Spectroscopic Properties of Inorganic and Organometallic Compounds: v. 6: A Review of Chemical Literature (Specialist Periodical Reports)

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A Specialist Periodical Report

Spectroscopic Properties of Inorganic and Organometallic Compounds Volume 6

A Review of the Literature Published during 1972

Senior Reporter N. N. Greenwood, School of Chemistry, University of Leeds Reporters D. M. Adams, University of Leicesfer J. H. Carpenter, University of Newcastle upon Tyne 6. Davidson, University of Nottingham M. Goldstein, North London Polytechnic R. Greatrex, University of Leeds B. E. Mann, University of Shemeld S. R. Stobart, Queen's University, Belfast

@ Copyright 1973

The Chemical Society Burlington House, London, W l V OBN

ISBN: 0 85186 053 2

Library of Congress Catalog No. 74-6662

Organic formulae ronrposcd by Wright's Symbolset method

PRINTED I N GREAT BRITAIN BY JOHN WRIGHT AND SONS LTD., AT THE STONFBRIDCE PRESS, BRISTOL

Foreword

This Report provides a comprehensive review of literature published during 1972 on the n.m.r., n.q.r., microwave, vibrational, and Mossbauer spectra of inorganic and organometallic compounds. The coverage and arrangement closely parallel those adopted last year. The Reporters have made strenuous efforts to contain the growing weight of material within the confines of a readable narrative of similar length to those produced in previous years. Extensive use of tabular material at appropriate points has enabled much factual and bibliographical information to be presented without destroying the flow of textual commentary. It has been our aim not only to record results, but to indicate the wide variety of ways in which spectroscopic information is being used. Each chapter is self-contained and its length, and the number of references it contains, indicate the extent to which each technique is being applied to the study of inorganic and organometallic compounds. Each chapter states the range of work covered and the areas which have been omitted. The references have been obtained by means of the techniques outlined in previous volumes and we have tried to include all significant information published during 1972, though a few papers of Russian origin have had to be held over until next year. We have been greatly heartened to read the many warm reviews of earlier volumes-it is always gratifying to have one’s work appreciated-- but equally we would greatly value suggestions from users on the ways in which the coverage of material or its presentation could be improved. N. N. G .

Contents

Chapter 1 Nuclear Magnetic Resonance Spectroscopy By B. E. Mann 1 Introduction Techniques, Coupling Constants, Chemical Shifts, and Relaxation Measurements Techniques Coupling Constants 'H and lBFChemical Shifts 13C Chemical Shifts llB, 14N,16N,29Si,slP, 33S,35Cl,37Cl,77Se,7BBr, slBr, and lzgXeChemical Shifts Metal Chemical Shifts Relaxation Measurements 2 Stereochemistry Complexes of Complexes of Complexes of Complexes of Complexes of Complexes of Complexes of Complexes of Complexes of

Li, Be, Mg, Sc, Y,La, and U Ti, Zr, Hf, Th, V, Nb, and Ta Cry 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

1

1 4 4 6

8 10

12 14 15 15 16 18 20 27 29 43 52

60 61

3 Dynamic Systems Fluxional Molecules Equilibria Solvation Studies of Ions Ionic Equilibria Equilibria among Uncharged Species Course of Reactions

64 64 74 74 77 80 84

4 Paramagnetic Complexes Compounds of the &Block Transition Elements Compounds of the Lanthanides and Actinides

87 88 94

Contents

vi 5 Solid-state N.M.R.

Motion in Solids Structure of Solids

99 100

103

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

112 112 118 121

7 Compounds of Silicon, Germanium, Tin, and Lead

123

8 Compounds of Group V

138

9 Compounds of Group VI, VII, and Xenon

145

10 Bibliography Chapter 2 Nuclear Quadrupole Resonance Spectroscopy By J. H . Carpenter

148 154

1 Introduction

154

2 Instrumentation and Techniques

155

3 Main Group Elements Group I (Sodium-23, Potassium-39, Potassium-40, Potassium-41, Rubidium-85, and Rubidium-87) Group 111 (Aluminium-27, Gallium-69, and Gallium71) Group V (Nitrogen-14, Arsenic-75, Antimony-121, Antimony-1 23, and Bismuth-209) Group VI (Oxygen-1 7) Group VII (Chlorine-35, Chlorine-37, Bromine-79, Bromine-8 1, and Iodine-1 27)

156

4 Transition Metals M anganese-55 Cobalt-59 Copper-63 and Copper-65 Niobium-93 Tantalum-1 8 1

172 172 172 173 173 174

Chapter 3 Microwave Spectroscopy By J. H. Carpenter

175

156 156 157 162 162

1 Introduction

175

2 Instrumentation and Technique

176

3 Diatomic Molecules

177

Contents

vii

4 Triatomic Molecules

181

5 Tetra-atomic Molecules

183

6 Penta-atomic Molecules

187

7 Molecules containing Six or More Atoms

191

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

196

1 General Introduction

196

2 Spectra of Small Symmetric Species Diatomic Species Triatomic Species Tetra-atomic Species Pen ta-atomic Species Hexa-atomic Species Hepta-atomic Species Larger Symmetric Species

198 198 200 207 210 218 22 1 225

3 Single-crystal and other Solid-state Spectroscopy 'Simple' Lattice Types Mixed Oxides and Fluorides Sheet and Chain Structures Complex Halides Oxoanion-containing Crystals Complex Cationic Salts Complex Anionic Salts Molecular Crystals Others

227 227 230 23 1 233 235 237 238 243 244

Chapter 5 Characteristic Vibrational Frequencies of Compounds containing Main-group Elements By S. R. Stobart

245

1 Group I Elements

245

2 Group I1 Elements

246

3 Group I11 Elements Compounds containing B-H Bonds Compounds containing AI-H or Ga-H

248 248 253

Bonds

viii

Contents Compounds containing M-C Bonds (M = B, Al, Ga, In, or T1) 254 Compounds containing M-N Bonds (M = B, AI, or Ga) or B-P Bonds 257 Compounds containing M-0 Bonds (M = B, Al, Ga, In, or TI) 260 Compounds containing M-S Bonds (M = A1 or In) or M-Se Bonds ( M = B or Al) 262 Compounds containing M-Halogen Bonds (M = B, AI, Ga, In, or TI) 262

4 Group IV 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, Ge, or Sn) Compounds containing M-N Bonds (M = Si, Ge, Sn, or Pb), M-P Bonds (M = Si or Sn), or Si-As Bonds Compounds containing M-0 Bonds (M = Si, Ge, Sn, or Pb) Compounds containing M-S Bonds (M = Si, Ge, or Sn), M-Se Bonds (M = Si, Ge, or Sn), or Sn-Te Bonds Compounds containing M-Halogen Bonds (M = Si, Sn, or Pb)

264

5 Group V Elements Compounds containing E-H Bonds (E = N or P) Compounds containing E-C Bonds (E = N, P, As, Sb, or Bi) Compounds containing N-N or N-P Bonds Compounds containing As-N, Sb-N, or P-P Bonds Compounds containing E-0 Bonds (E = N, P, As, Sb, or Bi) Compounds containing N-S or P-S Bonds Other Compounds containing a Group V Element Bonded to a Group VI Element Compounds containing Group V-Halogen Bonds

282 282

6 Group VI Elements Compounds containing 0-H, S-H, or Te-H Bonds Compounds containing E-C Bonds (E = S, Se, or

299 299

Td

265 270 273 275 277 278 280

283 286 29 1 292 294 297 297

300

Contents

ix

Compounds containing 0-0,S- 0, Se-0, Te-0, S-S, S-Se, or Te-Te Bonds Compounds containing Group VI--Halogen Bonds

30 1 304

7 Group VII Elements

306

8 Group VIII Elements

307

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

309

1 Introduction

309

2 General

309

3 Scandium

314

4 Titanium, Zirconium, and Hafnium

315

5 Vanadium, Niobium, and Tantalum

318

6 Chromium, Molybdenum, and Tungsten

32 1

7 Manganese, Technetium, and Rhenium

327

8 Iron, Ruthenium, and Osmium

330

9 Cobalt, Rhodium, and Iridium

335

10 Nickel, Palladium, and Platinum

34 1

11 Copper, Silver, and Gold

348

12 Zinc, Cadmium, and Mercury

352

13 Lanthanides

356

14 Actinides

358

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

36 I

1 Carbon Donors

361

2 Carbonyls 3 Nitrogen Donors Molecular Nitrogen, Azido-, and Related Complexes Amines and Related Ligands

384 394 394 399

X

Contents

Oxi mes Ligands containing )C=N’ Cyanides and Isocyanides Nit rosyls

Groups

406 407

41 1 416

4 Phosphorus and Arsenic Donors

419

5 Oxygen Donors

423 423 424 427 434 436 437 439 443

Molecular Oxygen, Peroxo-, and Hydroxy-complexes Acetylacetonates and Related Complexes Carboxylates Keto-, Alkoxy-, Phenoxy-, and Ether Ligands 0-Bonded Amides and Ureas Nitrates and Nitrato-complexes Ligands containing 0-N, 0-P, or 0-As Bonds Ligands containing 0-S Bonds 6 Sulphur and Selenium Donors

445

7 Potentially Ambident Ligands Cyanate, Thiocyanate Complexes, etc., and Isoanalogues Ligands containing N and 0 Donor Atoms Ligands containing either N and As or N and S Donor Atoms Ligands containing 0 and S Donor Atoms

454

8 Appendix : Additional References to Metal Carbonyl

Complexes Vanadium, Niobium, and Tantalum Carbonyl Complexes Chromium Carbonyl Complexes Molybdenum Carbonyl Complexes Tungsten Carbonyl Complexes Manganese Carbonyl Complexes Technetium and Rhenium Carbonyl Complexes Iron Carbonyl Complexes Ruthenium Carbonyl Complexes Osmium Carbonyl Complexes Cobalt Carbonyl Complexes Rhodium Car bony1 Complexes Iridium Carbonyl Complexes Nickel, Palladium, and Platinum Carbonyl Complexes Mixed Transi tion-metal Carbon yls

454 458 463 463 466 466 467 469 473 475 477 47 8 485 48 7 488 489 490 49 1 49 I

xi

Contents

Chapter 8 Mossbauer Spectroscopy By R. Greafrex

494

1 Introduction Books and Reviews

494 494

2 Theoretical

497

3 Instrumentation and Methodology

500

4 Iron-57 General Topics Nuclear Parameters, Hyperfine Interactions, and New Effects Pressure-dependence Studies Lattice Dynamics Alloy-type Systems 67FeImpurity Studies 6 7 C Source ~ Experiments and Decay After-effect Phenomena Compounds of Iron High-spin Iron(ir) Compounds High-spin Iron(m) Compounds Spin-crossover systems, Unusual Electronic States, and Biological Compounds Low-spin and Covalent Complexes Oxide and Chalcogenide Systems containing Iron Binary Oxides Spinel Oxides and Garnets Other Oxide Systems Minerals C halcogen ides

502 502

5 Tin-119 General Topics Tin([[) Compounds Tin(1v) Compounds

567 567 574 575

6 Other Elements Main Group Elements Germanium ('"e) Krypton (83Kr) Antimony (121Sb) Tellurium (IzSTe) Iodine (lZ7I, 9 ) Caesium ( 133Cs)

590 590 590 59 1 59 1 594 595 600

502 505 506 507 509

512 516 516 524 530 537 542 542 547 552 558 565

xi i

Confen t s

Transition Elements Nickel (61Ni) Zinc ("'zn) R utheni um (09Ru) Hafnium (178Hf,leoHf) Tantalum (IslTa) Tungsten (laow,IS2W, Ie3W, lE4W,lasW) Osmium (lesOs, leaOs,lEQOs, leoOs) Iridium (lQ11r) Platinum (le5Pt) Gold (lQ7Au) Lanthanide and Actinide Elements Samarium (la9Sm) Europium (151Eu, 1 5 3 E ~ ) Gadolinium (155Gd,157Gd) Dysprosium (161Dy) Holmium (lsaHo) Erbium (lssEr) Ytterbium (170Yb, 171Yb) Uranium (236U, 238U) Neptunium (237 N p) Plutonium (239Pu) 7 Bibliography

Author I ndex

60 1

60 1 60 I 60 I 60 1 602 604 605 607 607 607 608 608 609 61 1 612 61 2 612 612 613 61 3 616 616 623

Abbreviations

acac astp ata azb biPY bn CNDO 1,7-~th cyd ta dbm depe DHMB diars diars’ dien dimetrien diphos) Pf-Pf dmaq DMF dmgH dmg DMSO dPm dPPa dPt ed3a edda

edpa edta eee en

acetylacetone anion tris(o-diphenyIphosphinopheny1)arsine N(CH2C02)33azobenzene bipyridyl butylenediamine complete neglect of differential overlap

5,7,7,12,14,14-hexamethyl-l,4,8,11-

tet ra-azacyclotetradecane cyclohexanediaminotetra-aceticacid dibenzoylmethane anion 1,2-bisdiethylphosphinoethane Dewar hexamethylbenzene

0::::

Ph,AsCH,CH,AsPh, diethylenetriamine H,NCH,CH,NHCH(Me)CH( Me)NHCHaCH2NH2 PhaPCHZCH2PPh2

8-dimethylarsinoquinoline di met hy lformamide dimethylglyoxime monoanion of dimethylglyoxime dimethyl sulphoxide di pivaloylmethane 1,2-bisdiphenylphosphinoacetylene dipropylenetriamine (HO,CCH2)2NCH,CH2NHCH,CO,H ethylenediaminediacetic acid H02CCH2 CHzCOaH \

/

/

NCHzCH2N \

H02CCH(Me) CH( Me)CO,H (HO2CCH2)2NCH2CH2N(CHzCO2H)a

HzNCH2CH2SCH2CH2SCHZCHaNHz

ethylenediamine

xiv ffars

ffos f,fOS

f*fos fod H,dtpa hfac nta mida ida 4-mpdpa OECy pdta Pf= Pf phen pic y-pic0 Pm-Pm Pn p tas PY PYO 9P R-en sal salen sbtp SMCy SP tcne terPY terPYO3 tetren THF tmed TPP trien tripyam tta ttn tu

-- 1, X = Me,As IZ = 1 , X = Ph2P n = 2, X = Ph2P ti

I

Abbreviations X

\ / ,c=c \

(CF2),--CF2 n = 4, X = Ph2P 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyloctane-4,6dionato (HO2CCH2)2NCH2CH,N(CH,C02H)CH,CH,N(CH2CO,H)2 hexafluoroacetylacetonato R = CH,C02H R = Me RN(CH,CO,H), R = H 4-methyl-2-pyridyldi-(2-pyridyl)amine -SCH2CH(NH2)C02Et propylenediaminetetra-acetic acid Ph2PCH=CHPPhz 1 ,lo-phenanthroline picol i ne y-picoline N-oxide Me2PCH,CH2PMe2 propylenediamine tris(o-diphenylarsinopheny1)phosphine pyridine pyridine N-oxide tris(o-diphenylphosphinopheny1)phosphine RNHCH2CH2NH2 salicylate anion NN’-et hylenebis(salicyla1diminato) tris(o-dipheny1phosphinophenyl)sti bine MeSCH2CH(NH2)C02o - C H ~ =CHC8HdPPh2 te tracy anoethylene 2,2’,2”-terpyridyl 2,2’,2”-terpyridyl NN’N”-trioxide tetraethylenepentamine tetrahydrofuran Me2NCH2CH2NMe2 tetraphenylporphorin triethylenetetramine tri-(2-pyridy1)amine anion of thenoyltrifluoroacetone 1, I ,1-tris(dimethylaminomethyl)ethane thiourea

1

cm-I J mol-' eV kcal mol-l Mc s-l (MHz)

1 1.957 1 9.6484 x 104 4183.3 3.9903 x 10-4 1

4.3359 x 10-2 4.1344 x 10-9

1.2394 x 1O-O 1.0364 x

Conversion factors J mol-l eV

For other nuclides multiply the above conversion factors by €7 (keV)/14.413.

J mol-l kcal mol-l

2.8584 x 2.3904 x 2.3063 1 9.5345 x 10-8

kcal mol-'

Mossbauer spectra For 57Fe(Ey = 14.413 keV): 1 mm s-l = 3.879 x lob4cm-1 = 4.638 x = 4.809 x 10-8eV = 1.109 x = 11.63 MC s-' (MHz)

I 8.3626 x 8068.3 349.83 3.3356 x

cm -l

2.9979 x 104 2506.2 2.4188 x lo8 1.0487 x 10; 1

Mc s-l (MHz)

X

1

Nuclear Magnetic Resonance Spectroscopy BY B. E. MANN

1 Introduction This year has been marked by the welcome appearance of a Specialist Periodical Report devoted to Nuclear Magnetic Resonance.’ Consequently, the terms of reference of the present Report have been modified to include only inorganic and organometallic compounds, and many developments in instrumentation and techniques have been omitted. In spite of this, the number of references abstracted have increased yet again. In order to reduce the volume of the Report, tables have been incorporated into the text. The use of the Chemical Society’s n.m.r. Macroprofile (UKCIS) has been changed. All 1972 references obtained via this Macroprofile have been incorporated into the text and only 1971 references which were not discussed in last year’s Report are included in the bibliography (pp. 148153).

As would be expected, lH n.m.r. spectroscopy continues to provide most of the information reported here. However, interest in other nuclei has been widespread and includes 2H, ‘Li, llB, 13C, 14N, 16N, 1 7 0 , l9F, 23Na, 2SMg,27Al,2gSi,31P, 33S,V l , 87Cl,3gK, 47Ti,“Ti, 61V, 66Mn,67Fe,50Co, 63Cu, 6gGa,71Ga, 7 6 A ~77Se, , 7gBr, 81Br, 85Rb, gSNb, Io6Pd, llOSn, 129Xe, lSSCs l87Re, lg9Hg,and 201Hg. The flood of relevant books and reviews has continued. It has proved necessary to split Volume 5 of ‘Annual Reports on N.M.R. Spectroscopy’ into at least two parts, with Part A occupying 696 pages.2 Volume 5A contains chapters on ‘General review of proton magnetic resonance’ by T. N. Huckerby, ‘Fluorine-19 N.M.R. spectroscopy’ by R. Fields, ‘N.M.R. spectroscopy in the study of carbohydrates and related compounds’ by T. D. Inch, ‘Heteronuclear magnetic double resonance’ by W. McFarlane, ‘Nitrogen N.M.R. spectroscopy’ by G. A. Webb and M. Witanowski, ‘N. M.R. spectroscopy in liquids containing compounds of aluminium and gallium’ by J. W. Akitt, and ‘The application of Fourier transformation to high resolution N.M.R. spectroscopy’ by D. G. Gilles and D. Shaw. ‘Advances in Magnetic Resonance’ has continued with the publication of Volume 5, which contains chapters on ‘Pulsed-Fourier-transform nuclear 9

1

*

‘Nuclear Magnetic Resonance’, ed. R. K. Harris (Specialist Periodical Reports), The Chemical Society, London, 1972, vol. 1, 1973, vol. 2. ‘Annual Reports o n N.M.R. Spectroscopy’, ed. E. F. Mooney, Academic Press, London and New York, vol. 5A, 1972.

1

2

Spectroscopic Properties of Itiorganic and Organometallic Corllpounlis

magnetic resonance spectrometer’ by A. G. Redfield and R. K . Gupta,

‘Spectrometers for multiple-pulse N.M.R.’ by J. D. Ellett, juii., M . Ci. Gibby, U . Ha e b e r l e n , L. M . Huber, M . M eh ri ng, A. Pines, and J. S.

