, 126 Wanczek, K.-P., 271 Wandiga, S. O., 85, 265

542 Wang, C. H., 218 Wang, D. K. W., 305 Wang, J. H., 184 Wang, J. T., 74 Wang, S.-M., 7 Wannagat, U., 242, 296 Ward, H. K., 43 Ward, J. E. H . , 10, 31, 32, 79 Wardell, J . L., 139, 476 Warner, L. G . , 401 Warning, K., 141 Warren, B., 75 Warren, R. F., 103, 321 Warren, S. E., 464 Wartel, M., 269 Warthmann, W., 263, 270 Wasserstein, P., 72 Wasson, J . K.,314 Watanabe, E., 230, 277, 360 Watanabe, H., 235, 505 Watari, F., 261 Watkins, C. L., 81 Watkins, J. J., 79, 233 Watkiss, P. J., 273, 473 Watson, D. G., 393 Watson, R. E., 505 Watters, K. L., 307 Watts, J. B., 366 Watts, K . O’H., 138, 141 Watt, W. E., 23 Waugh, J . S., 113 Wayland, B. B., 201 Waysbort, D., 95 Wazeer, M . 1. M., 150, 156 Webb, J., 77 Webb, M . J., 15 Webb, T. R., 283 Weber, L., 502 Weber, M . A., 304,430 Weber, U., 76 Weber, W., 81, 130, 232 Webster, A. H.. 465 Wedd, A. G., 364 Wegener, H., 433 Wegener, H . H. F., 407 Wehniann, A. T., 331 Wehmeier, E., 501 Wei, 11. H., 422 Weibcl, A. T., 65, 76 Weichniann, H., 137, 241 Weiden, N., 105, 1 1 1 , 113, I69 Weidenbrucli, M., 138 Weidlein, J., 133, 234, 247, 336, 379, 385 Weigand, E. F., 102 Weigel, F., 318 Weigelt, G.. 266 Weill, G., 43 Weinniaier. J . H.. 151 Weir, J . R:, 45 Weise, M., 276 Weiss, A., 105, 1 I I , 113, 169 Weiss, R. Z., 505 Weiss, E., 8, 117, 344 Weiss, J., 240 Weiss. K.. 106. 295 weisser, b., 367 Weitkamp, H., 191 Welch, A. J., 19, 34, 129, 234 Welleman, J . A., 315 Weller, F., 316 Wells, A. G., 72

A uthor Index Wells, P. R., 76, 88 Welsh, L. B.. 479 Wclr, E., 292 Wenckebach, W. Th., 104 Wenschuh. t.. 270 Werneke, M. k., 306 Werner, F., 89 Werncr, H., 85 Weser, U., 75, 76, 440 West, €3. O., 26, 320 West. K. W., 495 Westlake, D., 372 Westland, A., 289, 363 Weston. A. F., 235 Weulersse, J . M . , 110, 176 Weyer, G . , 413, 468 Whalley, E., 191, 195 Wharf, I., 218 Whatley, C., 316 White, A . H., 290 White, A . J., 48 White, T. R., 225 White, W. B., 212, 319 Whitesides, G. M., 64 Whitesides, T. H.. 18. 47, 86 Whjtfield, H. J . , 169 Whiting, R., 178, 315 Whittaker, B., 285, 321 Whynian, R., 332. 345 Wiberly, S. E., 190 Wicholas, M., 95 Wicke, H. G., 180 Widler, H. J., 234 Widersatz, G . O., 46 Wiegel, K., 287 Wieghardt, K., 29, 376 Wieker, W., 144, 145, 251 Wiesendanger, E., 209 Wiessflog. E., 243 Wiezer, H . , 270 Wiger, G., 34, 312 Wight, C. A., 192 Wikholm, G . S., 128 Wjlde, R. E., 221 Wildner, W., 505 Wiles, D. R., 462 Wiley, J. C . . jun., 249 Wilke, C i . , 7, 323 Wilkins, H., 30, 332 Wilkins, B. T., 131 Wilkins. J . D.. 291. 292..~293. 296, 387 Wilkinson. G . , 15, 103, 206, 215, 217, 299 Wilhinson, J. R., 5 , 10, 50, 54, 127 Wilhinson, M., 233 Willcott, M. R., 21 Willemse, J., 58 Willett, R. D., 176, 275, 426 Willey, G . R., 285 Williams, A. F., 25, 29, 492, 493 Williams, C. M., 505 Williams, 0.H., 92 Williams, D L., I14 Williams, E. H., 68 Williams, J . M., 408, 410, 501, 505 Williams, J. P., 15, 16 Williams, M . L., 185 Williams, R. J. P., 92, 96, 102 Williamson, D. E., 92