Waugh, ‘N.M.R. and ultraslow motions’ by D. C. Ailion, and ‘N.M.R. in helium-three’ by M. G. R i ~ h a r d s . ~ One volume of a new series of books has been devoted to magnetic resonance and contains chapters on ‘Nuclear spin relaxation in gases’ by M. Bloom, ‘N.M.R. studies of molecular motion in solids’ by P. S. Allen, ‘Carbon-13 nuclear spin relaxation’ by J. R. Lyerla, jun. and D. M. Grant, and ‘N.M.R. and E.S.R. in liquid crystals’ by J. Bulthuis, C. W. Hilbers, and C. M a ~ L e a n . ~ A number of books devoted to aspects of n.m.r. spectroscopy have been published, including ‘The Sadtler Guide to N.M.R. Spectra’ by W. W. Simons and M. Zanger,6 ‘Magnetic Resonance’ by K. A. M c L a ~ c h l a n , ~ ‘Theory and Interpretation of Magnetic Resonance Spectra, by W. T. D i ~ o n ‘Introductory ,~ Fourier Transform Spectroscopy, by R. J. Bell,8 ‘Carbon-13 Nuclear Magnetic Resonance for Organic Chemists’ by G. C. Levy and G. L. Nelson,* ‘Carbon-13 N.M.R. Spectra’ by L. F. Johnson and W. C. Jankowski,’* ‘The Nuclear Magnetic Resonance of Polymers’ by J. Ya. Slonin and A. N. Lyubimov,” and ‘Large-field Nuclear Magnetic Resonance Spectrometer’ by P. Thomas and C. Zermati.12 Also a number of books have been published which contain at least one chapter devoted to n.m.r. s p e c t r o ~ c o p y , ~ ~and - ’ ~ the book ‘Computers in Chemical and ‘Advances in Magnetic Resonance’, ed. J. S. Waugh, Academic Press, New York and London, vol. 5, 1972. MTP International Review of Science, Physical Chemistry’, Series One, ed. A. D. Buckingham, Volume 4, ‘Magnetic Resonance’, ed. C. A. McDowell, Butterworths, London, and University Park Press, Baltimore, 1972. W. W. Simons and M. Zanger, ‘The Sadtler Guide to NMR Spectra’, Sadtler Research Laboratories, Inc., Philadelphia, 1972. K. A. McLauchlan, ‘Magnetic Resonance’, Oxford University Press, Oxford, 1972. W. T. Dixon, ‘Theory and Interpretation of Magnetic Resonance Spectra’, Plenum Press, London and New York, 1972. R. J. Bell, ‘Introductory Fourier Transform Spectroscopy’, Academic Press, New York and London, 1972. G. C. Levy and G. L. Nelson, ‘Carbon-13 Nuclear Magnetic Resonance for Organic Chemists’, Wiley-Interscience, New York, 1972. l o L. F. Johnson and W. C. Jankowski, ‘Carbon-13 N.M.R. Spectra’, Wiley-Interscience, New York, 1972. ‘The Nuclear Magnetic Resonance of Polymers’, I. Yo. Slonin and A. N. Lyubimov, Heyden, London, 1972. P. Thomas and C. Zermati, ‘Large-field Nuclear Magnetic Resonance Spectrometer’, C.N.R.S., Paris, 1970. l 3 ‘Comprehensive Analytical Chemistry’, ed. C. L. Wilson and D. W. Wilson, Elsevier, Amsterdam, Volume IIC, 1971. l4 ‘An Introduction to Spectroscopic Methods for the Identification of Organic Compounds’, ed. F. Scheinmann, Pergamon Press, Oxford, 1970. lb‘Coordination Chemistry’, ed. A. E. Martell, A.C.S. Monograph 168, Von Nostrand Reinhold Co., New York, 1972. 18 L. A. Kazitsyma and N. B. Kupletskaya, ‘Uses of Ultraviolet, Infrared, and N.M.R. Spectroscopy in f)rganic Chemistry’, Vyssh. Shkoia, Moscow, 1971. C. J. Hawkins, Absolute Configuration of Metal Complexes’, Wiley-Interscience, New York, 1971. 4

Nuclear Magnetic Resonance Spectroscopy

3

Biochemical Research’ contains a chapter on Fourier transform spectrometry by S. T. Dunn, C. T. Foskett, P. Curbelo, and P. R. Griffiths.l8 A number of reviews have also been published on various topics, including a general review of n.m.r. spectroscopy,lB !Applications of 220 MHz N.M.R.’,20 ‘N.M.R. in solutions’,21 ‘Recent developments in high resolution n.m.r. spectroscopy,22 ‘Pulse Fourier transform n.m.r. spectros~opy’,~~ ‘Application of Fourier transform n.m.r. spectroscopy’,24 ‘Signal-to-noise enhancement through instrumental technique^',^^ ‘The use of a computer in nuclear magnetic resonance spectroscopy’,26~ 27 ‘Interference effects in nuclear magnetic resonance’,28‘Nuclear magnetic double r e ~ o n a n c e ’ ,‘Spin-spin ~~ coupling between geminal and vicinal “H N.m.r. spectra of the AA’XX’ and AA’BB’ type:analysis and clas~ification’,~~ ‘The application of n.m.r. and e.s.r. to coordination compounds in solution and the solid ‘Spectroscopy and structure of pentacoordinated ‘The application of proton magnetic resonance to the investigation of organophosphorus com‘N.m.r. studies of carbon-lithium p o u n d ~ ’ ,‘The ~ ~ use of 31P n.n-~.r.’,~~ bonding in organo-lithium ‘Chemically induced nuclear polarization, I : Phenomenon, examples and application^,^^ I1 : The radicalpair a review of hydride complexes of the transition metals which contains a useful, but incomplete, listing of many hydride chemical shifts,3gand ‘N.M.R. of molecules orientated by electric fields’.40 The attention of the reader is drawn to the I.U.P.A.C. publication ‘Recommendations for the Presentation of N. M.R. Data for Publication In

2o

21

za as 2p

zs 2E 27 28

** 30 31 Ba

33 34

35 a6

37

3R

a* 40

‘Computers in Chemical and Biochemical Research’, ed. C. Klopfenstein and C. Wilkins, Academic Press, New York and London, 1972. D. L. Rabenstein, Guide Mod. Methods Instr. Analysis, 1972, 231. A. A. Grey, Canad. J . Spectroscopy, 1972, 17, 82. N. H. Velthorst, Chem. Tech. (Amsterdam), 1972, 27, 341. E. D. Becker, Appl. Spectroscopy, 1972, 26, 421. D. A. Netzel, Appl. Spectroscopy, 1972, 26, 430. E. D. Becker and T. C. Farrar, Science, 1972, 178, 361. G. M. Hieftje, Anulyr. Chem., 1972, 44, No. 6, 81A; No. 7, 69A. E. G. Hoffmann, W. Stempfle, G. Schroth, B. Weimann, E. Ziegler, and J. Brandt, Angew. Chem. Internat. Edn., 1972, 11, 375. R. R. Ernst, Chimia (Swirz.), 1972, 26, 53. J. S. Blicharski, Insr. Nuclear Phys., Cracow, Rep., 1972 792/PL. R. B. Johannesen and T. D. Coyle, Endeavour, 1972, 31, 112. V. F. Bystrov, Russ. Chem. Reo., 1972, 41, 281. H. Giinther, Angew. Chem. Internat. Edn., 1972, 11, 861. H. J. Keller, Ber. Bunsengesselschaft phys. Chem., 1972, 76, 1080. R. H. Holmes, Accounts Chem. Res., 1972, 5 , 296. B. I. Ionin and T. N. Timofeeva, Russ. Chem. Rev., 1972, 41, 390; Uspekhi Khim.. 1972, 41, 758. E. Fluck, Chem.-Ztg, 1972, 96, 517. L. D. McKeever, Ions Ion Pairs Org. React., 1972, 1, 263. H. R. Ward, Accounts Chem. Res., 1972, 5 , 18. R. G. Lawler, Accounts Chem. Res., 1972, 5 , 25. H. D. Kaesz and R. B. Saillant, Chem. Rev., 1972, 72, 231. C. W. Hilbers and C. Maclean, Nuclenr Mugn. Resonance, 1972, 7, 1 .

4

Spectroscopic Properties of Inorganic and Organometalfic Cornpounds

in Chemical journal^'.^^ Few papers reach the high standards recommended. The invited lectures presented at the Fourth International Symposium on Magnetic Resonance, Rehovot/ Jerusal em, Israel, have been published.42 They include ‘Multi-site chemical exchange by n.m.r.’ by E. A. Allan, M. G. Hogben, L. W. Reeves, and K. N. Shaw, ‘Fourier transform studies of nuclear spin relaxation’ by W. A. Anderson, R. Freeman, and H. Hill, ‘Developments in the motional narrowing of the n.m.r. spectra of solids microscopic and macroscopic’ by E. R. Andrew, ‘13CN.M.R. spectroscopy: relaxation times of 13Cand methods for sensitivity enhancement’ by E. D. Becker and R. R. Shoup, ‘New spin echo techniques in the earth’s magnetic field range’ by G. J. Bene, ‘Solvent effects on n.m.r. spectra of gases and liquids’ by H. J. Bernstein, ‘Nuclear magnetic resonance and nuclear spin symmetry in molecular solids’ by M. Bloom, ‘Study intramolecular motion by n.m.r. of orientated molecules’ by P. Diehl, ‘N.m.r. satellites as a probe for chemical investigations’ by S. Fujiwara, Y. Arata, H. Ozawa, and M. Kunugi, ‘N.m.r. studies of paramagnetic molecules’ by R. M. Golding, ‘Nuclear magnetic ordering’ by M. Goldman, ‘Intermolecular nuclear relaxation and molecular pair distribution in liquid mixtures’ by R. Goller, H. G. Hertz, and R. Tutsch, ‘N.m.r. study of induced dielectric alignment, in pure and binary liquids’ by C. W. Hilbers, J. Biemond, and C. MacLean, ‘Biologically important isotope hybrid compounds in n.m.r. : ‘H Fourier transform n.m.r. at unnatural abundance’ by J. J. Katz and H. L. Crespi, ‘Developments in n.m.r. in liquid crystalline solvents’ by S. Meiloom, R. C. Hewitt, and L. C. Snyder, ‘Isotropic n.m.r. shifts in the “solid” and “liquid” states’ by A. J. Vega and D. Fiat, ‘Spin echoes and Loschmidt’s paradox’ by J. S. Waugh, W.-K. Rhim, and A. Pines, ‘N.m.r. in superconductors’ by M. Weger, and ‘N.m.r. study of the electronic structure of solid and liquid metals’ by D. Zamir and U. El-Hanany. Techniques, Coupling Constants, Chemical Shifts, and Relaxation Measurements.-The papers reviewed in this section are concerned primarily with the development of techniques, or the measurement of coupling constants, chemical shifts, or relaxation times. The section is thence split into six subsections covering (a) techniques, (b) coupling constants, (c) lH and leF chemical shifts, (d) 13Cchemical shifts, (e) lrB, 14N,16N,2eSi,31P,33S,3aCI, 37Cl, 77Se,78Br,81Br,and 128Xe chemical shifts, and (f)metal chemical shifts. Techniques. The ASIS (aromatic solvent induced shifts) effect has been exploited for a number of inorganic and organometallic compounds. It has been applied to trisubstituted borazine derivatives to assess aromatic for H3BPR3 and H3BNMe3 it was found that the hydridic protons were shifted upfield in C6D8and downfield in C ~ F I .These results 41

4’

I.U.P.A.C. ‘Recommendations for the Presentation of N.M.R.Data for Publication in Chemical Journals’, Pure Appl. Chem., 1972, 29, 625. Pure and Applied Chemistry, 1972, 32. M. Pasdeloup, J.-P. Laurent, and G. Commenges, J . Chim. phys., 1972, 69, 1022.

Nuclear Magnetic Resonance Spectroscopy 5 demonstrate for the first time that the ASIS effect can be reversed when the proton bears a partial negative charge.44 In order to explain the A S I S effect in some complexes of the types NiL4, (OC),-,FeL,, and (OC), .,ML, (M = Cr, Mo, or W ; n = 1 or 2), it was necessary to postulate that they can be induced by local dipolar regions in absence of a net solute dipole,45 whereas for complexes (acac),R,Sn and (acac)R,Sb it was found that the derived charge distribution correlates better with the inductive effect of the substituents at the metal atom than with the molecular dipole moments.46 ASIS has also been used to assist in interpretation of the lH n.m.r. spectrum of 2-ferrocenyl-4-n-butylquinolineand 1,2-dihydro-2-ferrocenyl-4-n-butylq ~ i n o l i n e .An ~ ~ alternative way to induce changes in the lH n.m.r. shifts of diols is to add borate.48 An interesting new application of n.m.r. is to follow moderately rapid reactions using flow methods,,@and this method was applied to the determination of the rate of the reaction

Good agreement with optical measurements was found.50 It has been reported that for isotopically rare nuclei, e.g. 13C, 15N, 2H, in the presence of other nuclei, e.g. lH, it is possible to irradiate the abundant nuclei, get spin polarization of the isotopically rare nuclei, and record free induction decays with greatly increased sensitivity. This technique has been used to obtain the principal components of the chemical shielding tensor of 13C for adamantane,61 and calcium of 16N for (NH4),S0, and NH4N03,63 and of 29Sifor polycrystalline organosilicon Interest in 13Cn.m.r. spectroscopy has continued with the report of the

13C chemical shifts of many reference compounds with respect to Me,Si, and the solvent effects on Me,Si have been inve~tigated.~~ The problem of sensitivity of 13Cn.m.r. signals has attracted attention and it has been found that addition of a paramagnetic compound, e.g. Cr(acac),, can produce up

to a 40-fold increase in sensitivity for Fe(CO), with no significant chemical

46

47

4D 6o

b4 bs

A. H. Cowley, M. C . Damasco, J. A. Mosbo, and J. G. Verkade, J . Amer. Chem. SOC., 1972,94, 6715. J. A. Mosbo, J. R. Pipal, and J. G. Verkade, J . Magn. Resonance, 1972, 8 , 243. A. Mackor and H. A. Meinema, Rec. Trao. chim., 1972, 91. 911. D. J. Booth, B. W. Rockett, and J. Ronayne, J. Organometallic Chem., 1972, 44, C29. W. Voelter, C. Biirvenich, and E. Breitmaier, Angew. Chem. Internat. Edn., 1972, 11, 539. Y. Ashai and E. Mizuta, Talanta, 1972, 19, 567. J. Grimaldi, J. Baldo, C. McMurray, and B. D. Sykes, J . Amer. Chem. Soc., 1972, 94, 7641. A. Pines, M. G. Gibby, and J. S. Waugh, J . Chem. Phys., 1972, 56, 1776. A. Pines, W.-K. Rhim, and J. S. Waugh, J. Magn. Resonance, 1972, 6, 457. M. G. Gibby, R. G . Griffin, A. Pines, and J. S. Waugh, G e m . Phys. Letters, 1972, 17, 80. M. G. Gibby, A. Pines, and J. S. Waugh, J. Amer. Chem. SOC.,1972, 94, 6231. G. C. Levy and J. D. Cargioli, J. Magn. Resonance, 1972, 6, 143.

6

Spectroscopic Properties of Inorganic and Organometallic Compoundlr

shift 5 7 When this technique was applied to 15Nn.m.r., increases up to only six-fold were A calculational procedure for substituent effects has enabled the calculation of chemical shifts in lH, llB, 13C, and 31P n.m.r. spectroscopy and the explanation of additivity of substituent effects. An exception was found for l19Sn chemical shifts.69 Coupling Constants. lJ(13C-'H) and 1J(29Si-1H) of some methylphenylsilanes have been shown to correlate with Hammett (T constants, and the mechanisms of transmission of substituent effects across carbon-silicon and silicon-silicon bonds were discussed.60~ 81 1J(76As-1H)and 1J(75As-2H) in ASH, and AsD, have been measured using pulse n.m.r. techniques. It was possible to show by 7'' measurements that the arsine molecule reorientates as a free rotor at high temperatures.62 It has been found that for [SnH,]-, lJ('l9Sn-lH) is 109.4 Hz, compared with 1933 Hz for SnH,. These coupling constants were discussed in terms of the Pople-Santry treatment.63 The llB n.m.r. spectrum of B5Hgwith complete 'H decoupling at + 46 "C shows a well-resolved lJ(llB-llB) = 19.4 Hz, but cooling to - 51 OC produces decoupling.64 'H, llB, and 19F n.m.r. and INDOR have been used to determine the relative signs of coupling constants for F3BNMe3.6e 1J(11B-31P) has been reported for a number of adducts F2XP,BH3 and F2X,PB4H8(X = F, C1, Br, or I), and a linear correlation was found between 1J(11B-31P)and V ( B - H ) . ~ ~ The 13C n.m.r. spectra of a number of silicon compounds have been reported and it was found that the magnitude of 1J(13C-20Si)is roughly proportional to the s-character of the carbon.67 lJ(lg5Pt-l3C) = 1035 Hz has been reported for [Pt(CN),I2- in a review on the application of n.m.r. and e.s.r. to co-ordination compounds.68 In a study on the 13C n.m.r. spectra of ButCH2HgR, many linear relationships between coupling constants, including J(1ggHg-13C),were noted.69 The first report of lJ(CI-19F) has appeared for [CIF,]+, where lJ(3SC1-19F) = 337 Hz and 1J(37C1-1eF)= 281 Hz.'O The compound

L7 68

6o

aa

a6 87

as 70

S. Barcza and N. Engstrom, J. Amer. Cheni. Soc., 1972, 94, 1762. 0. A. Gansow, A. R. Burke, and G . N . LaMar, J.C.S. Chem. Comm., 1972, 456. L. F. Farnell, E. W. Randall, and A. I. White, J.C.S. Chem. Comm., 1972, 1159. L. Phillips and V. Wray, J.C.S. Perkin I t , 1972, 214. F. K. Cartledge and K. H. Riedel, J . Organomefalfic Chem., 1972, 34, 11. Y. Nagai, M.-A. Ohtsuki, T. Nakano, and H. Watanabe, J. Organometullic Chem., 1972, 35, 81. L. J. Burnett and A . H. Zeltmann, J . Chem. Phys., 1972, 56, 4695. T. Birchall and A . Pereira, J.C.S. Chem. Conim., 1972, 1150. D. W. Lowman, P. D. Ellis, and J. D. Odom, J . Mugn. Resonance, 1972, 8, 289. V. V. Negrebetskii, V. S. Bogdanov, and A. V. Kessenikh, Zhur. strukt. Khim., 1972, 13, 327. R. T. Paine and R. W. Parry, Znorg. Chem., 1972, 11, 1237. G. C. Levy, D. M. White, and J. C. Cargioli, J. Magn. Resonance, 1972, 8, 280. H. J. Keller, Ber. Bunsengesellschaft phys. Chem., 1972, 76, 1080. G. Singh and G. S. Reddy, J. Organometallic Chem., 1972, 42, 267. K. 0. Christe, Inorg. Nuclear Chem. Letters, 1972, 8, 741.

Nuclear Magnetic Resonance Spectroscopy 7 [IF,]' shows 1J(1gF-12771) = 2730 Hz. It is interesting to note that the linewidth of the outermost line is 110 H z whereas for the inner lines the linewidth can be up to 170 Hze71A linear relationship has been found between 1J(31P-1H3 W) for W(CO)5L and the electronegativity of the phosphorus ligand. Points due to L = PCI,, PBr,, or PI, fall off this line, forming another linear relationship, with PF3 falling on both lines.72 The lH n.m.r. spectrum of B5HB with llB decoupling shows signals 4:1:4 in intensity with the apical hydrogen split into a nine-line pattern by ~ an analysis of the the other eight hydrogens, 3J(1H-1H) = 5.7 H z . ~From 13C-H satellite magnetic resonance spectrum of (C,H,)SnMe,, J(H-H) have been determined. I t is found that these coupling constants can be useful in differentiating between fluxional 0- and n-cyclopentadienyl groups.74 J(llB-lH) has been determined indirectly for some vinyl compounds of boron. It is found that J[B-H(uic)] = J[B-H(trans)] > J[B-H(cis)] > J [B-H(gem)] .J [B-H(cis)], and as J [B-H(gem)] decreases with increased electronegativity of substituent, the signs are probably positive.75 The 'H n.m.r. spectra of B2H6,MeB2H5,1 ,I-Me2B2H4,1,2-Me2B2H4,1,1,2-Me,B,H,, 1,1,2,2-Me4B,H,, and ClB2HBhave been fully analysed. It was found that J(HT-H,) is 7.5-8.7 Hz, J(Me-H,) is 2.4-3.5 Hz, and J(Me-HT,,,,,) is 5.0-5.3 H z . ~ ~ The observation that 2J(11gSn-C-1H)increases as r(C-Sn) decreases for a variety of methyl-tin complexes has been explained using the Fermi contact equation," and for Me6W, 2J(183W-1H) is 3.0 H z . ~Double~ resonance experiments on compound (1) show 2J(1g5Pt-CH) and 3J(1v5PtCH,) to be opposite in sign.79 Calculations of J(lg9Hg-CH3) for some methylmercury complexes indicate that the Fermi contact mechanism is dominant.8o J(205Tl-1H) coupling constants in various monoarylthallium

71 7a

73 74

M. Brownstein and H. Selig, Itiorg. Chem., 1972. 11, 656. E. 0. Fischer, L. Knauss, R . L. Keiter, and J. G. Verkade, J . Orgaiiumeiallic Chem., 1972, 36, C7. T. Onak, J.C.S. Chem. Cornm., 1972, 351. Yu. K. Grishin, N. M. Sergeyev, and Yu. A. Ustynyuk, J . Organornetallic Chem., 1972, 34, 105.

76

V. S. Bogdanov, A. V. Kessenikh, and A. Y. A. Shchteinshneider, Zhur. strirkt. Khitri.,

70

J. B. Leach, C. B. Ungermann, and T. P. Onak, J . Magn. Resonance, 1972, 6 , 74. M. K. Das, J. Buckle, and P. G. Harrison, Inorg. Chim. A d a , 1972, 6, 17. A. Shortland and G. Wilkinson, J.C.S. Chem. Comm., 1972, 318. D. F. Gill and B. L. Shaw, J.C.S. Chem. Comm., 1972, 65. H. F. Henneike, J . Amer. Chem. Soc.. 1972, 94, 5945.

77 713 79

80

1972, 13, 226.

Spectroscopic Properties of Inorganic and Organometallic Compounds dichlorides and substituted inonoarylthalliuni dichlorides have been determined in DMSO solutions in order to compare the couplings with the corresponding J('H-'H) coupling constants, and close resemblances were found.H The measurement of 2J(31P-31P)has once again attracted attention. The IBF and 31P n.m.r. spectra of (F,P(=E)},Z have been measured and analysed as AA'XX'X"X". For (SPF2),0 it was found that 2J(31P-31P) shows a marked temperature dependences2 Similarly, 2J(31P-31P)has been evaluated from 19F n.m.r. spectra of cis-L2M(C0)., (M = Cr, Mo, or W) and it is found that for M = Mo, L = (CFs)2PR or (CFs)PR2, 2J(31P-31P) decreases in the order R = F > C1 > Br > I > H.83 1H{31P}INDOR has been used to show that for compound (2), 2J(P1-CHS) = ca. T 10.7 Hz, 8

(2)

4J(P3-CH3) = ca. f 2.2 Hz, and 2J(P1-P3) = ca. +440 Hz, but was significantly different when X = NO2 (It 408 Hz), py ( k 398 Hz), or CO ( + 3 2 0 H Z ) . ~It~ is often assumed that 2J(P-M-P) for mutually trans tertiary phosphines is large, but for trans-SnC1,(PEt3)(PEt2Ph),2J(P-Sn-P) is only 43.2 Hz. Unlike tungsten, rhodium, and platinum complexes, 1J(11gSn-31P)decreases as the number of phenyl groups on the tertiary phosphine is increased.86 lH and lgF Chemical Shuts. Me3SiCH2CH,CH2SO;Na+is commonly used as a reference in aqueous solution, but it has been found that it will react with Hg(OAc), to give MeHg(0Ac) and Me2Si(OAc)CH2CH2CH2SO;Na+. Thus care must be exercised in using Me3SiCH2CH2CH2SO;Na+as internal reference.s6 For the complexes (3 ; M = Ti, Zr, or Hf), a correlation has been found between the angle between the cyclopentadienyl rings and the chemical

J. P. Maher, M. Evans, and M. Harrison, J.C.S. Dalton, 1972, 188.

** T. L. Charlton and R. G. Cavell, Inorg. Chem., 1972, 11, 1583. 89 J. F. Nixon and J. R. Swain, J.C.S. Dalton, 1972, 1038. ns 86

B. E. Mann, C. Masters, and B. L. Shaw, J.C.S. Dalton, 1972, 48. J . F. Malone and B. E. Mann, Inorg. Nuclear Chem. Letters, 1972, 8, 819. R. E. DeSimone, J.C.S. Chem. Comm., 1972, 780.

Nuclear Magnetic Resonance Spectroscopy 9 shift difference between the a: and protons on the From lH, IQF, and P ' n.m.r. measurements on (C5H5)Fe(CO),X and (C,H,)Fe(CO)(PPh3)C,H4R-p, it was concluded that the effects of X and R substituents upon the cyclopentadienyl-ring chemical shifts are predominantly inductive.** The 'H n.m.r. spectra of MeCo(dmg),(base) have been measured for a wide variety of bases. For substituted pyridines, the slope of the dependence of the chemical shift of the methyl group on the Hamniett cr constant is 2/3 that for Hammett u constant in the N-methylpyridinium salts. It was therefore concluded that a cobalt atom will conduct about 2/3 of the electronic effect of a s u b ~ t i t u e n t . ~ ~ The Buckingham-Stevens theory has been applied. For HIr(piperidine),(NCX),(X = 0, S, or Se), the theory is only partly in accord with results and the chemical shift is more dependent on the covalent character of the trans ligand.@O[IrHCI,(PBut,R),] shows a very high-field hydride signal at T 60.5 for R = Me. This very large high-field shift was explained as due to a small value for AE. N.m.r. data were also reported.@' Molecular properties of diborane and decaborane( 14), including 'H and llB chemical shifts, have been calculated from a minimum basis set and extended Slater orbital wavefunctions, but agreement with experiment was p 0 0 r . ~@3~ Variable-temperature ~ lH n.m.r. spectra of borazine and ['OBIborazine have been analysed for chemical shifts, coupling constants, and linewidths. It was concluded that the broadening is due to a combination of quadrupolar relaxation resulting from the high-spin nuclei present and long-range spin coupling.u4 A correlation has been established between the chemical shifts of the silicon methyl groups and the resonance constant of the para substituent in P - X C ~ H ~ S ~AMsimilar ~ ~ . ~relationship ~ has been found for (MeO)Me,SnCeH4X.QeThe lH chemical shift and 2J(11nSn-CH3)for MeSnR, have been determined and interpreted in terms of (d-p)n bonding between tin and the n-system of R ; MeHgR is ana10gous.~~ Del Re calculations have been extended to correlate and interpret the n.m.r. data in organotin compounds. The methyl proton chemical shifts have been correlated with the partial charge on the methyl hydrogen atom. Variations in lJ(13C--'H) 88

89

O3

D6 y7

M. Hillman and A. J. Weiss, J . Organomefallic Chem., 1972, 42, 123. A. N. Nesmeyanov, I. F. Leshcheva, I. V. Polovyanyuk, Yu. A. Ustynyuk, and L. G . Makarova, J. Organometallic Chem., 1972, 37, 159. J. P. Fox, R. Banninger, R. T. Proffitt, and L. L. Ingraham, Jnorg. Chern., 1972, 11, 2379. E. R. Birnbaum, J . Jnorg. Nuclear Chem., 1972, 34, 3499. C. Masters, B. L. Shaw, and R. E. Stainbank, J.C.S. Dalton, 1972, 664. E. A. Laws, R. M. Stevens, and W. N. Lipscomb, J . Amer. Chern. Soc., 1972, 94, 446 1. E. A. Laws, R . M. Stevens, and W. N. Lipscomb, J . Amer. Chem. SOC.,1972, 94, 4467. E. K. Mellon, B. M. Coker, and P. B. Dillon, Inorg. Chem., 1972, 11, 852. A. P. Kreshkov, V. F. Andronov, and V. A . Drozdov, Russ. J . Phys. Chem., 1972, 46, 574. J. Pijselman and M. Pereyre, J . Organometcrllic Chem., 1972, 44, 309. G . Barbieri and F. Taddei, J.C.S. Perkin I J , 1972, 1323.

Spectroscopic Properties of Inorganic and Organometallic Compounds and 2J(Sn-C-H) have been correlated with the calculated Coulomb integrals.98 It is usual to use the rule that when Me,NCS,- is bidentate it gives a signal at 7 6.72 and when it is unidentate at T 7.24. However, Me,SnS,CNMe, is known to contain Me2NCS,- as a unidentate ligand but the signal is at 7 6.55. Thus caution is required.uu From lH and lUF shift measurements on HOF it has been concluded that the hydrogen and fluorine atoms carry charges of +0.5 e and -0.5 e, respectiveIy.loOThe temperature dependence of the lH shielding constant of HCI gas has been measured and the shielding constant factorized. There is an isotope shift between H35Cland H3’Cl of 0.001 p.p.m.lol From the lUFchemical shifts of m- and p-FC6H4HgX, 01 and aR have been determined for the mercury substituents.102A number of substituted a(1)- and /3(2)-fluoronaphthalenes with metallo-substituents of the type HgX or MRs (M = Group IVB metalloid) have been synthesized and their fluorine n.m.r. spectra have been measured. The fluorine chemical shifts have been used to provide experimental evidence for d,,-p, and pn-pn bonding.lo3 Similarly, lgF n.m.r. chemical shifts of some aryl silicon compounds have been measured in order to assess n-bonding.lo41lo5 13C Chemical Shifrs. The use of CND0/2 calculations to determine 13C chemical shifts, lJ(13C-lH), and 2J(1H-C-1H) for CH3X compounds has been described.lop For the complexes (PhCH2),X (X = Ti, Zr, Hg, B, Al, Si, or Sn) a linear relationship has been reported between both the lH and 13C chemical shifts of the CH, group and the electronegativity of X. The deviations found for titanium and zirconium were attributed to electronic interactions of the CH, with the metal.1o7The 13Cand 19Fn.m.r. chemical shifts of (C5H5),TiX2have been discussed in terms of bonding.lO* For Grignard reagents, a linear relationship has been reported between the 13C chemical shift and that of the corresponding h y d r ~ c a r b o n . ~ ~ ~ The effect of changes in the electronic environment of the sp2 hybridized carbene carbon atom bound to the metal in a series of 18 complexes of the type (OC),MCXY (M = Cr or W ; X = OR or NR1R2; Y = organic 10

R. Gupta and B. Majee, J . Organontetnllic Chern., 1972, 40,97. B. W. Fitzsimmons and A. C. Sawbridge, J.C.S. Dalton, 1972, 1678. l o o J. C. Hindman, A. Svirmickas, and E. H. Appelman, J . Chem. Phys., 1972, 57, 4542. W. T. Raynes and B. P. Chadburn, Mol. Phys., 1972, 24, 853. l o 8 0. N . Kravtsov, B. A. Kvasov, L. S. Golovchenko, and E. I . Fedin, J . Orgnnometallic Chem., 1972, 36, 227. l o 9 W. Adcock, S. Q. A. Rizvi, W. Kitching, and A. J. Smith, J . Anter. Chem. Sac., 1972, 94, 369. l o o J. Lipowitz, J . Amer. Chem. Soc., 1972, 94, 1582. l o b A. P. Kreshkov, V. F. Andronov, and V. A. Drozdov, Zhur.jiz. Khim., 1972,46,977; R i m . J. Phys. Chem., 1972, 46,5 6 4 . l o o R. Radeglia and E. Gey, J . praki. Chem., 1971, 313, 1070. l o 7 L. Zelta and G . Gatti, Org. Mogn. Resonance, 1972, 4, 5 8 5 . l o 8 A. N. Nesmeyanov, 0. V. Nogina, E. I . Fedin, V. A . Dubovitskii, B. A. Kvasov, and P. V. Petrovskii, Doklady Akad. Nauk S.S.S.R., 1972, 205, 857. l o @ D. Leibfritz, B. 0. Wagner, and J. D. Roberts, Annafen, 1972, 763, 173.

Nuclear Magnetic Resonance Spectroscopy 11 group) has been examined with the aid of 13Cn.m.r. spectroscopy.l10 The 13C n.m.r. spectra of (OC)&MCXYhave been measured and the carbene 13C n.m.r. signals found at very high frequency.lll Similarly, the 13C chemical shifts of (C,H,)Fe(CO),X have been reported. The carbonyl chemical shifts are linearly dependent on the Taft a1 values of the substituent and on the measured CO stretching frequencies.”, It has been shown that for rner-RhCl,(C0)(PB~”,Ph)~,trans-RuC1,(CO),(PEt,),, and rrans-PdCl,(PBun,But),, the 13C signals of the mutual trans tertiary phosphine ligands are either triplets or singlets, thus offering useful stereochemical information. Similarly, for IrClIMe(CO)(AsEt,Ph), the 13C signals of the ethyl group are doubled, showing the absence of a plane of symmetry through the iridium-arsenic bond.l13 The 13C n.m.r. spectra of [(1-MeC3H4)NiX],and [(C3H4R)PdX],have been reported, and a trans influence 1 < Br -= C1 has been found; lJ(13C-’H) = ca. 160 Hz is 115 The 13C n.m.r. spectra of (4)and consistent with sp2

2

(4)

related compounds have been measured. Linear relationships have been found between 13Cchemical shifts of various atoms.l16 The 13C n.m.r. spectra of some olefinic and acetylenic complexes of platinum have been reported. It was felt that the data (which bear considerable similarity to data on cyclopropane) were best interpreted in terms of a rr-bonding mechanism!l17 Data have also been reported for olefinsilver complexes.118 The 13Cnuclear Overhauser enhancement of 1.65 has been measured for Me,Si.llB 13C Chemical shifts of Me,Si have been determined at infinite

11”

113

114

lls 116

lI7

’la

lle

J. A. Connor, E. M. Jones, E. W. Randall, and E. Rosenberg, J.C.S. Dalton, 1972, 2419. C . G . Kreiter and V. FormaEek, Angew. Chem. Infernat. Edn., 1972, 11, 141. 0. A. Gansow, D. A. Schexnayder, and B. Y . Kimura, J . Amer. Chem. Soc., 1972,94, 3406. B. E. Mann, B. L. Shaw, and R. E. Stainbank, J.C.S. Chem. Comm., 1972, 1 5 1 . L. A. Churlyaeva, M. I. Lobach, G . P. Kondratenkov, and V. A. Kormer, J . Orgairometallic Chem., 1972, 39, C23. V. N. Sokolov, G . M . Khvostik, I . Ya. Poddubnyi, and G . P. Kondratenkov, DokIrdy Akad. Nauk S . S . S . R . , 1972, 204, 120. D. G. Cooper, R. P. Hughes, and J. Powell, J. Anier. Chetn. Soc., 1972, 94, 9244. M. H. Chisholm, H . C. Clark, L. E. Manzer, and J . B. Stothers, J . Amer. Chem. Soc., 1972, 94, 5087. C. D. M. Beverwijk and J. P. C. M. van Dongen, Tetrahedron Letters, 1972, 4291. T. C . Farrar, S. J. Druck, R. R. Shoup, and E. D. Becker, J . Arner. Chem. Soc. 1972, 94, 699.

12

Spectroscopic Properties of Inorganic and Organometallic Conipounds

dilution in sixteen solvents: shifts of up to 4.68 p.p.m. were found. Cyclohexane was also examined and found to be a much better choice of internal reference. External referencing was considered to be even better.120 llB, 14N, lSN, 2QSi,31P, 33S, 35Cl,37Cl,V e , 7QBr,BIBr,and lzQXeChemical Shifts. The chemical shifts of the boron 1s binding energies of some gaseous compounds have been measured but no correlation was found with the llB n.m.r. chemical shifts.lel For the pair of compounds [BH4]- and [BH3D]- a 2H isotope effect of 4.5 Hz has been observed in the llB n.m.r, spectra.122 Use can be made of the different values of to extract unresolved lines in the llB n.m.r. spectrum and was applied to n-BsHls.123 The lSN n.m.r. spectra of [CO(~~NH,),X]"+ have been measured but are relatively insensitive to X.lZ4 For a number of amino-boranes, a decrease in shielding of the l*N nucleus is observed with increasing boron-nitrogen bond order. Neighbour anisotropic effects can also be important.126 From lH and 14N n.m.r. measurements on aminosilanes it has been concluded that as the number of RO groups is increased on the silicon, ( p d ) n bonding is reduced.lZ6The 14Nchemical shifts of N3- and NCO- have been calculated by the procedure developed by Karplus and Pople and compared with the method of Grinter and Mason.lZ7 For a number of azides, 14N chemical shifts have been measured and related to the electronic characteristics of the atom or groups to which the azide is covalently attached and to the mode of attachment.lZ8 The use of 2QSin.m.r. has been examined and applied to a wide variety of silicon c o m p o ~ n d s130 . ~ ~For ~ ~P(SiMe,),, 1J(2QSi-31P) = 25 Hz. There is a linear relationship between the 31P chemical shift of the free tertiary phosphine and the change in chemical shift on co-ordination for the complexes (C&&,)RUC~,PR~'~~ and mer-MC1,(PR3), (M = Rh or Ir).lS2 For IrC1,(PEt3)2(PMe2Ph),2J(P-P) (trans) is 427 HZ.',~ The 31P chemical shifts of (R3M),PX3-, ( M = Si, Ge, or Sn) have been discussed using the theory of Letcher and Van Wazer. It was shown that, in both the Ge-P and Sn-P bond, t~ interactions are i r n ~ 0 r t a n t . lThe ~ ~ 31Pchemical I20 121 lap

12'

126

IZs

lap 133

D. Ziessow and M. Carroll, Ber. Bunsengesselschaft phys. Chem., 1972, 76, 61. P. Finn and W. L. Jolly, J. Amer. Chem. Soc., 1972, 94, 1540. M . M. Kreevoy and J. E. C. Hutchins, J. Amer. Chem. SOC.,1972, 94, 6371. A. Allerhand, A. 0. Clouse, R. R. Rietz, T. Roseberry, and R. Schaeffer, J. Amer. Cliem. SOC.,1972, 94, 2445. J. W. Lehman and B. M. Fung, fnorg. Chem., 1972, 11, 214. W. Beck, W. Becker, H. Noth, and B. Wrackmeyer, Chem. Ber., 1972, 105, 2883. K. A. Andrianov, V. F. Andronov, V. A. Drozdov, D. Ya. Zhinkin, A. P. Kreshkov, and M. M. Morgunova, Doklady Akad. Nauk S.S.S.R., 1972, 202, 583. K . F. Chew, W. Derbyshire, and N. Logan, J.C.S. Faraday 11, 1972, 594. W. Beck, W. Becker, K. F. Chew, W. Derbyshire, N. Logan, D. M . Revitt, and D. B. Sowerby, J.C.S. Dalton, 1972, 245. G. C. Levy, J. D. Cargioli, P. C. Juliano, and T. D. Mitchell, J. Magn. Resonance, 1972, 8, 399. H. C. Marsmann, Chem.-Ztg., 1972, 96, 287. R. A. Zelonka and M. C. Baird, J . Organometallic Chem., 1972, 44,383. B, E. Mann, C. Masters, and B. L. Shaw, J.C.S. Dalton, 1972, 704. G, Engelhardt, 2. ariorg. Chem., 1972, 387, 52.

Nuclear Magnetic Resonance Spectroscopy 13 shift of phosphorus vapour relative to liquid white phosphorus has been measured. A linear relationship between shift and pressure was found and extrapolated to zero pressure to obtain the shift of free P4.134The 31Pn.m.r. chemical shifts of P4 have been measured in substituted benzenes and halogen-free solvents. The shifts are mainly due to van der Waals intera c t i o n ~ . ' There ~ ~ has been discussion on the application of the Van WazerLetcher theory to interpret the 31P chemical shifts and to calculate phosphorus-nitrogen bond orders in pho~phazo-derivatives.~~~~ 137 The deuterium isotope effect in (MeO),PHO has been studied by INDOR and ~ ~ gas-phase and isotope shifts of up to 0.49 p.p.m. have been f 0 ~ n d . lThe solvent chemical shifts of PBr, have been measured and found to be temperature dependent.13B The 3sSchemical shifts, covering a range of nearly 600 p.p.m., have been reported for 12 compounds and linewidths of up to 16 G (1200 p.p.m.) found. It is interesting to note that when concentrated H2S04is diluted to 10 mol 1-l, the 33Sresonance moves 90 p.p.m. and sharpens ten-fold.140 1H-{77Se) INDOR has been used to determine "Se chemical shifts in 80 organoselenium compounds. The shifts cover a range of over 1500 p.p.m. and are relatively insensitive to solvent effects. The behaviour of the chemical shifts parallels that found in similar phosphorus compounds but the shifts are several times larger. Correlations are found with the extent of a-chain branching in alkyl derivatives and with Hammett a-constants in substituted aryl derivatives.141 Even for R3PSe, where 77Se does not couple to lH, 77Se shifts could be determined by 1H-{77Sef INDOR.14, Similarly, 77Sechemical shifts have been measured for (PF,),Se and (GeH,),Se. 'H, lBF,and 3lP n.m.r. spectra were also ~ e c 0 r d e d . l ~ ~ The magnetic screening constants of the halogen nuclei in CuCl and CuBr have been calculated on the basis of the overlap of electron shells of the ions. Satisfactory correspondence with the experimental data has been obtained.14436ClN.m.r. chemical shifts and linewidths in alkylchlorosilanes have been correlated with the polar constants of the substituents attached to the silicon atom and the quadrupole resonance frequencies. The 3sCl chemical shifts can be used to assess the acid-base properties and reactivity of Si-CI The variations of the 36Cl,alBr, and 2H n.m.r. signals G. Heckmann and E. Fluck, Mof. Phys., 1972, 23, 175. G. Heckmann and E. Fluck, 2. Naturforsch., 1972, 27b, 764. lS6 E. S. Kozlov and S. N. Gaidamaka, Teor. i eksp. Khim., 1972, 8, 420. IY7 Yu. P. Egorov and A. S. Tarasevich, Teor. i eksp. Khim., 1972, 8, 422. 138 W. McFarlane and D. S. Rycroft, Mol. Phys., 1972, 24, 893. 13@ G. Heckmann, Mol. PAYS., 1972, 23, 627. H. L. Retcofsky and R. A. Friedel. J. Amer. Chem. SOC.,1972, 94, 6579. 141 W. McFarlane and R. J . Wood, J.C.S. Dalton, 1972, 1397. I r a W. McFarlane and D. S. Rycroft, J.C.S. Chem. Comm., 1972, 902. D. E. J. Arnold, J. S. Dryburgh, E. A. V. Ebsworth, and D. W. H. Rankin. J.C.S. Dalton, 1972, 2518. 14' V. M. Bouznik and L. 0.Falaleeva, J . Magn. Resonance, 1972, 6, 197. A. P. Kreshkov, V. F. Andronov, and V. A. Drozdov, Russ. J . Phys. Chenz., 1972, 46, 183; Zhur. fiz. Khim., 1972, 46, 309. lS6

14

Spectroscopic Properfies of Inorganic and OrganometaZZic Compoirnds

with concentration, the ratios of 35Cl, 37CI, 'OBr, and 81Br relative to 2H, and the solvent isotope effect have been measured in H 2 0 and D20.1d6 Analysis of the large 12gXen.m.r. shifts induced by gaseous O2 and N O indicates that they arise from a 'contact-overlap' mechanism.147 Metal Chemical Shifrs. The resonance frequencies of 47Tiand 49Tiare so close that both isotopes are observed in a normal sweep. 47Tiand 4gTi n.m.r. spectroscopy were used to investigate halogen exchange between TiCI,,, TiBr,, and TiF62-.148 The paramagnetic component of the magnetic screening constant a* has been discussed for the case of the octahedral molecular a-bonds in AXs-nYn, where A is a transition element with the nds electronic configuration, and applied to W o chemical shifts.14@"Co Chemical shifts have been reported for a number of complexes of the type CO(NH,),-,,X, and it was possible to explain the chemical shifts using the theory of Griffith and Orge1.l5O It has been concluded from V o n.m.r. measurements on Co(NO),(PR,)X that covalency increases X = C1 < Br < I. The 6BCochemical shifts have also been used to set up an order of acceptor ability for PR3.151 llgSn Chemical shifts have been determined by lH-{llgSn} INDOR for a wide range of tin complexes. For 32 ethyltin complexes it is found that high-field shifts occur when an unsaturated group is attached to tin, indicating that n-bonding involving the tin 5d orbitals is important.162 The solvent dependence of the llOSnchemical shift of Me,SnCl has been attributed to complex formation and both stability constants and AH were derived.lK3 A linear relationship has been reported between the pK, of RC0,H and the l%n chemical shift of Ar3Sn02CR.154For the complexes (YC6H,CH,)nSnC14-n, it was concluded from llgSn n.m.r. spectra that one conformation predominates. The lloSn chemical shifts were related to inductive and neighbour anisotropy effects and to (p,-d,) interactions.lK6lleSn N.m.r. spectroscopy has also been used to investigate association in Bun2Sn(OR),and Bun,SnOR 166 and chemical shifts have been reported for a variety of tin c~mplexes.'~'

at

148

J. Blazer, 0. Lutz, and W. Steinkilberg, Z . Naturfursch., 1972, 27a, 72. A. D. Buckingham and P. A. Kollman, Mot. Phys., 1972, 23, 65. R. G. Kidd, R. W. Matthews, and H. G. Spinney, J . Amer. Chem. SOL-.,1972, 94,

6686. S. P. Ionov and V. S. Lyubimov, Russ. J. Phys. Chem., 1971, 45, 1407. lb0 N. S. Biradar and M . A. Pujar, 2. anurg. Chem., 1972, 391, 54. 161 D. Rehder and J. Schmidt, Z . Naturforsch., 1972, 27b, 625. lS2 W. McFarlane, J. C. Maire, and M . Delmas, J.C.S. Dalron, 1972, 1862. l S s V. N. Torocheshnikov, A. P. TupEiauskas, N. M. Sergeyev, and Yu. A . Ustynyuk, J . Organometallic Chem., 1972, 35, C25. lS4 W. McFarlane and R. J. Wood, J. Organometallic Chem., 1972, 40,C17. l b 6 L. Verdonck and G. P. Van der Kelen, J . Organometallic Chem., 1972, 10, 139. lL8 P. J. Smith, R. F. M. White, and L. Smith, J . Organometallic Chem., 1972, 40, 341. 15' A. G. Davies, L. Smith, and P. J. Smith, J . Organometallic Chem., 1972, 39, 279.