Williamson, D. H., 15, 26. 299 Williamson, D. L., 503 Willich, P., 208 Willis, S., 330 Wlllner, H., 201 Willsch, K., 112 Willson, M., 157, 160 Wilputte-Steinert, L., I I Wilson, D., 305 Wilson, J . M., 418 Wilson, L. J., 99, 100, 360, 43 5 Wilson, N. K., 39 Wilson, R. D., 160, 198, 206, 446 Wilson, R. S., 104 Wilson, W., 194 Wilson, W. W., 267, 274 Wimmer, K., 505 Windhorst. K. A., 355 Window, B., 432 Winfield, J . M., 15, 299 Winfree, W. P., 416 Wingfield, J. N., 261, 378 Winkelman, A., 26, 309 Winkler, E., 96 Winkler, H., 120, 405 Winnewisser, M., 184 Winograd, R. A . , 309 Winstead, J . A., 23 Winter, G., 271 Winter, W., 27, 28 Winterbottom, A . P., 449 Winterling, G., 210 Winterton, N., 5 Winterton, K. C., 302 Winther, F., 271 Wit, H. P., 415 Wittern, K . P., 123 Wittich, E. K . H . , 118 Witts, A. D., 494, 496 Wdfle, P., 505 Wohlfahrt, K., 405, 413 Wojcicki, A. J., I I , 15, 16, 328, 359, 378, 403 Wojciechowski, W., 314 Wojtowiecki, W. K., 407 Wold, A., 17 Wolf. J . - G . . 63 Wolf, R., 159 Wolf, W., 41, 83, 137, 1419 Wolfe, S., 240 Wolfsberger. . , I W.. 151. 249, 259 Wolmershaiiser, G., 264 Wolters, J., 140 Wong, A. M., 183 Wong, C. F. C., 293 Wong, C.-H., 7 Wong, C. S., 31 I Wong, H. S., 128 Wong, P. T. T., 195, 317 Wong, T. C. T., 385 Wong, Y . S., 316 Wood. L., 409 Wood; T. E., 214 Woodhams, F. W. D., 217, 476 Woodland, J. H. R., 150 Woodruff, R. A., 40 Woodruff, W. H., 361 Woods, M., 151 Woods, R . C., 182 ,

Author Index Woodward, P., 19, 20, 22, 48, 364 Woolf, A. A., 315 Wooten, J., 102 Wootton, R., 373 Woplin, J. R., 150 Worrall, I . J., 233 Worsfold, D. J., 6 Worth, J., 116, 445 Wortmann, G., 407, 492, 49 3 Wozniak, W. T., 276, 343 Wrackmeyer, B., 129, 136, 150 Wright. J. L. C.. 4 Wright; P. E., 96 Wright, R., 138 Wright, T. L., 230 wu. c. s.. 439 Wuethrich; K., 4 Wulfnian, D. S., 38 Wurrey, C. J., 204 Wursthorn, K. R., 140, 336 Wurtinger, W., 428 Xavier, A. V., 92 Yablonskii, 0. P., 75, 81, 93 Yadav. B., 111 Yagi, T.. 440 Yaglov, V. N., 288 Yaiima. T.. 462 Yikerson, V. I., 250 Yakimov, S. S . , 420, 454, 457 Yakinthos, J. K., 505 Yakovleva, 0. N., 287 Yakthinos, J. K., 497 Yakubov, Kh. M., 434 Yalymova, G. F., 148 Yalymova, S. V., 148 Yamada, K., 171, 174, 175, 176 Yamada, S., 296, 363 Yamaguchi, H., 72 Yamakawa, K., 330 Yamamoto, A., 216, 354, 376 Yarnamoto, H., 450, 505 Yamamoto, J., 304 Yamamoto, K., 210, 241 Yamamoto, O., 95, 133 Yamamoto, T., 127, 354 Yamamoto, Y., 38, 129, 130, 150, 315, 359 Yamanouchi, K., 296 Yamasaki, K., 29 Yamashita, K., 142 Yamauchi, M., 125 Yaniazaki, A., 330 Yamazaki, H., 359 Yampol’skii, V. I., 202 Yang, E. S., 74 Yang, Y. S., 197 Yanovskii, V. K., 420 Yanovsky, K., 406, 499 Yariv, S., 212 Yariv, Y., 440 Yarkevich, A. N., 299 Yarkova, E. G., 84 Yarmarkin, V. K., 421 Yarmukhamedov, Yu. N., 420 Yarosh. 0. G.. 243 Yarosh; V. V.,.235 Yarwood, J., 226 Yastrebov, V. V., 83, 101, 123