Nirclear Magnetic Resonance Spectroscopy

15

IH-(leaHg) INDOR has been used to derive lQaHgchemical shifts for a number of dialkyl- or diaryl-mercury compounds.158

Relaxation Measurements. The 13C nuclear spin-lattice relaxation time Tl was studied in liquid Ni(C0)4 and Fe(CO),. Only anisotropic chemical shift and spin-rotation interaction contribute to the relaxation rate. It was possible to derive the anisotropy of the chemical shift and both spinrotation interaction From Tl measurements on substituted ferrocenes it has proved possible to measure the correlation time and to show that the unsubstituted ring is spinning up to seven times faster than the substituted ring.lSo has been measured for 15N in 15NH3(186 s) and 15ND3(413 s).lel The use of 29Si n.m.r. spectroscopy has been examined. However, as a consequence of the long TIand the negative nuclear Overhauser enhancement the total destruction of the signal can result. As Me4Si has a relatively short T' at room temperature and a small Overhauser enhancement it makes a good reference.lB2 From the measurement of 7" for lH, ,H, and 31P for PhPH,, PhPD,, C6D6PH2,and C6DbPD2it has proved possible to determine the diffusion coefficient and the rotational diffusion coefficient, and the potential barrier to rotation was also The complete rotational diffusion tensors, and hence average correlation times, of the three symmetric top molecules PCI,, PBr,, and POCl, have been obtained from viscosity and halogen n.m.r. relaxation time data.ls4 Similarly, 1J(31P-36C1)= 127 Hz for PC13 and 1J(31P-7QBr) = 296 Hz for PBr, have been measured.lB5 The relaxation rates of 69Gaand 71Ga have been measured in aqueous solution and compared with the theoretical ratio of relaxation rates of 2.5. This ratio is only approached in concentrated solution.166 Contrary to a commonly held myth, T,and T2for 11QSnC14 (TI = ca. 2 s, T, = ca. 2 ms) and l19SnI, (T, = ca. 0.5 s, T2= ca. 10 ms) are short. It was possible to derive 1J(11QSn-35CI) = 470 Hz and 1J(119Sn-1271) = 940 Hz.ls7

2 Stereochemistry This section is subdivided into nine parts, which contain n.m.r. information about lithium, beryllium, magnesium, calcium, 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-referencesare 1*8 A. P. TupEiauskas, N. M. Sergeyev, Yu. A. Ustynyuk, and A. N. Kashin, J. Magn. Resonance, 1972, 7 , 124. H. W. Spiess and H. Mahnke, Ber. Bunsengesellschaft phys. Chent., 1972, 76, 990. l e o G . C. Levy, Tetrahedron Letters, 1972, 3709. W. M. Litchman and M. Alei, jun., J. Chem. Phys., 1972, 56, 5818. laa G . C. Levy, J. Amer. Chem. SOC.,1972, 94, 4793. ll)s S. J. Seymour and J. Jonas, J. Magn. Resonance, 1972, 8, 376. la' K. T. Gillen, J. Chem. Phys., 1972, 56, 1573. Ieb A. D. Jordan, R. G. Cavell, and R. B. Jordan, J. Chem. Phys., 1972, 56, 483. le6 V. P. Tarasov and Yu. A. Buslaev, Mol. Phys., 1972, 24,665. 16' R. R. Sharp, J. Chem. Phys., 1972, 57, 5321.

lliD

16

Spectroscopic Properties of Inorganic and Organometallic Compounds

given at the beginning of each subgroup 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 on dynamic systems, paramagnetic systems, and solid-state n.m.r. Thus many more compounds of relevance to this chapter appear in these sections. Complexes of Li, Be, M g , Ca, Sc, Y, La, and U.-Information concerning complexes of these elements can be found at the following sources: R2Mg loS and (C6H6)Ni(PPh3)MgBr.7eo lH N.m.r. spectroscopy has been used to show that ButCH,CH=CHLi is a cis-trans mixture,lB8and to investigate the reaction of (D,C),CLi with isoprene to yield oligomers such as (5).lse Data have also been reported (CD,)jCCNMe, /'C\

Li ,CH,-CHMe fH2 \ Me CH=-CMe

I-.

for LiCHzCN and PhCHLiCN.170 lH N.m.r. spectroscopy is useful in determining the ratio of LiOBun to LiBun by observation of the 3-methylene resonances.171 The lH and 7Li n.m.r. spectra of a variety of meta- and para-substituted aryl-lithium and aryl Grignard compounds in ether have been examined. In contrast to covalently substituted benzenes, the inherently large chemical shifts between the ring protons permit a detailed analysis of the spectra, and thus the influence of the substituent on both the chemical shifts and spin-spin coupling were investigated. A correlation between 7Li and o-hydrogen chemical shifts was The 13C n.m.r. spectrum of (6; R = H or Me) shows a quartet due to 1J(13C-7Li). Both the NMe and NCH, proton resonance patterns are temperature dependent, e.g. NMe, is a singlet at 25 "C and two singlets at -60 OC.17, The lH n.m.r. spectra of (7; M = Li, Na, MgBr, or K) have been ~ e p 0 r t e d . l ~ ~ m The lH n.m.r. spectra of H2C=CHCH2CDzMand CH2CH2CHCH2CD2M (M = Li or MgBr) have been examined in an unsuccessful search for rearrangement^.^^^ The 7Li n.m.r. spectrum of p-t-amylbenzyl-lithium is The lH n.rn.r. spectrum of the addition product from ButLi and butadiene polymer has been used to show cis-trans isomerism.177

1'0

I7l 173 17' 175

W. H. Glaze, J. E. Hanicak, M. L. Moore, and J. Chaudhuri, J . Organometallic Chem., 1972,44, 39. A. Ulrich, J. Cressely, A. Deluzarche, F. SchuC, J. Sledz, and C. Tanielian, Bull. SOC.chim. France, 1972, 3556. R. Das and C. A. Wilkie, J . Amer. Chem. SOC.,1972, 94, 4555. P. J. Reed and J. R. Urwin, J . Organometallic Chem., 1972, 39, 1. J. A. Ladd and J. Parker, J.C.S. Dalton, 1972, 930. G . van Koten and J. G. Noltes, J.C.S. Chem. Comm., 1972, 940. G . Fraenkel, C. C. Ho, Y. Liang, and S. Yu, J . Amer. Chem. SOC.,1972, 94, 4733. A. Maercker and W. Theysohn, Annalen, 1972, 759, 132. R. Waack, M. A. Doran, and A. L. Gatzke, J . Organometallic Chem., 1972, 46,1 . S. Bywater, D. J. Worsfold, and G. Hollingsworth, Macromolecules, 1972, 5, 389.

Nirrlear. Mcqvietic Resonmice Spectroscopy

I

cu

17

1

cu

The lowest recorded shift for protons bound to carbon which is itself bound to beryllium has been reported for (PhCH,),BeOEt (T 8.25).177a Data have also been reported for (ButO),Be,C1,, X2Be3(OB~t)4,177D Me,AIBe,(OBut),, [Be(OCEt2Me)2]3,178 [Me4N][(Et2Be)2SCN],17Q Be(acac),, and Be(ethy1 acetoacetate),.lsO 'H N.m.r. spectra of the cis-trans stereoisomers of vinylic organomagnesium compounds have been studied and the parameters discussed in terms of structural modifications.181 When Me,NCH,CH,NMe, is added to EtMgBr, two sets of resonances are observed due to Et,Mg( Me2NCH2CH2NMe,)and EtBrMg(Me2NCH2CH,NMe2).lA2lH N.m.r.

-

data have also been reported for (8; M = Mg or Hg), OCH2CH2Mg,ls3 After enrichment to 90% in 13C, and (tetraphenylp~rphyrin)Mg,(py),.~~~ the 13Cn.m.r. spectra of chlorophyll a and b have been recorded and many assignments made.ls5 Data have also been reported for (8) and M g{ N( SiMe3)2}2.187

G. E. Coates and R. C. Srivastava, J.C.S. Dalton, 1972, 1541. R. A. Andersen, N . A. Bell, and G . E. Coates, J.C.S. Dalton, 1972, 577. 17' R. A. Andersen and G. E. Coates, J.C.S. Dalton, 1972, 2153. 170 N. Atam, H. Miiller, and K. Dehnicke, J. Organontetallic Chem., 1972, 37, 15. In'' L. Maijs, I. Vevere, and 1. Strauss, Lato. Psr. Zinat. Akad. Vestis, Kim. Ser., 1972, 4, 486. B. MCchin and N. Naulet, J. Organometallic Chem., 1972, 39, 229. ln2 J. A. Magnuson and J. D. Roberts, J. Magn. Resonance, 1972, 37, 133. 1 H 3 C. Blomberg, G. Schat, H. H. Grootveld, A. D. Vreugdenhil, and F. Bickelhaupt, Ailrialen, 1972, 763, 148. H. Kobayashi, T. Hara, and Y. Kaizu, Bull. Chem. SOC.Japan, 1972, 45, 2148. I H 5 C. E. Strouse, V. H. Kollrnan, and N. A. Matwiyoff, Biochem. Biophys. Res. Comm., 1972, 46, 328. Ixa M . Kirilov and G. Petrov, Monatsh., 1972, 103, 1651. l H 7 U. Wannagat, H. Autzen, H. Kuckcrtz, and H.-J. Wismar, 2. anorg. Chem., 1972, 394, 254.

17:'

Li76

2

18

Spectroscopic Properties of Iriorganic arid Organometallic Compoirnds

An IH n.m.r. investigation has demonstrated the formation of 1:2 complexes of La3' and Y 3 +with edta,lseand the presence of a mole of water in aquoglyoxalbis-(2-hydroxyanil)dioxouranium.1us Data have also been reported for S C [ N ( S ~ M ~ , ) , ] ,UO,(salen), ,~~~ and related compounds.lB1 The 'H n.m.r. spectrum of (9) shows no evidence for co-ordination of -NRlR2 192

Complexes of Ti, Zr, Hf, Th, V, Nb, and Ta.-Information concerning complexes of these elements can be found at the following sources: TiCI,, TiBr,, [TiF6]2-,148(CH2)3(C5H4),MC12(3; M = Ti, Zr, or Hf),87 Ti(CH,Ph),, Zr(CH2Ph)4,107(C5H,),TiXz,108(C5H,),Ti(OCOPh),,483and N b(O Me), .31 When (C,Me,),TiMe, is heated, one mole of methane is formed. lH N.m.r. spectroscopy shows one C,Me, ring to have four methyl singlets and there is a high-field methyl signal. Structures such as (10) were suggested but the CH, resonance was not found. The Evans method of determining susceptibility was applied to (C,Me,),Ti and a hydride resonance at 6 0.28 was found in the decomposition product (C,Me,)2TiH2.1g3Data

(10)

(11)

have also been reported for (l1),lo4 (C,H,),M1Cl(M2Ph3) (MI = Ti, Zr, or Hf; M2 = Si, Ge, or Sn), (C5H5)zTi(SnPh3)2,195 (C,H,),M(CH,Ph), (M = Ti or Zr),lo6and (Et,N),Ti(vinylic Li,P4Ph4reacts with (C6H5),MX2(M = Ti or Zr) to yield (12; M = Ti or Zr), which gives an AX2 31Pn.m.r. spectrum with 1J(31P-31P)= 323 Hz. The 31Pchemical shifts are very metal-dependent.1B8I t has been concluded from 'H n.m.r. and i.r. spectroscopy measurements on (OC),CrCMeOTi(C,H,),Cl and {(OC),CrCMeO),Ti(C,H,) that the electronegativity of the N. A. Kostromina and T. V. Ternovaya, Zhur. neorg. Khim., 1972, 17, 1596. G. Bandoli, L. Caltalini, D. A. Clemente, M . Vidali, and P. A. Vigato, J.C.S. CI~etn Comm., 1972, 344. l o o E. C. Alyea, D. C. Bradley, and R. G . Copperthwaite, J.C.S. Dalton, 1Y72, 1580. A. Pasini, M. Gullotti, and E. Cesarotti, J . Inorg. Nuclear Chem., 1972, 34, 3821. M. Vidali, P. A. Vigato, G. Bandoli, D. A. Clemente, and U. Casellato, Inorg. Chirn. Acta, 1972, 6 , 671. J. E. Bercaw, R. H. Marvich, L. G . Bell, and H . H . Brintzinger, J . Amer. Chem. Soc., lB8

lMB

1972, 94, 1219.

K. Yasufuku and H. Yamazaki, Bull. Chem. SOC.Japan, 1972, 45, 2664. 195 B. M. Kingston and M. F. Lappert, J.C.S. Dalton, 1972, 69. lea G. Fachinetti and C. Floriani, J.C.S. Chem. Comm., 1972, 654. lB7 H . Burger and H.-J. Neese, J. Organometallic Chem., 1972, 36, 101. l B a K. Issleib, G. Wille, and F. Krech, Angew. Chem. Internat. Edn., 1972, 11, 527.

Nuclear Magnetic Resonarice Spectroscopy 19 (OC),CrCMeO group towards Ti is the same as that of Cl.lSe 'H N.m.r. spectroscopy has been used to determine the extent of deuteriation of (MeC,H,),Ti(allyl) after treatment with D, and conversion into (MeC6H4)2TiC1,.20nData have also been reported for (1 3).201 For MeTiC13(XCH2CH2Y) (X, Y = OMe, NMe,, or SMe), it was necessary to cool to stop the process (14) ~ ( 1 5 ) . ~ OlH ~ N.m.r. spectroscopy has been used to show that TICl,,HCO,R and TiCl4,2HCO,R do not dissociate in solution ,03 and data have been reported for (16),,04 C13TiS2PF,,

ClsNb(S2PF2)2,206 (C,H&ZrMe,, (C,H,),ZrMeX, (C6H5)2ZrC1,,206 P&I2 --,and HfAl2(OPri) 207 Hf(OPr*),,Pr'OH, [H f,(O Pri)J -, [Hf3(0 When (C6H&ZrH2is treated with AIMe, the hydrides become inequivalent and couple. The structure (1 7) was suggested.208lH N.m.r. spectroscopy has been used to investigate the reaction of (CAH8),Hfwith AlHEt, and data are also reported for (C,H8jHf(allyl),,209L,ThCl, (L = Schiff base),210 and (C6H6)3ThBH4.211 61V N.m.r. spectroscopy has been used to help to characterize M [V(CO),l, [J34N lY[V(C0)4(CN)212, WV(CO),NH31, [V(C0),(CN)I-, and [V(COj,(PPh3)]-.212The inethylene resonance of VO(CH,SiMe:,), is w. 150 Hz broad and this was attributed to 51V Data have also E. 0. Fischer and S. Fontana, J. Orgarioriretallic Chem., 1972, 40,159. H. A. Martin, M. Van Gorkom, and R. 0. D e Jongh, J . Organometallic Chem., 1972, 36, 93. rol C. Floriani and G. Fachinetti, J.C.S. Chem. Comm., 1972, 790. "us R. J . H. Clark and A, J. McAlees, Znorg. Chem., 1972, 11, 342. M. Basso-Bert, D. Gervais, and J.-P. Laurent, J. Chim. phys., 1972, 69, 982. " " I H. Burger and U. Dammgen, 2. anorg. Chem., 1972, 394, 209. R. G . Cavell and A. R. Sanger, Inorg. Chem., 1972, 11, 2016. ? 0 4 P. C. Wailes, H. Weigold, and A. P. Bell, J . Organometallic Chem., 1972. 34. 155. 207 R. C. Mehrotra and A. Mehrotra, J.C.S. Dulton, 1972, 1203. 2 0 8 P. C. Wailes, H. Weigoid, and A. P. Bell, J . Organometallic Chem., 1972, 43, C29. "09 H.-J. Kablitz, R. Kallweit, and G. Wilke, J . Organometallic Chem., 1972, 44, C49. " l o N. S. Biradar and V. H. Kulkarni, Z . anorg. Chem., 1972,387, 275. "I1 T. J. Marks, W. J. Kennelly, J. R. Kolb, and L. A. Shimp, Inorg. Chem., 1972, 11, 2540.

212

D . Rehder, J. Organometallic Chem., 1972, 37, 303. W. Mowat, A . Shortland, G . Yagupsky, N. J. Hill, M . Yagupsky, and G . Wilkinson, J.C.S. Dulton, 1972, 5 3 3 .

20

Spectroscopic Properties of Inorgaiiic aiid Organometallic Compoitnds (C,H,),ZrHAI Me, / \

H

H

\ /

(C5H,),Zr H A IMe,

(17)

been reported for (C6H5)V(C0)2(PF2NC5Hlo)2,214 VO(OH)(~upferron),,~l~ (C5H5),NbH(PMe2Ph), [(C5H6)NbH2(PMe2Ph)]+PF6-,216 ( I 8 ; M = Ni, Pd, or Pt),217and MenNbCl,-nL.2'8 The adducts of NbCl, and TaCI, with some aliphatic and cyclic oxides and sulphides have been studied by 'H n.m.r. spectroscopy and are found to have 1:l stoicheiometry at room temperature and lower. For O(CH2CH2),STaC15,two species were detected, with one co-ordinated via oxygen and the other via sulphur. The stability of the complexes appeared to be controlled by steric

Complexes of Cr, Mo, and W.-Information concerning complexes of these elements can be found at the following sources: (OC)6MCXY (M = Cr or W ; X = OR or NR1R2; Y = organic group),ll0~ 111 cisL,M(CO), [M = Cr or Mo; L = (CF3),PR or CF3PR2],s3 (C4H6)Cr(C0)4,414 (OC)+,ML, (L = phosphorus ligand; M = Cr, Mo, or W),45(C,H,)Mo(CO)(PF,NM~~)~CI,~'~ M,(CH,SiMe,), (M = M o or W),213 w ( c o ) g P x ~ , 7Me6W,78 2 and C r ( a ~ a c ) , . ~ ~ lH and I4N n.m.r. spectroscopies have been used to determine the mode of bonding in (19; M = Cr, Mo, or W ; X = 0, S, or Se). When the

ligand is complexed via N, the 14Nchemical shift is ca. 80 p.p.m., but when complexed via X is ca. 10 p.p.m.,,O An n.m.r. study of a series of bis-pphosphido-dimetallic species has demonstrated that large increases in J(P-P') occur on reduction to the dianion. These increases were attributed to an increase of the metal-metal distance and a marked decrease in the phosphorus-phosphorus distance. Activation parameters were measured for the inversion of (OC),M(p-PMe,),M(CO), (M = Cr, Mo, or W;

a15

*IE a17 21a

R. B. King, W. C. Zipperer, and M. Ishaq, Inorg. Chem., 1972, 11, 1361. A. T. Pilipenko, L. L. Shevchenko, V. V. Trachevskii, V. N . Strokan, and L. A . Zyuzya, Zhur. priklad. Spektroskopii, 1972, 16, 290. C. R. Lucas and M. L. H. Green, J.C.S. Chem. Comm., 1972, 1005. W. E. Douglas and M. L. H. Green, J.C.S. Dalton, 1972, 1796. G. W. A. Fowles, D. A. Rice, and J. D . Wilkins, J.C.S. Dalfon, 1972, 2313. A. Merbach and J. C. Bunzli, Helv. Chim.A d a , 1972, 55, 580. J. C. Weis and W. Beck, J. Organometallic Chem., 1972, 44, 325.


21

4 ; M = Fe or Ru; n = 3).,,l The lH n.m.r. spectra of (OC),MPMe,PMe2 (M = Cr, Mo, or W) are complex, and data have been given

tl =

for all combinations of the type (OC)6M1PMe2PMe2M2(CO),,222 Mo(CO),(PMePh2)2,223(OC)5M1PPh2SnMe3-,X, (including 31P n.m.r. data),224 [Ph&I[M'(CO)6M1(CO)5{(h2Sb)2CH2), (M1(CO)5)2(Me2Sb)2CH2,225 N4CR],22s Me3SnSMeM1(CO),, (C5H,)M3(CO)3SMe, (C,H,)(CO),228 (C6Hs)M1(CO)3HgS,CNEt,,229 (M1, M2 = Cr, Mo, FeSMeCr(C0)5,227s or W ; M3 = Mo or W), and [(C~Me~)Cr(C0),]2.230 The lH n.rn.r. spectrum of (20; M = Cr, Mo, or W) has been analysed as AA'BB'X. As the NH proton was most affected by co-ordination it was postulated that co-ordination via S=C( The lH n.m.r. spectra of (21 ; M = Cr, Mo, or W ; L = CO or PPh3) have been measured

The and used to show that when L = PPh3, L enters the cis ' H and 19F n.m.r. spectra of ML, and M(CO)L5 [M = Cr, Mo, or W ; L = PrnOPF2, P(OMe),F, P(OMe),, MeP(OMe),, or Me,P(OMe)] are very complex as they are of the [AX],, [AX,],, or AX3[BY3], type.233 lH N.m.r. spectroscopy has been used to investigate the protonation of (arene)Cr(CO),L (L = CO or PPh,). The observation of a signal at ca. T 14 led to the suggestion that protonation occurs on the meta1.234-236 The position of base-catalysed deuteriation of (arene)Cr(CO), has been

"' "" 2"3

225

226

227

Z2R 2:'o

'L3z 933 'Ly4 ":j5

ZM

R. E. Dessy, A . L. Rheingold, and G. D. Howard, J. Amer. Chem. SOC., 1972, 94, 746. M. Brockhaus, F. Staudacher, and H. Vahrenkamp, Chem. Ber., 1972, 105, 3716. P. M. Treichel, W. M. Douglas, and W. K. Dean, Znorg. Chem., 1972, 11, 1615. H. Noth and S. N. Sze, J . Organometallic Cheni., 1972, 43, 249. T. Fukumoto, Y. Matsumura, and R. Ohawara, J. Organometallic Chem., 1972, 37, 113. J. C. Weis and W. Beck, Chem. Ber., 1972, 105, 3202. W. Ehrl and H. Vahrenkamp, Chem. Ber., 1972, 105, 1471. W. J. Schlientz and J. K. Ruff, Znorg. Chem., 1972, 11, 2265. W. K. Glass and T. Shiels, Znorg. Nuclear Chem. Letters, 1972, 8, 257. R. B. King and A. Efraty, J. Amer. Chem. SOC.,1972, 94, 3773. D. De Filippo, F. Devillanova, C. Preti, E. F. Trogu, and P. Viglino, Znorg. Chim. Acta, 1972, 6 , 23. H. Brunncr and W. A. Herrmann, Chem. Ber., 1972, 105, 770. R. Mathieu and R. Poilblanc, Inorg. Chem., 1972, 11, 1859. C. P. Lillya and R. A. Sahatjian, Znorg. Chem., 1972, 11, 889, B. V. Lokshin, V. I. Zdanovich, N. K. Baranetskaya, V. N. Setkina, and D. N. Kursanov, J. Orgnmtnetallic Chem., 1972, 37, 33 1. D. N. Kursanov, V. N. Setkina, P. V. Petrovskii, V. I. Zdanovich, N. K. Baranctskaya, and I. D. Rubin, J. Organometallic Cheni., 1972, 37, 339.

22


investigated by 'H n.m.r. s p e c t r o ~ c o p y238 . ~ ~The ~ ~ lH n.m.r. spectra of the Cr(CO), and Mn(CO), complexes of 2-R-pyrrole (R == Ph or PhCH2) have been interpreted in terms of electronic effects transmitted through the a-electron system and ring-current lH N.m.r. spectroscopy has been used to show that Cr(CO), co-ordinates to a phenyl group in Zn(tetraphenylp~rphyrin),~~~ and the spectrum of (22) is of the AA'BB' type.241 Data have also been reported for (arene)C~(CO),,~~~* 243 (23) (including 31Pn.m.r. data),244(C7H8)Cr(C0)2{P(OPh)3},245 (24),246 (OC),CrCPh(NR1R2),247 (OC)5CrCR1(SR2),248(OC)5Cr(CHNMe2),24B(OC),-

CrPh(OMe)(PHMe2),260 C4F7(NO),(C5H5)Cr (l°F

n.m.r.

data),251

(C,H,)Cr(CO)(N0)(0lefin),~~~ [(C,H,)Fe(C,H,)]3PCr(CO)5,253 Me,PCH,-

CHaPh.le2Cr(C0)5,2S4 and (alko~ynorbornene)Cr(CO),.~~~ Extensive use has been made of the Karplus equation i n order to determine the conformation of the chelate ring in (25).256 IH and lDF n.m.r. data have also been given for Cr(CO),(f,fars) [f,fars = (26)].257 When isocyanides co-ordinate to Cr(CO), or Mo(CO), to form (RNC),M(CO)+,, 2J(14N-1H)is lost. The ASIS effect was measured in an attempt 237 298

w 240 241 24a

2 43

arc 245

ara 247 248

24r 260

261

212 263 264

166 268

267

M. Ashraf, Canad. J. Chem., 1972, 50, 118. W. S. Trahanosky and R. J. Card, J. Amer. Cheni. SOC.,1972, 94, 2897. N. J. Gogan and C. S. Davies, J. Organometallic Chem., 1972, 39, 129. N. J. Gogan and Z. U. Siddiqui, Canad. J. Client., 1972, 50, 720. K. t)fele and E. Dotzauer, J. Organonretallic Chem., 1972, 42, C87. G. R. Knox, D. G. Leppard, P. L. Pauson, and W. E. Watts, J. Organometallic Chenr., 1972, 34, 347.

M. Ashraf and W. R. Jackson, J.C.S. Perhin I I , 1972, 103. H. Vahrenkamp and H. Noth, Chem. Ber., 1972, 105, 1148. W. P. Anderson, W. G. Blenderman, and K. A . Drews, J.

O r ~ t i i i o r t i c t t i l l iChern., ~~ 1972, 42, 139. J. A. S. Howell, B. F. G. Johnson, and J. Lewis, J. Organottiettrllic Chern., 1972, 42, c54. E. 0. Fischer and M. Leupold, Chem. Ber., 1972, 105, 599. E. 0. Fischer and M. Leupold, C. G. Kreiter, and J. Miiller, Chem. Ber., 1972, 105, 150. B. Cetinkaya, M. F. Lappert, and K. Turner, J.C.S. Chem. Comm., 1972, 851. F. R . Kreissl, C. G. Kreiter, and E. 0. Fischer, Angew. Chem. Internal. Erin., 1972, 11, 6 4 3 . R. B. King and W. C. Zipperer, Inorg. Chem., 1972, 11, 21 19. M. Herberhold and H. Ah, J. Organometallic Chem., 1972, 42, 407. C. U. Pittman, jun. and G. 0. Evans, J. Organometallic Chem., 1972, 43, 361. J. A. Connor, E. M. Jones, and G. K. McEwen, J. Organornetullic Chem., 1972, 43, 357. D. Wege and S. P. Wilkinson, J.C.S. Chem. Comm., 1972, 1335. W. R. Cullen, L. D. Hall, and J. E. H. Ward, J. Amer. Chem. Soc., 1972, 94, 5702. 3. P. Crow, W. R. Cullen, and F. L. Hou, Inorg. C h ~ m .1972, , 11, 2125.

Nirclear Mqvetic Resonance Spectroscopy

23

C'O

CF,-CF,

Mc, AsCI ==C I AsM c,

(26)

r

(27) to place the positive The lH, llB, and 13C n.m.r. spectra of (27; M = Cr or Mo) and 7,9- or 7,8-BDH,(3-Br-pyridine)CHPM(CO), have been The separation of the 01 and fl carbon protons of the substituted ferrocene ring has been used to estimate the Hammett substituent constant, (TP, and the resonance constituent constant, OR, for (OC),MCX(C5H4)Fe(C6)~5) ( M = Cr or W).2eoThe l H n.m.r. spectrum of PhC=C-C(OEt)Cr(CO), is invariant with temperature, implying a low-energy barrier to COEt rotation. Data were also given for PhC=CC(OEt)W(CO),, PhC(NMe)=CHC(N Me2)W(C0)5,261 (OC),CrC(OEt)NR,, (OC),WC(SeMe)Me, and c*is-(OC)4Cr{C(OEt)PMez}z.262 For ~ ~ S - ( O C ) ~ M [ C ( O E ~ ) P(M M ~=~ ]Cr , or W), the PMe, protons form an intermediate [AX,], pattern, implying a significant value for 4J(31P-31P).263 The methanolysis of (CIR,P)Mo(CO), has been followed by lH n.m.r. and data were reported for (XR,P)(OC),Mo (X = RO, NH,, NHMe, NMe,, or SH; R = Me or Ph),264 [Et,NH][Mo(CO),PPh,O], and (OC),MO(~-PR~~OPR~~)MO(CO)~.~*~ It is interesting to note that for the 25R

258 21io

"1 2E2 'LE3

"* 21)5

J. A. Connor, E. M. Jones, G . K . McEwen. M. K . Lloyd, and J. A . McCleverty, J.C.S. Dalton, 1972, 1246. D. C. Bccr and L,. J. Todd, J . Orgunottretallir Chem., 1972, 36. 77. J . A . Connor and J . P. Lloyd, J.C.S. Dnltoti, 1972, 1470. E. 0. Fischcr and F. R . Kreissl, J . Organonretallic Chern., 1972. 35, C47. E. 0.Fischer, Piire Appl. Chern., 1972 30, 353. E. 0. Fischer, F. R. Kreissl, C. G . Kreiter, and EL W. Meineke, Chetn. Ber., 1972, 105. 2 5 5 8 . C. S. Kraihanzel and C. M. Bartish, J . Organornerallic Chem., 1972, 43. 343. C. S. Krailianzel and C. M. Bartish, J . Atner. Chem. Sac., 1972, 94, 3572.

24

Spcv-troscwpicPropert ies oj' Inorganic and Orgcuionwtallic Cbmpoiinds

latter compound, when R1 = R 2 = Me, apparent triplets arc observed for the methyl groups. Compounds of the type 1 -X-2,4,6-trimethylbenzene have been synthesized in order to detect ring currents in X by measuring the chemical shift separation of the 2,6- and 4-methyl groups. When X = (28), the difference is 0.25 p.p.m., and when X = (29), 0.33 p.p.m., implying the presence of a ring current, but when X = (30), the difference is -0.15 p.p.m.26S Data were also given for (31 ; X = 0, NR, etc. ; L = CO or PPh,).267 lH N.m.r. spectroscopy has been used to provide evidence of donor-acceptor interactions in [C,H,NMe][ Mo(CO),I] and [N4P4Me9][Mo(CO)51],26B and (32; R' = Me, R2 = H ; R1 = H, R2 = Et) show the presence of two conformers on The 'H n.m.r. spectrum of (33) shows inequivalent methyl groups owing to restricted rotation about

the carbon-nitrogen bond. Methylation occurs at the sulphur atoms, as shown by the observation of three methyl resonances.27o Data have also (C,H,)Mo(CO),(PPh,H)Br, been reported on [(C,H,)MO(CO)~PP~~H]PF~, Cr(CO)4(PPh2H)2, Mo(CO),(PhPH,),, W2(CO)6(PPh2)2,271(C,H,)Mo(C0)2(PPh3)H,(C,H,)Mo(CO),(PPh,)(C,F,N) (and related complexes with 19F n.m.r. data),272 (C,H,)Mo(CO),(allylic ligand),273 (C,H,)MO(CO)~266 287

Lil

G. Hafelinger, R. G . Weissenhorn, F. Hack, and G. Westermayer, Angew. Chem. Internat. Edn., 1972, 11, 725. I. W. Renk and H. tom Dieck, Chem. Ber., 1972, 105, 1403. N. L. Paddock, T, N. Ranganathan, and J. N. Wingfield, J.C.S. Dalton, 1972, 1578. J . L. Roustan, C. Charrier, J. Y. Merour, J. Benaim, and C. Giannotti, J. Organometallic Chem., 1972, 38, C37. P. M. Treichel and W. K. Dean, J.C.S.Dalton, 1972, 804. P. M . Treichcl, W. K. Dean, and W. M. Douglas, J. Organometallic Chem., 1972, 42, 145.

27d

27''

M. I. Bruce, B. L. Goodall, D. N. Sharrocks, and F. G . A. Stone, J . Organometallic Chem., 1972, 39, 139. J . Y. MCrour, C. Charrier, J. BCnaim, J. L. Roustan, and D. C'ommereuc, J. Orgonoriietallic Chem., 1972, 39, 321.

Nircfcur Mapre fir Rcsonurtce Spec froscopy

LSnMe,,277",276

C N Me,277

R Mo(CO),(PMe,Ph)(C,H,

25

(C,H,) M o(CO),SnCI,S,-

(C5H5)M~(C0)2CN(A~Me2CH2CH=CH2),278 (C,H,)Mo-

{ (Ph2AsCH2CH2)2PPh}Mo(C0)2(C0 Me)(C0),(2-NR= CH-pyrrole),*" (C,H,), [(C5H5)Mo(CO),{(AsPh,CH,CH,),PPh}]PF,,280 and (C,H,),Mo(CO)? As the cyclopentadienyl resonance of (NC),C= C C ~ M O ( P P ~ ~ ) ~ ( C ~ H , ) consists of two 1 2 1 triplets in the ratio 4:1, it was suggested that this complex exists as a mixture of cis- and Irans-isomers.282 The 13C n.m.r. spectrum of (Bu~NC),MO(CN)~ has been examined over the temperature range of $40 to -47 "C, but no changes were Data have also been reported for (C5H5)Mo(NO)LX2,284(34),286 OMo(S2PF2),

I

OMe (34)

OMe

(l°F n.ni.r. data),286(C5H5),MHR (M = M o or W),287 [(C5H,),MH(C2H4)Ii-(M = M o or W),2R8 [Me4N],[(C5H5),M,Fe2(CO)~o]7280 (Ph3PCHCO)M(C0)5,290 (C7H,)M(CO)[P(OR)3]I,"91 K[(C,H,)M(CO),(COR)]~,~'~ CN],292 (CSH,)M(C0)3SCF,, [ ( C ~ H ~ ) M O ( C O ) , S C F ~(CSHS)M(C0)3COPh,204Me2T1[M(C,H,)(CO),]72g5and (C5H5)(CO)3MSiMe2X,296 where M = Mo or W. T. A . George, Inorg. Cheni., 1972, 11, 77. M. D. Curtis, Inorg. Chem., 1972, 11, 802. x6 P. J. Craig and J. Edwards, J . Organonietallic Chem., 1972, 46, 335. 2 7 7 W. K. Glass a n d T. Shiels, J . Organometallic Chetn., 1972, 35, C65. K. P. Wainwright and S. B. Wild, J . C . S . Chem. Cotnm., 1972, 571. 2'" H . Brunner and W. A. Herrmann, Chem. Ber., 1972, 105, 3600. 2yo R. B. King and P. N. Kapoor, Inorg. Chim. Acta, 1972, 6, 391. nd H . 11. Brintzinger, J . Amer. Chem. SOC.,1972, 94, 1386. 2y2 K. B. King and M. S. Saran, J . C . S . Chem. Conim., 1972, 1053. 2 * : ~ M. Novotny, D. F. Lewis, and S. J. Lippard, J . Atner. Chem. SOC.,1972, 94, 6961. 2 x 4 J. A. McCleverty a nd D. Seddon, J . C . S . Dalton, 1972. 2526. J. Chatt and J. R. Dilworth, J.C.S. Chem. Cotnm., 1972, 549. 2x6 R. G . Cavell and A. R. Sanger, Inorg. Chem., 1972, 1 1 , 2011. 2H7 A . Nakamura a n d S. Otsuka, J . Amer. Chem. SOC.,1972, 94, 1886. ?x8 F. W. S. Benfield, B. R. Francis, and M. L. H. Green, J . Organometallii, Chcm.. 1972, 44, C13. 2 H D A. T. T. Hsieh and M . J. Hays, J . Orgnnometallic Chem., 1972, 39, 157. A. Greco, J . Organometallic Chem., 1972, 43, 351. 2!11 T. W. Beall and L. W. Houk, Inurg. Chenr., 1972, 1 1 , 915. "I3 7'. Kruck, M. Hofler, and L. Liebig, Chent. Ber., 1972, 105, 1174. 2 n 3 J . L. Davidson and D. W. A . Sharp, J . C . S . Dnltorr, 1972, 107. w A . N . Nesmeyanov, L. G. Makarova, N. A. Ustynyuk, and L. V. Bogdtyreva, J . Organometallic Chem., 1972, 46, 105. 2flB B. Walther and C . Rockstroh. J . Orgonometallic Chetn., 1972, 44, C4. W. Malisch, J . Or~trrtometallicChern., 1972, 39, C28. "i4

2i5

?!I1]

26

Spectroscopic Properties of Inorganic and Organometallic Cornpour1d.y The 'H and O ' F n.m.r. spectra of FC6H4M(CO),L (M = Mo or W; L = CO or PPh,), FC,H,COMo(CO),PPh,, and (C,H,)W(CO),C,H,COMe-p, have been measured. The oh and 01 constants estimated from the Taft equation had negative values, indicating that metal carbonyl substituents display donor inductive and resonance effects with respect to the phenyl ring.2g7 The lH chemical shifts of Me3SnM(C5H5)(C0), The lH (M = Mo or W) have been measured as a function of n.m.r. spectra of (C5H6)M(CO),CONR'R2 (M = Mo or W) has been measured. When R1 = R2 = Me, only one methyl signal is observed at room temperature and two at - 30 0C.290The observation of only one methyl resonance for (C,H,)M(CO),N=C(p-tol), (M = Mo or W) over the temperature range -40 to +40 "C has been taken as evidence for a linear M-N-C skeleton. Data were also given for (C6H5)M(C0),{(P- tol),CNCb - tol),), (C,H,)M(CO),~(P- tol),CNC(p - tol),I(p - tol),CO (M = Mo or W),,Oo [(C,H,)MO(NO)XY]~,~~~ M(N0)2((Ph2As)2CH2),Xz (M = Mo or W; n = 1 or 2),,01a MOF,, [M202Fg]-(M = Mo or W),,02 and MO,CI,L,.~~~ The reaction of MoOF, and [WOF,]- with ethanol and MeCOCH,COMe in MeCN has been studied by l9F n.m.r. spectroscopy, and species such as MoOF,,MeCN and [WOF,(OEt)]- have been identified.304 Data have been reported for WH,(PR2Ph)3,305(C5H5),WH2, and (C5H,),WH,CHC1,.30e Me,W reacts with NO to yield compounds with two sharp singlets in the ratio 4:2 and X-ray structure determination shows the structure to be WMe4(0NMeN0)2.307The slP n.m.r. spectrum of (OC),WPPh2CH2PPh2shows 3J(31P-1e3W)= 6.3 Hz.,08 Data have been reported for W(CO),{ C ( 0 Me)(CH= C M e02CMe)),300(OC),W PPh2CH2PPh2, [(OC)5WPPh2CH2PPh,R]+,310 W(N2)z(PMe,Ph),, mer-W(CO),(PRPh2),, W(CO),(PBunPh,), (including 31Pn.m.r. data),," (OC),WEMe,XEMe,W(CO), (E = P or As; X = 0, S, NMe, or NPh) and related 287

*09

300

3n8

306 308 307

311

A. N. Nesmeyanov, L. G. Makarova, N. A. Ustynyuk, B. A. Kvasov, and L. V. Bogatyreva, J . Organomctallic Chcm., 1972, 34, 185. R. M . G. Roberts, J . Organometallic Chem., 1972, 40,359. W. Jetz and R . J. Angelici, J . Amer. Chem. Soc., 1972, 94, 3799. H. R. Keable and M. Kilner, J.C.S. Dalton, 1972, 153. J. A. McCleverty and D. Seddon, J.C.S. Dalton, 1972, 2588. J. A. Bowden, R. Colton, and C. J. Commons, Ausfral. J . Chem., 1972, 25, 1393. Yu. A. Buslaev, Yu. V. Kokunov, V. A. Bochkareva, and E. M. Shustorovich, Zhur. strukt. Khim., 1972, 13, 526. J. San Filippo, jun., Inorg. Chem., 1972, 11, 3140. Yu. A. Buslayev, Yu. V. Kokunov, V. A. Bochkaryova, and E. M . Shustorovich, J . Inorg. Nuclear Chem., 1972, 34, 2861. J. R. Moss and B. L. Shaw, J.C.S. Dalton, 1972, 1910. K. S. Chen, J. Kleinberg, and J. A . Landgrebe, J.C.S. Chem. Comm., 1972, 295. S. R. Fletcher, A. Shortland, A. C. Skapski, and G. Wilkinson, J.C.S. Chem. Comm., 1972, 922. R . L. Keiter and L. W. Cary, J . Amer. Chem. Soc., 1972, 94, 9232. C. P. Casey, R. A. Boggs, and R. L. Anderson, J . Amer. Chem. SOC.,1972, 94, 8947. R. L. Keiter and D. P. Shah, Inorg. Chem., 1972, 11, 191. B. Bell, J. Chatt, and G . J. Leigh, J . C . S . Dalton, 1972, 2492.


27

c o ni p lcxes,31 'L

(C, H :,) W (CO),( P F3)M e ,313 [-0S(=0)F 0W (= 0)X3- ] ,, ( X = OS0,F),314and (diphn~),Cl~W(N,HC0R).~~~ '14 N.m.r. spectroscopy has been used to show that Me,AI interacts with complexes such as W(N,),(diph~s),.~l~ Similarly, lH, lsF, and n.m.r.

spectroscopy have been used to investigate the reaction of WF6 with a wide variety of compounds such as Nb(OMe),, B(OMe),, (MeO),P=O, etc., and the stereochemistry of the resulting complexes has been determined.,17 ' H and lBFn.ii1.r. spectroscopy have been used to determine the stereochemistry of (MeO),WX,-, (X = F or Cl),,l* and to characterize the product formed between WF, and benzene or toluene.31s lSF N.m.r. spectroscopy has also been used to determine the structure of the products of reaction of WO, and HF. Species such as [WO,F,I2- and [W02F3(H,O)]- were Complexes of Mn and Re.- -Information concerning complexes of these elements can be found at the following sources : Re(C0)6CF2CFzMe,837 (OC)4Mn{CH2C(C02R1)CHR2),26s Mn(C0)4(PPhH2)Br,271M,(CO),Me,Ask= C(AsMe,)CF,kF,, (M = Mn or Re),257C4F,Mn(C0)5,261 (OC)5Mn-

Mn(CO),kCOCH2CH2CHMe,30B(OC),Mn(2-R-pyrr0le),~~~ (C,Me,)Mn(C,H,)Mn(CO),SMeSnMe,, (co)3,230 (MeC6H1)Mn(CO).,(PMePh2),223

(C,H,)M~(CO),SM~MO(CO),(C,H~),~~~ (C6H6)Mn(CO)(PF2NMe2)2,214 Re(C0)3(PFS)zBr,313 and Re2C16L2.303 'H N.m.r. spectroscopy has been used to follow the reaction of Me,SnMn(CO), with SnC14.321 For the complexes (RC,H,)Mn(CO), [R = asymmetric group, e.g. -CH(OH)CF,] the a-protons of the ring are i n e q ~ i v a l e n t .The ~ ~ ~*H chemical shifts of (C,H,)Mn(CO),L have been reported and compared with data for RC5H,Mn(CO),L and EtC,H,Mn( C O ) ( d i p h ~ ) s ) The . ~ ~ ~inductive effects deduced from the lSF n.m.r. spectra of (OC),MC6H4C6H4F(M = Mn or Re) agreed with those deduced from redox potentials.324 The compound (35) shows three llB n.m.r. signals, Data have also been reported consistent with the proposed 313

316 31(1

317 318

y20

:121

324

:Iz6

H . Vahrenkamp, Clirni. Bcr., 1972, 105, 3574. R. B. King and A , Efraty, J . Amer. Chem. Soc., 1972, 94, 3768. R. Dev and G . H. Cady, /norg. Chem., 1972, 11, 1 1 34. J. Chatt, G . A. Heath, and G. J. Leigh, J.C.S. Chem. Comm., 1972, 444. J. Chatt, R. H. Crabtree, and R . L. Richards, J.C.S. Chem. Comm., 1972, 534. D. W. Walker and J. M. Winfield, J . Inorg. Nuclear Chem., 1972, 34, 759. L. €3. Handy, K . G . Sharp, and F. E. Brinckman, Inorg. Chem., 1972, 11, 523. R. R. McLcan, D. W. A . Sharp, and J. M . Winfield, J.C.S. Dalton, 1972, 676. Yu. A. Buslaev, S. P. Petrosyants, and V. 1. Chagin, Zhiu. neorg. Khim.. 1972, 17, 704. R . A . Burnham, F. Glockling, and S. R . Stobart, J.C.S. Dalton, 1972, 1991. D. N. Kursanov, Z. N. Parnes, N . M. Loim, N . E. Kolobova, I . B. Zlotina, P. V . Pctrovskii, and E. I . Fcdin, J . Organonietallic Chem., 1972, 44, C15. A. G. Ginzburg, B. D. Lavrukhin, V. N . Sctkina, and P. 0. Okulevich, Zhur. obshchei Khim., 1972, 42, 514. S. P. Gubin, A. A. Koridze, N . A. Ogorodnikova, and B. A . Kvasov, Doklady Akad. h'nrrk S . S . S .R . . 1972, 205, 346. J . W. Howard and R . N . Grimes, Iizorg. Cheai., 1972, 11, 263.