Yastrebova, L. F., 381 Yasufuku, K . , 31 Yasui. T.. 29 Yatirajam, V., 300 Yatsenko, A. P., 114 Yatsimirskii, K. B., 102, 226, 286. 349 Yeagle, P. L., 147 Yee, K . C., 262 Yeh, H. J. C., 21, 74 Yel’chaninova, S. D., 212, 294 Yen, C. S., 439 Yen Lung Chung, 309 Yesinowski, J. P., 37, 134 Ylinen, E. E., 109 Yoder, C. H., 61 Yokezeki, S., 502 Yokogama, A., 97 Yokono, T., 72 Yokoyama, A., 72 Yokoyama, Y., 210 Yolles, S., 150 Yoneda, H., 29, 86 Yonetani, T., 361 Yoshida, C. M., 361 Yoshida, G., 58 Yoshida, S., 321 Yoshida, Z., 230, 277, 360 Yoshihashi, T., 420 Yoshikawa, K., 4 Yoshino, Y., 148 Youll, B., 128, 232, 472 Young, D., 8, 287 Younger, D., 88 Yu, N.-Y., 362 Yu, S. H., 41 Yu, S.-L., 162 Yucupov, R . A., 207 Yuhnevich, G. V., 196 Yunusov, N . B., 176 Yurchenko, E. N., 474, 478 Yurchenko, G. K., 291 Yurchikov, E. E., 502, 505 Yurinov, Yu. V., 227 Yurkevich, A. M., 130 Yusfin. Yu. S., 458 Yushchuk, S. I., 455, 469 Zabotina, L. N., 381 Zabransky, €3. J., 484 Zack, N . R., 36, 371 Zadorozhnii, A. I . , 470 Zaev, E. E., 98 Zagurskaya, L. M., 62 Zaimovskaya, T. A., 302 Zaitsev, B. E., 352, 382, 400 Zaitseva, L. l., 300 Zaitseva, M. G., 381 Zaitseva, V. A., 352 Zakharkin, L. I., 128, 233 Zakharov, A. V., 68 Zakharov, K . S., 62 Zakharov, V. A., 79 Zakharova, 1. A., 302, 333 Zakirov, R. R., 457, 461 Zamaraev, K. I., 68, 80, 93, 97 Zambrzhitskii, V. N., 504 Zamir, D., 106 Zamkovoi, V. I., 102 Zanobi, .A., 25, 306 Zanobini, F., 306 Zarif’yants, Yu. A., 288 Zarli, B., 285

543

Zarubin, V. N., 420, 473 Zasimov, V. S., 483, 486 Zassinovich, G . , 306, 33 1 , 333, 396 Zavalishin, N. I.. 266 Zavarzina, N. N., 116 Zaw, K., 75 Zbieranowski, W. T., 117 ZcurkovB, L., 290 Zdanovich, V. I., 12 Zecchin, S., 306, 346 Zecchina, A., 294 Zeegers-Huyskens, T., 273, 274 Zeidler. M. D.. 43 Zeigan,‘ D., 144 Zeil, W., 187 Zeile, J. V., 325 Zeiss. R.. 122 Zeldin. M.. 61, 131, 239. 246. 250, .47 1 ,.472 Zelenev, S. V., 290 Zelentsov. S. S.. 68 Zelentsov; V. V’., 376 Zelionkaite, V.. 271 Zeltmann, A. H., 102 ZemEik, T., 462, 504, 505 Zemnukhova, L. A., 161, 386 Zemskov. S. V., 107, 116 Zerina, E. N., 234 Zhabrova. G. M.. 505 Zharavova, E. V., 294 Zharkova, G. I., 107 Zhdanov, A. A., 143 Zheligovskaya, N . N., 35 Zheludev, I. S.. 420, 463 Zhidomirov, C i . M., 123, 124, 130, 147 Zhilinskaya, V. V., 349 Zhiz,hin, G. N., 213 Zhuravlev, E. F., 382 Ziborova, T. A., 212 Ziegenfuss, G. H., 434 Ziegler, A., 312 Ziegler, M. L., 240, 372 Ziemann, H., 195 Zimina, G. V., 481 Zimmer, H., 3 Zimmerman, R., 410, 423, 424, 426, 427, 430, 439 Zingales, F., 18 Zingaro, R. A., 261 Zinich, J. A., 285 Zink, J. I., 77 Zinn, W., 103, 495, 497 Zinner, L. B., 384, 385, 404 Zinovjeva, T. I., 154 Zins, D., 201 Zinsius, M., 313 Zipp, S. G., 206 Zitkova-Wilcox, J., 412 Zlomanov, V. P., 480 Zobin. D.. 501 Zocchi, M.,374 Zogal, 0. J., I 1 3 Zolotov. Yu. A.. 267 Zolotoyabko, E.’ V., 41 3, 503 Zon, G., 157 Zonn, 2. N., 114 Zonnenberg, Yu. D., 501 Zoroatskaya, E. I., 99 Zsako, J., 307, 355 Zschunke, A., 148

Author Index

544 Zuckerman, J. J., 60, 139, 140, 243, 254, 374, 473,

50 1

Zuiderweg, L. H . , 71 Zukrowski, J., 502 h m e r , S., 104, 105, 110 Zundel, G., 223

Zunger, A., 220 Zuppiroli, L., 11 1 Zuur, A. P., 366 Zvarikina, A. V., 417 Zverev, V. V., 41 Zvyagin, A. I., 213, 294 Zwijnenburg, A., 7, 322

Zwolle, S., 71 Zyablikova, T. A., 99 Zyatkovskii, V. M., 7 3 Zykova, T. V., 148 Zyontz, L. E., 315 Zyvagin, A. I., 212