28

Spectroscopic Properties of Inorganic and Organoniettrllic Conipoirntls

n‘

for H,GeMn(C0)5,328Me3SiCF2CF2Mn(CO)5,327 (OC),Mn2PH3,3z28 (OC),M,C(OMe)R (M = Mn, Tc, or Re).329M ~ ( C O ) , ( P M ~ , B Z ) , M(OC),~,~~~ M(C,H,CH=NR) (M = Mn or Re),331cis-MnCl(~OCH2CH2b)(CO)4,3”2 (Et5C5)Mn(C0)2PPh3,333 (C5H4COR)Mn(C0)3,334 (C5H5)Mn(C0)2NH =NH Mn(C0)2(C5H5),335 Mn(CO),- .(CN Me),Br, [M n(CO),- ,,(CNMe),]+,336 [ ( B u ~ N C ) ~ M ~(C5H5)Re(C0)2N2, ]+,~~~ (C5H5)Re(CO)3,33H (OC)3Re(S,PEt,)PPh2CHzCH2PPh2Re(CO),(S2PEt2),33e[ReBr(CO),(THF)],340 Cl,SiHRe,(CO),, PhC1,SiHRe,(CO)9, HRe,(C0),4,341(C5H5)ReMe(CO)(NO), [(C,H5)ReH(CO)]+,342 ~is-ReCl(C0),(PMe,Ph),,~~~ ReCl,(N=CH,)(PMe,Ph),, and ReC12(N=CHMe)(py)(PMePh,),.s1” sari

327 328

32D

330

3n1

332

333

3j4

33E

s37 33u

33D 340

343 344

R. D. George, K. M. Mackay, and S. R. Stobart, J.C.S. Dalton, 1972, 1505. H. C. Clark and T. L. Hauw, J. Organotnetallic Chem., 1972, 42, 429. E. 0. Fischer and W. A. Herrmann, Chetn. Ber., 1972, 105, 286. E. 0. Fischer, E. Offhaus, J. Muller, and D. Nothe, Chem. Ber., 1972, 105, 3027. R. L. Bennett, M. I. Bruce, and F. G. A. Stone, J. Organometallic Chetn., 1972, 38, 325. R. L. Bennett, M. I. Bruce, B. L. Goodall, M. Z. Iqbal, and F. (3. A. Stone, J.C.S. Dalton, 1972, 1787. M. Green, J. R. Moss, I. W. Nowell, and F. G . A. Stone, J.C.S. Chem. Comm., 1972, 1339. B. L. Lokshin, A.G.Ginzburg, V. N. Setkina, D.N. Kursanov,and I. B. Nemirovskaya, J. Organometallic Chem., 1972, 31, 347. M. Le Plouzenncc and R. Dabard, Bull. Soc. chim. France, 1972, 3600. D. Sellmann, J. Organometallic Chem., 1972, 44, C46. P. M. Treichel, G. E. Dirreen, and H. J. Mueh, J. Organometallic Chem., 1972, 44, 339. R. B. King and M. H. Saran, Inorg. Chem., 1972, 11, 2112. D. Sellmann, J. Organometallic Chem., 1972, 36, C27. E. Lindner and H. Berke, J. Organometallic Chetn., 1972, 39, 145. D. Vitali and F. Calderazzo, Gazzetta, 1972, 102, 587. J. K. Hoyano and W. A. G. Graham, Inorg. Chrm., 1972. 11. 1265. R. P. Stewart, N . Okamoto, and W. A . G. Graham, J. Orycitionictnllir. Chem.. 1072. 42, C32. D. J. Darensboiirg, Inorg. Nidenr Chein. Lettrrs, 1972, 8, 529. J. Chatt, R. J. Dosser, and G. J. Leigh, J.C.S. Chem. Comm., 1972, 1243.


29

Complexes of Fe, Ru, and 0s.--Information concerning complexes of these elements can be found at the following sources: Fe(C0)5,67elt9 Fe(CO),(Ar,SbCH,SbAr,), {Fe(CO)4)2(Me2SbCH2SbMe2),225 Fe(CO),_,L,,,45t330 Fe(CHNMe2)(C0)4,249(OC)3Fe(p-PMe2)2Fe(CO)3,221 Fe(CO),(PMePh,), Fe2(cO)6(PMe2Ph)2,223 Fe(CO),(C,F,)(C,F,), C,F,Fe(CO),(C6H5),251RU,(CO)~(PM~,BZ),,R U ( C O ) ~ ( P M ~ ~ B Z )[(Ph,PCHCO)~CI~,~~~ Fe(C0),]-,290 [Fe(C0)3SCF3]2, [Fe(CO)2PPh,SCF3]2,293Ru(CO),(C,H,CH=NR)2,331 (Me5C5)Fe(CO)2COMe,230 (C,H,)Fe(CO),SMe, (C,H,)Fe(CO),SMeM(CO), (M = Cr or W), (C,H,)Fe(CO),SMeMn(CO)2(C5H5),227(C6H,)Fe(CO)2X,s8~ 112 [(C,H,)Fe(C0),(PHPh,)l+, (C5H5)Fe(CO)(PHPh,)X, [~(C5H,)Fe>2(P2Ph,)2(~~~2H)212+,271 (C5H5)WCO)(PF3)1,,13 (C5H,),Fe2(C0)3(PF2NEt2),(C5H5)Fe(PF2NEt2)21,214 {(Ph,AsCH2CH2)2PPh}Fe(CO)(COMe)(C5H,),280 K[(C,H,)Fe(CO),(COR)(CN)], (C5H,)Fe(CO)(COR)(CNMe),292 (C5H5)(CO)2FeSiMe2X,296 (C,H,)RuRC1PPh3,131(OC),M-CFcX (M = Cr or W),,,O F c , P C ~ ( C O ) ~ F ,C~X~,~' ~160 ~ Fe(NMe=CH-CR=N [(1,7-B9HQCHE),Fel2-, and [{ 1,7-B9HBCHEMo(CO),),FeI2- (E = P or For H,Fe,(CO),{P(CF,),),, the hydride resonance is a triplet and one [AX,], pattern is found for the fluorine spectrum, which is consistent with (36). On standing, another species, which is thought to be (37), The lH n.m.r. spectrum of (tol,P),RuLH, shows a hydride resonance as a

(37) R. C . Dobbic, M .J. Hopkinson, a n d D. Whittaker, J.C.S. Dalton, 1972, 1030.

30

Spectroscopic Properties of Inorgniiic a i d Orgaiionictcillic Coiiiporrncis

Zi L

(38)

doublet of triplets with hydrogen coupling, i.e. the stereochemistry is ( 3 8 ) : (Ph8)3RuHCl N 2 €3 IOH$Me, and (Ph,P),Ru HCl(N C Me)N,B , 14 S Me, were also prepared.34s A linear correlation has been reported between the hydride chemical shift of H2Ru,(CO),E (E = S, Se, or Te) and the electronegativity of E.347The hydride signal of H2Ru3(CO),C,Ph, shows doubling due to two inequivalent The lH n.m.r. spectrum of H,Ru,(CO),CMe shows two singlets at T 5.88 and T 27.63 and the 13C n.m.r. spectrum shows two carbonyl Compound (39) shows coupling between the hydride signal and the central proton of the ally1

. Geschke, H. Pfeifer, and H . Winkler, Porous Struct. Cafnl. T r a m p . Processes Heterogeneous Catal., 1968, 1972, 281.

111

Niiclear Magnetic Resonance Spectroscopy

'H N.m.r. spectroscopy has been used to examine salt-gel solutions at room temperature and low temperatures. Salts with a large KU value displace more water from the 'H N.m.r. and i.r. spectroscopy have been used to show that in metamict cyrtolite, water is present both as H 2 0 and OH-.1580The molecular motions of SnMe,F in the solid state have been examined by continuous-wave and pulsed n.m.r. spectroscopy. Me,Sn rotates at high temperature and the methyl groups rotate even at 77 K.15*l A simple method has been proposed which enables chemical shifts in solids to be detected where only one chemical shift tensor contributes to the spectrum. The measurements of anisotropic chemical shifts have been made The for lH and 31Pin a single crystal of KH2P04by using this solid-state 31Pn.m.r. spectra of some adducts of POCI, and Lewis acids have been reported and it was concluded from the chemical shifts that in each case co-ordination is via oxygen.1583The compounds [PCInBr4-,]+ have been characterized in the solid state by 31P n.m.r. As the ferroelectric Curie temperature of KH,AsO, is approached from the paraelectric phase, additional resonance lines appear in the 7 5 An.m.r. ~ spectrum. These lines were shown to result from polarization fluctuations with lifetimes greater than 1 ms.1585 The electric-field gradient (E.F.G.) at the caesium sites in CsH2As04and the 133Csspin-lattice relaxation rate in CsD,AsO, have been determined. The results show that the timeaveraged value of the E.F.G. tensor at the caesium site in the paraelectric phase is the average of the two ferroelectric E.F.G. tensors for opposite directions.1586 Wide-line lH n.m.r. spectroscopy has been used to determine water in anodic coatings.1587 The n.m.r. spectra of ice crystals have been examined.16** The lH n.m.r. lineshape and second moment have been studied in H2S and H2Se at 58 K, and it was concluded that the lattice is rigid. Hydrogen-hydrogen distances of 1.883 5 0.007 8, for H2S and 2.014+0.011 A for H2Se were Tl has been measured for solid SF,.1500 Rigid-lattice n.m.r. spectra characteristic of intramolecular spinI

I

spin interactions have been measured for SF6, OCH2CH2CH2,and cyclo~~~ 1°F n.m.r. tineshapes butanone in cages of D20 ~ 1 a t h r a t e . lResolved J. J. Pesek and R. L. Pecsok, Analyt. Chem., 1972, 44, 620. E. S. Rudnitskaya and I. M. Lipova, Izuest. V.U.Z., Geol. Razved., 1972, 15, 43. 15L)1 S. E. Ulrich and B. A. Dunell, J.C.S. Faraday 11, 1972, 68, 680. Ibn2 T. Terao and T. Hashi, J . Magn. Resonance, 1972, 7 , 238. lSR3 K. B. Dillon and T. C. Waddington. J . Inorg. Nuclear Chem., 1972, 34, 1825, 1584 K. B. Dillon and P. N. Gates, J.C.S. Chem. Comm., 1972, 348. lSH5 G. J. Andriaenssens, J. L. Bjorkstam, and J. Aikins, J . Magn. Resonance, 1972, 7 , 99. lGHB R. Blink, M. Mali, J. Slak, J. StepiSnik, and S. h m e r , J . Chem. Phys., 1972, 56,

1579

1687 159n

16y9

lsuo lZu1

3566. B. R. Baker and R . M. Pearson, J . Electrochem. Sor., 1972, 119, 160. H. Graenicher, Pulsed Magn. O p f . Resonance, Proc. Ampere I t i t . Summer Sch. 2nd, 1971, 1972, 223. Z. M. El. Saffar, and P. Schultz, J . Chern. Phys., 1972, 56, 2524. 0.P. Revokatov and S. V. Parfenov, Pis'ma Zhur. eksp. i teor. Fiz., 1972, 15, 151. S. K. Garg and D. W. Davidson, Chem. Phys. Lefters, 1972, 13, 73.

1 12

S p t v .t roscopic Proper tics oj ' !no rgtoiic at id Orgatlome tullic Compo imdx

have been observed for SF, deuterioclathrate hydrate at 4.2 K and lower temperatures. By comparison with computer-simulated spectra, it was postulatcd that a distribution of correlation times exists in this system and that there is a 19Fchemical shift anisotropy of at least 100 p.p.ni.15u2 6 Group I11 Compounds

Information concerning complexes of these elements can be found at the following sources: [BH,D] - , l Z 2 (CsH5)3ThBH4,211H3BPR3,4JvO 6 (PPh,),,Ag(NCBH3),846 C O , ( C O ) ~ C O B H , N E ~ , , ~{H2B(N,C,H,),),Fe(CO),,12' ~~ B,HB,92 Me,tB,HB-n,7fi2,4-Me,C3B,H,, ( T - M ~ C , B , H , ) M ~ ( C O ) , , p~ ~ - (~( ~ C, H,)Fe(CO).)).C,B,H 7,364 BgH9,6Jy73 p-Fe(CO),B,H B9H 15,123 B, ,H ,4,u:i [(1 ,7-B9H9CHE),FeI2 -, [{ 1 ,7-B9H9CHEMo(CO),},Fe]2-,259 rr-cyclopentadienyl-n-dicarbollyl derivatives of (C5H,)CoB8C2H,,CO(C,H,),~:~~' ( P I ~ , P ) , R U H C I ( N C M ~ ) N , B , , H , S M ~[(C,H,)CO(~-B,CH,)]-,~~~ ,,~~~ (C,H,)C~(X-(~)-~,~-B,C,H~~),~~, ~ ~ . T - P ~ ( C , M ~ B , , H , , ) ,M(CH,Ph), L,,~~~ (M = B or AI),lo7 Et,BN(NO)OEt,2*G MeB(p-NMe2)2B(p-NMe,),BMe,1771i B ( ~ i n y l ) , , ~R1,B(NR2,), ~ ,,12, b o r a ~ i n e sO,4 ~ ~ B(OMe),,,17 ~ F,B,NMe,,05 [L2PtX2PtL2]2'[BX4]a-,817 Me,A1Be:3(OBut),,178 [Me,AIH,Zr(C5H,),],,20M [Me,AISCH,],, (Me,A1SPh),Ni(COD),,781 (vinyl),MNMe, (M = Al, Ga, or In),8e1 (OC)4FeC(NMe,)OAI(NMe,),.36B HfA1,(OPri),,,207 Me,TI{M(C5H5)(C0)3M}(M = Mo or W),2g5and ArTIC1,.81

Boron Hydrides and Carbaboranes.--"B N.m.r. spectroscopy has been used to show that acidic hydrolysis of [BH4]- produces [BH,OH]- and borate,lSB3 but if the hydrolysis is carried out in the presence of CN-, then some [BH,CN]- is formed.159* lH N.m.r. spectroscopy, coupled with i.r. and Raman spectroscopy, has been used to show that in Me,NNH2BH3, the BH, group is indeed attached to the NH2.1595As H F is added to Me,N,BH,, the initial 'H n.m.r. signal vanishes to give Me,N,BH,F, Me,B,HF,, Me,N,BF,, and, finally, [Me,N H ] BF,-. llB and lgF n.m.r. data were also reported.15DG The previously unreported compounds CH3SPF2,(MeS),PF, MePF,,BH,, MeSPF,,BH,, and (MeS),PF,BH, have been prepared and characterized by lH, llB, 19F, and 31Pn.m.r. spectroscopy. A series of base-displacement reactions established the base strengths towards borane as MePF, > Me,NPF, > MeOPF, > MeSPF, 2 (MeS),PF, while lJ(llB -,lP) for the fluorophosphine-borane adducts decreases in the series Me,NPF, > MeOPF, > MePF, > MeSPF, > (MeS)zPF.1597For Cl,-n(MeN),PBH,, lJ(llB-lH) and lJ(llB-,lP) increase linearly with n.159a I

M. B. Dunn and C . A . McDowell, Chetm Phys. Letters. 1972, 13, 268. F. T. Wang and W . t. Jolly, Itzorg. Chrnr., 1972, 11, 1933. Iw4 L. A. Levinc and M. M . Kreevoy, J . Arrzer. Chrni. Soc., 1972, 94, 3346. 1m9 J. R . Lhrig, S. Chatterjec, J. M . Casper, and J. D. Odom, J . Iitorg. Nuclear Chern., 1972, 34, 1805. lSQe J . M. Van Pvasschen and R. A. Cieanangel, J . Amer. Chem. SOC., 1972, 94, 2680. lm7 K. Fozstcr and K. Cohn, Inorg. Chc~trr.,1972, 11, 2590. IGnq C'. Jouany, C i . Jugic, and J.-P. Lnurent. Bit//. .Yoc. chim. France, 1972, 880.

15L'2

lLR3


113

Data have also been reported for K3NAIH3BH3,15nnL(CH2)nNMH2 (M = B, Al, or Ga),lsoo(MeO)3PBH3-,Br,,1G01R3BPF2NMe,(R = H, Me, or F),lGo2[Me3NBH20R]+[PFs],loo3 S7NBH2,1G04 Et3NBH2C6H,Me,loo5 (Et,N),BH,_,, and p-RNHB2H5.100G 'H and llB n.m.r. spectra of Me3NBH2PMe,BH, have been reported. I t is interesting that the llB n.m.r. spectrum of BH3 shows no phosphorus coupling but BH2 shows phosphorus coupling of ca. 60Hz.1607 The l l B n.1n.r. spectrum of F4P2,2BH3is a 1:3:3:1 quartet while the leF n.ni.r. spectrum is of the [AX2I2type.160* l H and l l B n.ni.r. spectra of CQB2Ho, Me,zC.,B2H6--n,1609 K[EtS(BH3)2],1610 (148), and (149) have been measured.lol1

llB and l n F n.m.r. spectroscopy have been used to characterize 2-CF3SPCF3B3H,. O n standing for two days, isomerization to the 1-isomer occurs.1612 The llB n.m.r. spectrum of Me2MB3H8(M = A1 or Ga) is temperature dependent, showing signals 2: 1 at low temperature (M = G a ) and a nine-line multiplet at room temperature. The structure is thought to be (15O).l6l3 'H and llB n.m.r. spectroscopy have been used to help characterize B-(cis-prop-] -enyl)-closo- 1,5-dicarbapentaborane(5) and [C2B3H,],.1614 The 'H n.ni.r. spectrum of AI(BH,),,NHMe, shows a dodecet for the BH, resonance, in the ratio 1 :1 :2:2:3:3:3:3:2:2: 1:1, owing to coupling to llB and 27A1with J(A1-H) z 4J(B-H).ls15 The llB n.m.r. spectrum shows a 1:2:1 triplet and 1:4:6:4:1 quintet, and structure (151) was suggested.lsls lH and llB n.m.r. spectroscopy have been used to follow the separation of (152) and (153),lo1' and the llB n.m.r. spectrum of M . Ehemann, N.Davies, and H. Noth, Z . m o r g . Chem., 1972, 389, 235. A. Storr, B. S. Thomas, and A. D. Penland, J.C.S. Daltoti, 1972, 326. l g o l G . Jugie and J. P. Laussac, Conipf. rend., 1972, 214, C , 1668. l u o p S. Flcming and R . W. Parry, Znorg. Chem., 1972, 11, 1. l a u s D. L. Reznicek and N. E. Miller, fnorg. Chem., 1972, 11, 858. I B u 4 M. H . Mendelsohn and W. L. Jolly, Iitorg. Chem., 1972, 11, 1944. l E uH. 6 C. Brown, E. Nrgishi, and J.-J. Katz, J . Aiiier. Chem. Soc., 1972, 94, 5893. l u u B L. D. Schwartz and P. C. Kellcr, J . Anier. Chem. Soc., 1972, 94, 3015. loo' L. D. Schwartz and P. C . Keller, Inorg. Chem., 1972, 11, 1931. 1 u 0 8 R. T. Paine and R. W. Parry, fnorg. CIietn., 1972, 11, 210. I u o 9 V. R. Miller and R . N.Grimes, fnorg. Chem., 1972, 11, 862. l u l u J. J . Mielcarek and P. C. Keller, J . C . S . Chetit. Comm., 1972, 1090. l H 1 l E. Negishi, P. L. Burke, and H . C. Brown, J . Amer. Chetn. SOC.,1972, 94, 7431 Iel2 I. B. Mishra and A. B. Burg, Znorg. Chein., 1972, 11, 664. I e L 3 J. J. Borlin and D. F. Grimes, J . Amer. Chem. SOC.,1972, 94, 1367. l u I 4 A. B. Burg and T. J. Reilly, Inorg. Chem., 1972, 11, 1962. l U l 6 N.Davies and M. G . H. Wallbridge, J.C.S. Duifoti, 1972, 1421. l e I 6 P. C. Keller, J . Amer. Chem. SOC., 1972, 94, 4020. I e L 7 0. T. Beachley, jun., J . Amer. Chen1. SOC.,1972, 94, 4223. I'WJ

luoo

5

114


(154) shows two llB triplets.lBls ‘H and llB n.m.r. spectroscopy have been used to assign structures to (155; X = Me,Si, Me,Ge, Me,B, or Me2ClSi),l6lgand (1 56).lezo Pyrolysis of (Me2B)2CH2yields among the products B3CSHIl,which shows two CH and three CHI groups in the ‘H n.m.r. spectrum.ls21 C2H,B,H8 reacts with PMe, to yield a solid C2H4B4H8(PMe,),. The llB n.m.r. spectrum shows four llB resonances, which is consistent with

N Me,

H

I

I Me\N/B\N

M e \ N/B,N/H

I

I

I

N /B\ H I

H’

B

N ‘’

Me, H,

I

B

I

FB\ SMt.

H ,

N-B Me, H,

‘NM~,

H

( 1 54)

( 1 53)

H I

/

HIB\

Me I

t 155) I

H

( 156)

(157).lSz2 lH and llB n.m.r. data have also been reported for silyl and germyl derivatives of C2B4Hs.1623 The lH and llB chemical shifts of XB5H8 and p-XC6H,B(OH), have been examined and linear correlations found.ls2* The llB n.ni.r. spectrum of decomposition products of [B6H8]- in solution contains resonances at lel*

leso lBZ1 loZ2 1625 1624

A . B. Burg, Inorg. Chem., 1972, 11, 2283. C. G . Savory and M . G . H. Wallbridge, J.C.S. Dalron, 1972, 918. R. N. Grimes, W. J. Rademaker, M. E. Denniston, R. F. Bryan, and P. T. Greene, J . Amer. Chem. SOC.,1972, 94, 1865. M. P. Brown, A. K. Holliday, and G. M. Way, J.C.S. Chem. Comm., 1972, 850. R. E. Bowen and C. R. Phillips, J . Znorg. Nuclear Chem., 1972, 34, 382. M . L. Thompson and R. N. Grimes, Inorg. Chem., 1972, 11, 1925. A. R. Siedel and G . M. Bodner, Inorg. Chem., 1972, 11, 3108.

Nuclear Magneiic Resonance Spectroscopy

115

/I1- BH,

Me,P BH,CH2CH,BII \

H-B,

//I] PMe,

(157)

6 - 10.3 and 36.7, which cannot be assigned to known species.160sThe product from the reaction of 1- or 2-MeB5H, and Me,N gives the same llB n.m.r. The SiH, resonance in 1-CISiH,B5Hd is a 1:1:1: 1 quartet at room temperature, but on cooling to - 8 5 "C much of this fine structure is l l B N.m.r. data have also been reported for (BH2CN),.I6** Protonation of B6H10 and 2-MeB6H, occurs on the basal boron and [BC14]- is formed.1629 Low-temperature lH and llB n.m.r. spectra of B6Hlo and 2-MeB6H, have been used to demonstrate that (a) the bridge proton exchange rate is slow on the n.m.r. time-scale, (6) the spectrum is consistent with the solid-state structure, and (c) the static structure of 2-MeB6H, is without a plane of sy1~11lletry.l~~~ SiHaC12reacts with NaC2B4H, to yield p,p'-SiHz(C2B4H,)z. The llB n.m.r. spectra show four doublets of equal area: therefore there are no boron-silicon terminal bonds. Two possible isomers, (158) or (1 59), were suggested.ls31 The 19F chemical shifts of l-(m- or -p-FC,H4)-1,6-B8C2HB or 1,10-B8C2H9have been used to calculate resonance substituent constants. Both carbaboranes had weak electron-acceptor ability.1632 Alkaline ethanolysis of 5,6-dicarba-nido-decaborane(12) produces C2H14B8. The llB n.m.r. spectrum shows three doublets in the ratio 2:4:2 and the structure (160) is suggested.1633llB N.m.r. spectroscopy has been used to characterize the low-temperature product from the reaction of NHS with n-BgH15.1R34 lH and llB n.m.r. spectra of B8H12, B8Hll(,and 2,2'-(B,H8), have been measured at 5 1.7 kG.1635 llB and 13C n.m.r, chemical shifts of a number of carbaboranes have been reported. It is found that six-co-ordinate carbon atoms are at ca. 1 30 p.p.m., five-co-ordinate carbon atoms ca. 115 p.p.m., and fourco-ordinate carbon atoms ca. 90 p.p.m. from CS2.1636The lH and llB n.m.r. 16tG

V. T. Brice, H. D. Johnson, sec., D. L. Denton, and S. G. Shore, Znorg. Chem., 1972, 11, 1135.

Kodama, J . Amer. Chem. SOC.,1972, 94, 5907. T. C. Geisler and A. D. Norman, Inorg. Chem., 1972, 11, 2549. l e Z u B. F. Spielvogel, R. F. Bratton, and C. G. Moreland, J . Amer. Chem. SOC.,1972, 94, 8597. 1 a 3 ~ H. D. Johnson, sec., V. T. Brice, G. L. Brubaker, and S. G. Shore, J . Amer. Chem. ma G.

Ian

SOC.,1972, 94, 671 1. V. T. Brice, H. D. Johnson, sec., and S. G. Shore, J.C.S. Chem. Comm., 1972, 1128. lSY1 A. Tabereaux and R. N. Grimes, J . Amer. Chem. SOC.,1972, 94, 4769.

L. I. Zakharkin, V. N. Kalinin, E. G . Rys, and B. A. Kvasov, Zzuesf. Akad. Nuuk S.S.S.R., Ser. khim., 1972, 507. lHY3 B. Stibr, J. PleSek, and S. Hefmanek, Chrm. and Id., 1972, 649. R . Schaeffer and L. G . Sneddon, Inorg. Chem., 1972, 11, 3102. lS30 K . R . Rietz, R. Schaeffer, and L. G. Sneddon, Inorg. Chem., 1972, 11, 1242. J . L. Todd, Pure Appl. Chem., 1Y72, 30, 587. 1692

116

Spectroscopic Properties of Inorganic and Organometailic Comyound.y

oBH

0 C H

O H

(158)

spectra of CsB8H14(161) are consistent with the delocalization of the bridge hydrogen atoms and one hydrogen atom from each BH2 group around the open face of the icosahedral fragment, despite the X-ray The 70.6 MHz llB n.m.r. spectrum of [(3)-1,2-B9C2H12]-shows five doublets in intensity ratio 2:3:2:1 : I , whereas [{(3)-1,2-C9B2H11}2C~]shows five doublets in the ratio 1:1:4:2:1.1638 On the basis of lH and llB n.m.r. spectroscopy, the (3)-1,7-structure has been suggested for ( I ,5-C8H,,)Ni( Me2C2BgH9).163g Reduction of 1,2-BloC2H12yields [B,,C2H,,12- and protonation yields two isomeric [BloCzH,,]- anions. For one, the llB n.m.r. spectrum shows seven doublets with an intensity ratio 1:2:1:2:1:2:1; for the other, the IlB 1637

laas

N. N. Greenwood, J . A. McGinnety, and J. D. Owen, J.C.S. Dalton, 1972, 986. A. R. Siedle, G . M. Bodner, and L. T. Todd, U . S . Nut. Tech. Inform. Serv., A D Rep., 1972, No. 735932. J. L. Spencer, M. Green, and F. G . A. Stone, J.C.S. Chem. Comm., 1972, 1178.

117

Nuclear Mcignetic Resoriarice Spectroscopy

0

5

O B H

7 ) s

@ c ( 162)

O H

11.111.r. spectrum shows six doublets with an intensity ratio 2:l:l:2:2:2.1640 The 80.5 M H z l l B n.m.r. spectrum of Rb,B,,H,, consists of doublet: c1oublet:triplct:doublet with an intensity ratio 2:4:2:2, which was considered to be consistent with 2632 t o p 0 1 o g y . l ~Data ~ ~ have also been reported for BIOCSHIU (162h [ M ~ ~ N I [ C ~ ( B Q C ~and H ~ “~~) (, IB,Q C ~ H I E M I - ’ ~ ~ ~ LK4‘1

1*342

Ci. R. Dunks, R. J. Wiersema, and M . F. Hawthorne, J.C.S. Chem. Comm., 1972, 899. W . N. Lipscomb, R . J. Wiersema, and M . F. Hawthorne, Irtorg. Chem., 1972, 11, 651. T. E. Paxson, M . K. Kaloustian, G . M . Tom, R. J . Wiersema, and M. F. Hawthorne, J . Amer. Chetn. Soc., 1972, 94, 4882.

1 18

Spcctroscopic Properties of Irtor.gnrric arid Organometnllic C'onipourttis

Hydrolysis of hexadecaborane(20) gives Bl4HL8.The llB n.m.r. spectrum shows seven doublets and six unresolved resonances in the ratio 2: 1:6:1 :1 :1 :1 :1 -'H, llB, and 13C n.m.r. data have been reported for ( 163).lsa4 The temperature dependence of the n.m.r. spectra of polymerized 1-vinyl-o-carbaborane has been examined.1a45

Other Compounds of Boron.--'H N.m.r. spectroscopy has been used to determine the stereochemistry of the ring in (164; X = NMe or O).l6.I6 For (165; R = Me) the CH, groups give a triplet of intensity 4.lR4' The 'H n.m.r. spectrum of (166; R = 2,4,6-Me,C,H2) shows that the methyl groups are different, implying restricted rotation of the boron-carbon bond.lA4*Data have also been reported for R1nB(OR2)3-n,1649-1661 Bun3B, B u ~ ~ Bun2BK, B , ~ ~B u~" *~B R , ' ~ ~ (A ~ I C H & B , ~ (167), ~ ~ ~ (168),loS6MeEtBX, Me,BCH,Y (X = NH,, NMe,, N3, OH, OMe, F, or C1; Y = PMe,, S. Hefmanek, K. Fetter, and J. PleSek, Chem. and Ind., 1972, 606. J. N. Francis, C. J. Jones, and M. F. Hawthorne, J. Anrer. Chem. Soc., 1972, 94,

4878.

m6 J. R. Wright and T. J. Kiingen, J. Inorg. Nuclear Chew., 1972, 34, 3284.

F. A . Davis, I. J. Turchi, B. E. Maryanoff, and R. 0. Hutchins,J. Org. Chern., 1972, 37, 1583. 104f R. H. Fish, J. Organometallic Chern., 1972, 42, 345. R. Van Veen and F. Bickelhaupt, J. Organometallic Chcm., 1972, 43, 241. 164* S. Korcek, G. B. Watts, and K. U. Ingold, J.C.S. Perkin f i , 1972, 242. l e o 0 I. Kronawitter and H. Noth, Chem. Ber.. 1972, 105, 2423. E. Negishi, J.-J. Katz, and H. C. Brown, J. Amer. Chem. SOC.,1972, 94, 4027. laaa A. G. Davies, B. P. Roberts, and J. C. Scaiano, J.C.S. Perkin / I , 1972, FO3. D. J. Pasto and P. W. Wojtkowski, J. Organometallic Chem., lo??, 34, 751. B. G. Ramsey and N. K. Das,J. Amer. Chem. Soc., 1972, 94, 4227. 16hh P. Jutzi, Angew. Chenr. infernat. Edn., 1972, 11, 53. 1646

1 I9

Niicfciir M q n e t i c h'esorimce Spectroscopy

AsMe,, SMe, C1, or I),1656 F2C=CHBX2,1657 (S=PF2NH),BPh,166* (C5H5)BSN3Me3,1s50 (169),1660 (170) or (171),1se1 (172),lse2 (173), (174),1663 R,SnCH,CH,B FX'B-Ph Mt

0-CMe, \ CH, \ / 0-CHMe /

( 164)

& '\

I

/

b

(172)

Li

+

\ - ' - J

SK'

J. Rathke and R. Schaeffer, Inorg. Chem., 1972, 11, 1150. J. J. Ritter, T. D. Coyle, and J. M. Bellama, J. Organometallic Chem., 1972, 42, 25. 1 R 6 8 H. W. Roesky, Cheni. Ber., 1972, 105, 1726. lRG B.9L. Therrell, jun. and E. K. Mellon, Inorg. Chem., 1972, 11, 1137. l G U oW. Kliegel, Annalen, 1972, 763, 61. T.-T. Wang and K. Niedenzu, J . Organometallic Chem., 1972, 35, 231. 1n62 J. Cueilleron and B. Frange, Bull. SOC.chim. France, 1972, 107. lRn3 A. Grote, A . Haag, and G . Hesse, Annalen, 1972, 755, 67. lflSR

lRS7

120

SpiJctros t nopic Proper t ics of It lorgar1 ic orid 0rgiinonii>t tillic Conipo rincls I

-

-

I

-I

( 1 75),lss4 adducts of C5H, nC1, and ( V ~ ~ ~ I ) B O C H , C H RBOCH,,O,~~~~ I _

1

CHgO,les6(176),lss7 [MeSeBRI],,,166H PhBX2,1RR9 and Cl,BCH,CH,BCl,.1670 B,F,, has only one 19F singlet over the temperature range - 8&0 Data have also been reported for complexes of the type (Si2F5)(SiF:%)(BF,)BPF, lR71and F3SiBF,.1672 'H N.m.r. spectroscopy has been used to show that Me,N,BF,,CI:, ,, formed from Me3N,10BF3still contained 1°B in the same amount as the starting material. It was concluded that halogen exchange occurs without breaking nitrogen-boron A direct lH and l9F n.m.r. chemical shift and integration study of BF, and BCI, complexes with a number o f aromatic nitrogen heterocycles has been completed. The chemical shifts and stability constants were discussed.'6i4 'H N.ni.r. shift data of tlic pyridine and y-picoline complexes of (MeO),B and (MeS),B have been taken as providing evidence that pn-cln bonding in the boron -sulphur bond is much weaker than p r y , , bonding in the boron-oxygen bond.1F75The llB n.m.r. shift of 32 5 4 p.p.m. for Bu",C=NBR, is consistent with three co-ordination, and the lH signal of But indicates nitrogen-boron doublebonding.1676 lH Chemical shifts of [B(O,CR),NH,], have been attributed to electron-withdrawing effects of R.16" Data have also been reported for OC7.

-

7-

B(OC2H,)3N,1s7*Me,SiNRBFN(Si Me3)2,1679( Me,Si),HN,B3F3,16H0OCH,-

CH,OBCIN RB, OCH,CH20BCIPR3,16s1 Me,N,BX,16*' and CF,CON(N Me,)B F,.1683 (RO),PBH, reacts with Br, to give (RO),PBBr,. 1J('31P--11J3) = ( CI. 280 Hz whereas (Pr'O),PBH, has 1J(31P-11B)= 80 H Z . ' ~1J(11B-:3'P) ~~ has H. C. Brown, E. Negishi, and P. L. Burke. J. Amer. Chetii. Soc., 1972, 94, 3561. G . Coindard and J. Braun, Bull. SOC.chitti. Frtrnce, 1972, 817. l R R R G. Coindard, J. Braun, and P. Cardiot, Bull. SOC. chirn. France, 1972, 8 1 I . I R R 7 W. Siebert and A. Ospici, Chent. Bet-., 1972, 105. 464. lRCR W. Siebert and A . Ospici, Chem. Ber., 1972, 105, 454. l R R 8 F. C. Nahm, E. F. Rothergy, and K. Niccfenzu, J. Orgtrrioriic~ttrlli~ Chem., 1972. 35, lRR4

IRR6

9.

M. Zeldin and A. Rosen, J. Orgntiotrietallir Chew., 1972, 34, 259. R. W. Kirk, D. L. Smith, W. Airey, and P. L. Timms. J.C.S. Drrltoii, 1972, 1392. 1 6 7 2 D. L. Smith, R. Kirk, and P. L. Timms, J.C.S. Chem. C u m t ~ i . ,1972, 295. lais B. Benton-Jones and J. M. Miller, Inurg. Nrcclenr Cheni. Letters, 1972, 8 , 485. IRi4A. Fratiello, R. E. Schuster, and M . Geisel, Inorg. Chem., 1972, 11, 11. l R i 6 R. H. Cragg, J. P. N. Husband, and P. R. Mitchell, Org. Mngri. Kesorrntic~e,1972. 4, lR70

lR71

469.

M. R. Collier, M. F. Lappert, R . Snaith. and K. Wade, J.C.S. D N / I C ) 1972, I ~ , 370. G . J. Barrett and I). T. Haworth, ltrurg. Chitii. Actn, 1972. 6 , 504. 1 R 7 8 D. Fenske and H. J. Beckcr, Chctii. Ber., 1972. 105. 2085. IKTe C i . Elter, 0. Glcmscr, and W. Hcrmg, Itiorg. Niiclrar Chrrn. Z.et/crs. 1977. 8, 1 9 1 . lRX Go . Elter, 0. Glemscr, and W. Hcrzog. C'hem. B w . , 1972, 105, 115. l R n l S. G. Shore, J. L. Crist, B. Lockman, J. R. Long, and A . D. Coon, J . C . S . Dnltuti, 1972, 1123. lRnz B. Hessctt, J. B. Leach, J. H. Morris, and P. G. Perkins, J.C.S. Drrltotr, 1977. 131. lRR3 G. Czieslik and 0. Glemser, Z.onorg. Chctn., 1972, 394, 26. l e n r T. Rectz, Inorg. Chem., 1972, 11, 650.

lRie

Niiclenr Mqqwefic Resonnitce Spectroscopy

121

also been measured for (Me2N),BER2(E = P, As, or Sb).16*, IH N.m.r. spectroscopy has been used to investigate the PH3-BX3-BY3 system and species such as H,PBCI,Br have been detected.laS6 Data have also been reported for H3P,B13.16*7 "B N.m.r. spectroscopy has been used to examine borate solutions and signals due to B(OH),, pentaborate, tetraborate, and metaborate were identified. A linear relationship was found between the Na,O to B,O:, ratio and I l B chemical shift.16**From the observation of a sharp IlB n.m.r. signal for S0,-K,B407 it was concluded that the boron is tetrahedral. I .r. spectroscopy indicates triangular co-ordination for the boron.16N9 'H, llB, and lBF n.1ii.r. spectroscopy have been used to study halogen redistribution in MeO,,BX, adducts in solution: the equilibrium is attained rapidly. A linear relationship was found between *J(llB--lBF)and the I0F chemical shift.16BoThe n.m.r. spectra of RSCl in SO2 and in the presence of BCI,, BF,, or SbF5 indicated an equilibrium involving a dimeric monocationic species.lSB1 Data have also been reported for ArCHOBF3,16B2 XnB(SCF3)3--n,16g3 and (Me,N)2COBF3.16B3 low-temperature n.m.r. Complexes of Other Group I11 Elements.-The spectrum of a mixture of Bul,AlH and Bui,AICl shows the presence of three species which are thought to be (177), (178), and (179).lsB5Data have also been reported for LiA1(C3F7)H21.16B6

For Lii[Me,MSnMe,]- (M = Al, Ga, In, or TI), it is found that ?J(llBSn-C-'H) increases with the size of M whereas 3J(119Sn-M-C-1H) is The reaction of Me,AI with PbO to in the order Al < Ga > In > give compounds such as (Me2AI),0 has been followed by lH n.m.r. The 'H n.m.r. spectrum of [R1,AICH=CHR2], shows W. Becker and H . Nijth, Chent. Ber., 1972, 105, 1962. J. E. Drake and B. Rapp, J . C . S . Dalton, 1972, 2341. l G H 7 M . Schmidt and H . H . J . Schroder, 2. iztiorg. Chrtn., 1972, 394, 290. lgnH H. D. Smith, jun. and R . J . Wiersema, Itrorg. Chem., 1972, 11, 1152. 1 6 r S S. N. Kondrat'ev and S. 1. Mel'nikova. Russ. J . Ittorg. Chem., 1972, 17, 489. IC"" M . J. Bula, D. E. Hamilton, and J. S. Hartman, J . C . S . Dalton, 1972, 1405. llbl'l G . Capozzi, V. Lucchini, and G . Modena, Cliitnica e Industria, 1972, 54, 41. 1 R U 3 M. Rabinovitz and A . Grinvald, J . Atner. Chem. Sor., 1972, 94, 2724. 18'13 A . Haas and M. Haberlein, Chem.-Ztg., 1972, 96, 412. J. S. Harltnan and G . J. Schrobilgen, Canad. J . Chem., 1972, 50, 713. I6O6 J. J. Eisch and S. G . Rhee. J . Organotnetnllic Chetn., 1972, 38, C25. l R Q 8 R. S. Dickson and G. D. Sutcliffe, Austml. J . Chetn., 1972, 25, 761. A . T. Weibel and J. P. Oliver, J . Atner. Chetn. Soc., 1972, 94, 8590. lbR8 M. Boleslawski and S. Pasynkiewicz, J . Orgnnotttetaliic Chem., 1972, 43, 81. lgX6

1 22

Spectroscopic Propertit.s of Ittorgarlic and Organometcrllic Compounds

that cther co-ordinates and breaks up the dirner.lpeeThe 'H n.m.r. spectra of R3M and R2MQ (R = Me, Et, or But; M = AI, Ga, or In; Q = anion of quinolin-8-01) have been reported. The nature of bonding of quinolin8-01 has been discussed from the shifts and coupling constants.1700 The interaction of Me3AI and acetylacetone has been investigated and the presence of Me,Al(acac)(OCMeCH=CMeOH), ~ u g g e s t e d1702 . ~ ~[Me,AI~~~ NHMe], can be separated into fractions which readily interconvert in The cyclopentadienyl resonance of TIMe(C,H,)X is a singlet even at -72 OC.1704 Data have also been reported for R,AIXSiMe,, PhMeC(OAlMe,)(NMeSiMe,),1705 R12A1NR2C02Me,1706(Me,Si),NAI,Me6,l7O791708 AIMe3(PPh3),1709[Me2Ga02PX2]2,1710 MeGa2X,,l7l1 MeIn(tetrapheny1porphyrin),l7l2 Me2InO3SMe,l7l3Me21nCI,SSbMe,,1714RlnBr2,1716Me,Tl(suc~inirnide),~~~~ [Me2T10PPh2]2,1717 Me,T1(OCOPri),-,,1718 and R(CICH2)T1X.171e The adduct formation of [Et,AI], or [Et,AICl], and Ph,P(CH,),PPh2 in benzene has been investigated by lH n.m.r. spectroscopy, and species such as (AlEt,),(diphosphine) have been In mixtures of Et,AIOEt and EtAICl,, a new species which may be [EtAICI(OEt)], is formed.1721For Ar(Me,NCS,CH,)TIX, a coupling of 7 Hz is observed over six H N.m.r. spectra of cyclohexene and AIBr, show that, as the concentration of AlBr, increases, the olefinic hydrogen moves to low field, implying formation of a complex.1723Data have also been reported for RC(0Me)(OAlEt2)(SAIEt2),1724 Et,IAI,NH Et21n(oxinate),1726 [(cyclopropyl),G . Zweifel and G. M. Clark, J. Organometallic Chem., 1972, 39, C33. B. Sen, G. L. White, and J. D. Wander, J.C.S. Dalton, 1972, 447. l i o l S. Pasynkiewicz and K. Dowbor, J. Organotiietallic Chem., 1972, 43, 75. 1702 S. Pasynkiewicz and K. Dowbor, J . Organometallic Chem., 1972, 39, C1. 1 7 0 3 K. J. Alford, K. Gosling, and J. D . Smith, J.C.S. Dalton, 1972, 2203. 1 7 0 4 T.Abe and R. Okawara, J. Organometallic Chem., 1972, 35, 27. l i o 6 T.Sakakibara, T.Hirabayashi, and Y. Ishii. J . Organometallic Chem., 1972, 46, 231. 1 7 0 6 T. Hirabayashi, T.Sakakibara, and Y. Ishii, J . Organometaiiic Chem., 1972, 35, 19. N. Wiberg, W. Baumeister, and P. Zahn, J . Organometallic Chcm., 1972, 36, 267. I7O8 N. Wiberg and W. Baumeister, J . Organometallic Chem., 1972, 36, 277. l 7 O B T. R. Durkin and E. P. Schram, Inorg. Chem., 1972, 11, 1054. l 7 l o B. Schaible and J. Weidlein, J. Organometallic Chem., 1972, 35, C7. 1711 W. Lind and I. J. Worrall, J . Organometallic Chem., 1972, 40,3 5 . 171a M. Bhatti, W.Bhatti, and E. Mast, Inorg. Nuclear Cheni. Letters, 1972, 8, 133. 1 7 1 3 H . Olapinski and J. Weidlein. J . Organometallic Chem., 1972, 35, C53. T. Maeda, G. Yoshida, and R. Okawara, J . Organometallic Chem., 1972, 44,237. 1 7 1 5 M. J . S. Gynane, L. G. Waterworth, and 1. J. Worrall, J . Orgnnometallic Chcm.. 1972, 43, 251. l i l a B. Walther and C, Rockstroh, J . Organometallic Chem., 1972, 42, 41. I 7 l 7 B. Walther, J. Organometallic Chem., 1972, 38, 237. l 7 I 8 R . Okawara, Pure Appl. Chem., 1972, 30, 499. l 7 l V T. Abe and R. Okawara, J. Organometallic Chem., 1972, 43, 117. liZo T. Kagawa and H . Hashimoto, Bull. Chem. SOC.Japan, 1972, 45, 1739. l i 2 1 A. C. L. Su and J. W. Collette, J. Organometallic Chem., 1972, 36, 177. 1722 T. Abe, S. Numata, and R. Okawara, Inorg. Nuclear Chem. Letters, 1972, 8, 909. 1723 H.-H. Perkampus and G . Prescher, 2. phys. Chem. (Frankfurt), 1972, 77, 333. 1721 T. Hirabayashi, H. Imaeda, K. Itoh, and Y. Ishii, J. Orgnnometallic Chem., 1972, 42, 33. K. Gosling and A . L. Bhuiyan, Inorg. Nuclear Chem. Letters, 1972, 8, 329. l x aT. Maeda and R. Okawara, J . Organometallic Chem., 1972, 39, 87.

lR@@

I7O0

Nirclenr Magnetic Resotmice Speclroscopy

M(NCH,CH,)],(M

123

= AlorGa),1727 RGa,Br,,1728[Tl(CH,COMe),]~3 tL)+,172g

or 3),17,0 M ~ C = C ( C M ~ , O M ~ ) T ~ ( O A Cand ),,~~~~ [phTl]2-t I 7 3 2 'H N.m.r. spectroscopy has been used to show that M{Al(OPr*),}, (M = Sc or In) has a structure similar to that of [AI(OPri),], and shows magnetic inequivalence of the methyl protons in the bridging as well as the terminal i s o p r o p ~ x y - g r o u p s1734 . ~ ~ ~A~ ~correlation has been found between the position of the C,-H signal in the 'H n.m.r. spectrum and the reactivity of AI(N=CPhCH,Me)XCI with H,C=CRCN.1735 Data have also been reported for (p-Me2NC,H,),M1(M2C1,), (M1= As or Sb; M 2 = Al, n = 4; M 2 = Sb, n = 6),17,, (2-HO-3,5-Pri2C,H,C0,),M ( M = Al, Ga, or In),1737and T1(02NPri).173* ln(C5i-15)n (tz = 1

7 Compounds of Silicon, Germanium, Tin, and Lead There have been many references to complexes of these elements in the preceding sections. The previously mentioned complexes are given here in the order of the Periodic Table. Information concerning complexes of these elements with magnesium and the transition metals can be found at the following sources : Mg{N(SiMe,),},,187 S C { N ( S ~ M ~ ~ (c5H5)2)~}~,~*~ M1Cl(M2Ph3)(M1 = Zr or Hf; M2 = Si, Ge, or Sn),lQ5Cr(CO),{Me,AsCH(SiMe3)CH2AsMe2},256(OC)5CrPPh2SnMe3,224 Me,SnSMeM(CO),(M = Cr or W),227M O ~ ( C H , S ~ M ~ , (C5H5)(0C),MSiMezX ),,~~~ (M = M o or W, IZ = 3; M = Fe, n = 2; X = Me, CI, or Br),2gS(C,H,)Mo(CO),(PPh,)(MR,) ( M = Ge or Sn),27e (C5H5)Mo(CO),LSnMe3,274(C5H5)(OC),h40SnC12SzCNMe,,277 W(CO)5MeSSnMe,,228

Me,MC(CF,)C(CF,)-

===C(CF,)C(CF,)Mn(CO), ( M = Si, Ge, or Sn),,,' Me,SnMn(C0)5,321 h4n(CO)6GeH3,326MeSiCI,HRe2(C0)g,341(C5H,)Fe(C0),MR3 (M = Si, Gc, or Sn; R = Me or Ph),l12 (Me,SiOCH=CHz)Fe(CO)4,372[Me,SiFe(COSiMe,)(CO), Fc(CO),( PMe,CHICH,Si {(C,H,)Fe(CSH4)SiMe,)2SiMe2,485 Me,CJeSiMe2C,H,FeC5H4SiMe,0SiMe,,5QB" (OC),-

1

~eC~-lzCH,CH,SiMe,,44~ Fe(C0)4(GeH3)z,440MezGeFez(CO),(C5H,),432 { (C,H,)Fe(C,H,CH,N Me,)},SnBu,,4a3 (C5H,)Ni(C0)SnC1,Fe(CO),(C5H5),445(C8H9)Ruz(CO)4(GeMez)2GeMe3,433 (C,H,),Co(CO)(Me,SiCCSiMe,),sg4 IrH2(CO)(PPh,),SnMe,,54Q(C,H,)Ni(CO)MX, (M = Ge or J . Miiller, K . Margiolis, and K. Dehnicke, J . Organometallic Chem., 1972, 46, 219. W. Lind and 1. J. Worrall, J . Organometallic Chem., 1972, 36, 35. li20 P. Abley, J. E. Byrd, and J. Halpern, J . Amer. Chem. Soc., 1972, 94, 1985. I i 3 0 J. S. Poland and D. G . Tuck, J . Organometallic Chem., 1972, 42,307. 17:11 R. K. Sharma and E. D. Martinez, J.C.S. Chent. Comm., 1972, 1129. I X S. Uemura, Y . Ikeda, and K . Ichikawa, Tetrahedron. 1972, 28, 3 0 2 5 . I x l A. Mehrotra and R . C. Mehrotra, J.C.S. C h o n . Cotrim., 1972, 189. lxi4A. Mehrotra and R . C. Mehrotra, Inorg. Chrm., 1972, 11, 2170. 1 7 ~ 1 s €-I. Hoberg and R . Kieffer, Annalen, 1972, 760, 141. L i B 6 J. M. Keck and G . Klar, 2. Nnturforsch., 1972, 27b, 596. Iia7 H.F. Eicke, V. Arnold, and F. L'Eplaitenicr, Angew. Chem. Internat. Edn., 1972, 11, 1096. A . G. LCC,Sprctroc~him.Actn, 1972, 28A, 133.

liX7

124

S p e c t rostwp i c Propert i p s o,f ' It lo rgcrnic mid Orgartome t n Nic Conipoitrids

Sn),443 ~ ~ S - P ~ ( C H , S ~ M ~ , ) , ( P R(Ph,P),PtSiF4,7ug ,),,~~~ R,PAuOS~M~,,~~" MePh,SnZnCl,sR4and Me:,Si HgCF,CFCISi Information concerning complexes of these elements with Group 1 IlB elements can be found at the following sources : SiH,(C2B4H7)2,1631 (K = H or Me; M = Si or Ge),lS2,Me,SiNRBFN(SiMe,)2,16S0 R3MC2B4H7 (Me,Si),NBF(SiMe,)NH,*680 Me,MC,Me,B,H, ( M = Si or Ge),lRlg F3SiBF2,1672 (Si,F5)(SiF,)(BF2)BPF3,1071 R,SnCH,CH,BOCMeHCH,kR,AIXSiMe,,1705[(Me,Si),N],A1,1707Li Me,SnM Me, (M = Al, Ga, In, or and (Me3Si),NAI,Me5.1708 Information concerning complexes of these elements with Group VB and VIB elements can be found at the following sources: (Me,Si),N,126 Me,SiX ( X = CN, CRF5,P{SiMe,},, e t c . ) 130 (R,M),PX,_, (M = Si, Ge, or Sn; R = H, Me, Ph, or Bu; X = H, Me, or Ph),13, SnCI,(PEt,),,H5 Me,SiO(SiMe20),SiMe,,12g Me,Si(OAc)CH2CH,CH2S0,-Nai ,R6 Si( a ~ a c ) , R , S n ,(MeO)Me,SnAr,96 ~~ B U ~ , S ~ ( O R )FC,H,OMR, ,,~~~ (M = Sn or Pb),a66Ar3Sn02CR,154(H,M),E ( M = Si or Ge; E = S, Se, or Te),14, and Me,SnS2CNMe2.g9 Information concerning other complexes of these elements can be found at the following sources: Me,SiC=CPh,s7 p-XC6H4SiMe3,g5 C6H4C2H,M Me, (M = Si or Sn),a87Me,SiCH,CHCH2~C1(C0,Me),aa8 MepSi,ll9~ 120 Me3SiCHISnMe,,as5 phenylmethylsilanes,61 phenyltetramethyldisilanes,60 alkylarylflu~rosilanes,~~~ alkylchlor~silanes,~~~ M(CH2Si (M = Sn or Pb),,13 (PhCH2),M ( M = Si or Sn),lo7 FC6H,SiXYZ,lo4 [SnH,] -,63 organotin C O ~ ~ O Umethyltin ~ ~ S , ~ * Me,SnC,H,,74 Me,SnCI ,I5, RSnC1,,167 MeSnR,,g7 EtSnX3,15, SnBut1,(C,F7),16B6 (ArCH,),,SnCI, and SnC1,.lS7 The effect of d,.-p,, interaction in organic compounds of Group IVB elements has been reviewed.1739 'H N.m.r. spectra of [GeH,]- and GeH, have been reported. The spectra were cation dependent, which was taken to indicate that there is a contact ion pair for Cs+[GeH,]- and a solvent-separated ion pair for Li+, Na+, and K+.17,0 For ArSi Me,H,_,, quantitative correlations of the chemical shifts with relative anisotropic contributions of the aromatic ring have been examined as a function of the molecular parameters, bond angles, bond lengths, and the dihedral angle. It was suggested that dn-p,. bonding may be responsible for the high-field chemical shift of the aryl and vinyl ~ i 1 a n e s . l 'H ~~~ Chemical shifts of disilanylamines are interpreted as indicating that the basicity decreases in the order Me,N > H,SiSiH,NMe, > (H,SiSiH,),NMe > (H,SiSiH,),N.1'42 'H N.m.r. spectroscopy has been 1738

Ii40

A. N. Egorochkin, N . S. Vyazankin, and S. Ya. Khorshev, Rum. Chenr. Reri., 1972,41, 425. T. Birchall and I . Drummond, I m r g . Chein., 1972, 1 1 , 250. R. J. Ouellette, J . M . Pang, and S. H . Williams, J . Organonretcillic Chrrtz., 1972, 39, 267. M . Abcdini. Qrrort. Bidl. Foc. Si-i.. Tehran Uniii., 1972, 3 , 1.

Nuclear. Magnetic Resonance Spectroscopy 125 used to investigate the mechanism of addition of Bun3SnH to acetylene~.I~4~ The effect of concentration on the chemical shifts of RaSiH has been examined.1744An equilibrium between MeCS(OSiH,) and MeCO(SSiH,) has been postulated and data have been reported for H,GeSSiMe, and related The Karplus equation has been used to determine the conformation of species such as H,SiCH2SiH,Me.174e Data have also been reported for {(H3Si)2N}2SiH,,’747 H,SiAsR,, M e , s i A ~ R , , l (GeH,~~~ CH2SiH2),0,1749 SiH30SiH2F,1750 Si3H6Me2,1751H,SiSiHBrSiH,,1752MeClSiHSiH,C1,1753 (PhHzGeGeH2)20,1754 Et,MeSiSiMe2SiMe2H,1755(indeny1)SiMe2H,175sH(SiMe2)4H,1767 (I-naphthyI)SiPhB~~~H,~~~~ (180; X = H or Me),1758(1 8 1),1760 Me2HSiC6Br5,1761 Me2SiHOCH2PEt2,Me,M(OCH,PEt,), (M = Si or Ge),1762HSi(Si F3),(Si2F,), 1, 1-(SiF4)nB2H4,1763 H Me2Si(CF2),SiMe2H,1764silacyclobutanes,1765Me3SiSilH2,1766 (GeH2)2A~Me,1767 Ph,SiHCH(OMe)Ph,1768HC1,SiR,1769and (182; R = H or Me).1770 H

K

J.-P. Quintard a n d M. Pereyre, J. Organometallic Chem., 1972, 42, 75. V. 0. Reikhsfel’d, V. B. Pukhnarevich, S. P. Sushchinskaya, and A. M. Evdokimov, Zhrrr. obshchei Khitn., 1972, 42, 163. 1746 S. Cradock, E. A . V. Ebsworth, and H. F. Jessep, J.C.S. Dalton, 1972, 359. 1746 R. J. Ouellette, D. Barton, J. Stolfo, A. Rosenblum, and P. Weber, Tetrahedron, 1972, 28, 2163. 1747 W. M. Scantlin and A. D. Norman, Inorg. Chem., 1972, 11, 3082. 174.5 J. W. Anderson and J. E. Drake, J. Inorg. Nuclear Chem., 1972, 34, 2455. 1748 C. H . Van Dyke, E. W. Kifer, and G. A. Gibbon, Inorg. Chem., 1972, 11, 408. 1760 E. W. Kifer and C. H. van Dyke, Inorg. Chem., 1972, 11, 404. 1761 P. S. Skell and P. W. Owen, J . Anrer. Cltem. Soc., 1972, 94, 5434. 1i62 T. C. Geisler. C. G . Cooper, and A. D. Norman, Inorg. Chem., 1972, 11, 1710. li63 A. J. Vanderwielen and M. A. Ring, Inorg. Chem., 1972, 11, 246. I764 P. Kiviere and J. SatgC, H d a . Chin?. Acta, 1972, 55, 1164. 1766 P. Ishikawa, T. ‘Takaoka, and M . Kumada, J. Organotnetallic Chem.. 1972, 42, 3 3 3 . 1768 P. E. Rakita a n d G . A. Taylor, Inorg. Chenr.. 1972, 11, 2136. 1757 M. Izhikawa and M . Kumada, J. Orgnnnmetallic Chctn., 1972, 42, 325. lib8 R. J. P. Corriu, G. F. Lanneau, and G. L. Royo, J. Organometallic Chern., 1972, 35, 35. 1768 M . R. Smith, jun. and H. Gilman, J. Organotnetallic Chem., 1972, 42, 1. 1700 H . Sakurai and M. Murakami, J. Amer. Chem. SOC.,1972, 94, 5080. 1761 C. F. Smith, G . J. Moore, and C. Tamborski, J. Organometallic Chem., 1972. 42, 257. 1782 C. Couret, J. Satgd, and F. Couret, Inorg. Chem., 1972, 11, 2274. 1783 D. Solan and A . B. Burg, Itiorg. Chem., 1972, 11, 1253. 1784 M. R . Smith, jun. and H. Gilman, J. Organometallic Chem., 1972, 46, 251. 1786 J. Dubac, P. Mazerolles, and B. Serres, Tetrahedron Letters, 1972, 3495. 1766 E. Hengge, G . Bauer, and H. Marketz, Z. anorg. Chem., 1972, 394, 93. 1787 J. W. Anderson and J. E. Drake, J.C.S. Dalton, 1972, 951. 17611 E. 0. Fischer a n d K. H. Dotz, J . Organometallic Chem., 1972, 36, C4. 1789 R. Nakao, T. Fukumoto, and J. Tsurugi, J. Org. Chem., 1972, 37, 4349. 1770 J. V. Scribelli and D. M . Curtis, J. Organometallic G e n t . , 1972, 40,317. li43

1714

Spectroscopic Properties of Inorganic nnd Organonietnllic Compounds

1 26

Infinite-dilution chemical shifts of Me,M(CH,),OH ( M = C, Si, or Ge) l H and 13C n.m.r. spectroscopy have been reported and have been used to determine the position of deuterium in complexes such as Me,MCMeDCHMeCHCI, (M = Si or Sn).1772The IH and lI9Sn n.m.r. spectra of R1,M(CH2),CH=CHR2 (M = Si, Ge, or Sn; R1 = Me, Et, Bun, or Ph; n = 1 or 2) have been analysed. It was suggested that the data provided no evidence of d,-p, overlap in these Data have also been reported for Me,SiCC1BrSnMe,,1774Me,S(O)=CH MMe, (M = Si or Ge), Me,Si{CH=S(0)Me,),,1776 and (183; M = Si or Ge).177G

The n.m.r. spectra of 18 silanes containing fluorine in the aliphatic and aromatic groups have been ~ e p 0 r t e d . l lH ~ ~ N.m.r. ~ Spectroscopy has beeii used to find the stereochemistry of the reaction products of Me,SiLi with alkyl halides.1778 Me3SiC=C- C=CSiMe, reacts with Na,Te to yield (184); lH n.m.r. data were (Me3Si)C3H2 can have either stereochemistry (185) or (1 86), but as the 13Csatellite of the allenic hydrogen shows a hydrogen-hydrogen coupling constant of 7 Hz, the stereochemistry is ( 1 86).17H0The n.m.r. spectra of p-triniethylsilylstyreneand its trichloroplatinic derivatives have been recorded. The chemical shifts observed for the ethylenic protons indicate that the SiMe, group exerts only a very slight electron-releasing effect on the ethylenic The 'H n.m.r. spectrum of [187; X = SiR, or Si(hal),] has been measured. The chemical shift

17'1 1772

J. D6dina, J. Schraml, and V. Chvalovsk9, Coll. Czech. Chem. Comni.. 1972, 37, 3762. D. Seyferth, Y . M . Cheng, and D. D. Traficante, J . Organometallic Cherrr., 1972, 46, 9.

177s 1774

1776 1778 1777

1778

1779 1780

R. C. Jones, P. Partington, W. J. Rennie, and R. M. G . Roberts, 1. Organoniernllic Chem., 1972, 35,291. D.Seyferth, F. M. Armbrecht, jun., R. L. Lambert, jun., and W. Tronich, J . Orgrrnometallic Chem., 1972, 44, 299. H. Schmidbaur and W. Kapp, Chem. Ber., 1972, 105, 1203. M. A, Weiner and P. Schwartz, J . Organometallic Chem., 1972, 35, 285. I. V. Romashkin, G . V. Odabashyan, V. F. Andronov, and V. A . Drozdov, Zfiur. obshchei Khim., 1972, 42, 1060. G . S. Koerner, M. L. Hall, and T. G. Traylor, J . Amer. Chem. Soc., 1972, 94, 7205. T . J. Barton and R. W. Roth, J . Organomeiallic Chem., 1972, 39, C66. P. S. Skell and P. W. Owen, J. Amer. Chem. Soc., 1972, 94, 1578. Y . Limouzin and J. C. Marie, J . Organotnetallic Chem., 1972, 39, 255.

I27


of the proton attached to carbon-3 decreases linearly with increasing Hammett (J* constant of X. The degree of &-p, conjugation between silicon and carbon was greater for SiR3 than SiC1,.1782Data have also been p-Me3SiC6H,CH(SiMe3)NPhMe,17A4 reported for Me,SiCH,(p-t~lyl),l~~~ MeSiCHPhCH,CO,Et, Et,SiCHPhCH=C(OEt)OSiMe3,17B5 Me,SiOCH-

-

=CHCHCH2CH2, C0$1787

I

I

Me,SiCH= -

MeSiCHCH,CH= CHCH20,17B*

(188),1788(189), (190),17a9 PhCH(SiMe,)EH (E I

=

0 or

S),17*0

t

SiMe,R,1791p 1782 Me3SiCHC12,17*3 Me,Si(MeO,C)CCH,CH,, R1K2C=C(OMe)OSiMe,,1794 (Me,Si),C,1795(Me,Si),CH,-,C02H,1786 Me,SiCH=CHC1,1787Ph3P=C(SiMe3)2,1788 (191),179s(192),1800(193),1801Me,SiCHMe,Si

(191)

N(SiMe,),

\ /

Me

(1 93) A. N. Egorochkin, N. S. Vyazankin, A. I. Burov, E. A. Chernyshev, V. I. Savushkina, and B. M. Tabenko, Khim. geterotsikl. Soedinenii, 1972, 911. 17Ms C. Eaborn, A. A. Najam, and D. R. M. Walton, J . Organometallic Chem., 1972, 46, 255. 1 7 ~ ‘ P. Bourgeois and N. DufFaut, J. Organometallic Chem., 1972, 35, 6 3 . 17y6 J.-P. Picard, J. Organometallic Chem., 1972, 34, 279. 17na V. Rautenstrauch, Helu. Chim. Acta, 1972, 55, 594. 1787 B. Martel and M. Varache, J. Organometallic Chem., 1972, 40, C53. 1788 A. J. Ashe, tert., J. Org. Chem., 1972, 37, 2053. 178Q C. Biran, J. Dkdier, J. Dunoguhs, R. Calas, and N. Duffaut, J. Organometallic Chem., 1972, 35, 263. 17Q0 A. Wright, D. Ling, P. Boudjouk, and R. West, J . Amer. Chem. SOC.,1972, 94, 4784. I7O1 M. Bolourtchian, P. Bourgeois, J. Dunoguks, N. Duffaut, and R. Calas, J. Organometallic Chem., 1972, 43, 139. 17** G. Miirkl and R. Fuchs, Tetrahedron Letters, 1972, 4691. 17Q3 D. R. Dimmel, C. A. Wilkie, and F. Ramon, J. Org. Chem., 1972, 37, 2662. 17Q4 C. Ainsworth, F. Chen, and Y.-N. Kuo, J. Organometallic Chem., 1972, 46, 59. l7O6 C. Chung and R. J. Lagow, J.C.S. Chem. Comm., 1972, 1078. 1796 0. W. Steward, J. S. Johnson, and C. Eaborn, J. Organometallic Chem., 1972, 46, 97. 17Q7 R. F. Cunico and E. M. Dexheimer, J. Amer. Chem. SOC.,1972, 94, 2868. 17QM H. Schmidbaur, H. Stuhler, and W. Vornberger, Chem. Ber., 1972, 105, 1084. 1700 L. Birkofer and M. Franz, Chem. Ber., 1972, 105, 1759. l S o o R. Calas, M. Bolourtchian, J. Dunogues, N. Duffaut, and €3. Barbe, J . Organometallic Chem., 1972, 34, 269. ln0* J. R. Pratt, F. H. Pinkcrton, and S. F. Thames, J. Organometallic Chem., 1972,38,29. 17ua

Spectroscopic Properties of Inorgariic arid OrganonictaNic ConlpoIlnrl.7

128

(1 94),lao2 CH,=C=CHSiMe,,

=CHSiMe,,

BrCH,C=CSiMe,,lHn3

(Ph~0,)PhC=C(SiMe,)P(0)(OEt),,1n03(1 95),lno5 ( 1 96),lgoti (Si Me%,),C6H4,lEo7 ( 1 97),lso8 (naphthy1)SiMeg,ltlo0and Me,Si(C=C'),,R (R At-, SiMe,, or H).lal0 MeOQOhk Slhle,

&-iMe,

( 194)

Q SOMe ~MCJ

SiMe,

OMe ( 195)

( 196)

(1 97)

The IH n.ni.r. spectrum of (198; M = Sn or Pb) shows only one set of methyl resonances even at -50 "C, although there should be two methyl resonances in the ratio 2:1.1811 Solvent effects have been used to distinguish I

between the cis- and trtrns-isomers of MeCHCH,CHSnMe,.1812 The reaction between Me,SnR or Ph,SnR and (SCN), appears to be quantitative, from lH n.m.r. data.1H13A n.m.r. study of a large number of mixed tetraorganotin compounds shows that the correlation between ?J(Sn-C-H) and z(Taft's a*) is invalid, even in the mixed tetra-alkyltin series. However, Malinovski's additivity rule may be used to predict tin--methyl, tin-benzyl, and tint-butyl coupling constants."14 Data have also been reported for (1 99 ; Me,M

, S y C N II

'yc,

CN

R'

CO,E1 M M c:,

D. Seyferth, H. Mcnzel, A. W. Dow. and T. C . Flood, J. Orgniior?ietollic*Chem., 1972, 44, 279.

lno3 lso6

P. Bourgeois and G . Merault, J. Orgcitiotiielallic Chetn., 1971. 39, C44. F. A . Carey and A. S. Court, J. Org. Chem., 1972, 37, 939. C. Eaborn, Z. S. Salih, and D. R. M . Walton, J. Organotnetnllic Chetn., 1972, 36, 47.

lnoa lao7 Inon

C. Eaborn, Z. S. Salih, and D. R. M. Walton, J. Orgattometallic Cheni., 1972, 36, 41. D. Seyferth and D. L. White, J. Amer. Cheni. SOC.,1972, 94, 3132. E. Heilbronner, V. Hornung, F. H. Pinkerton, and S. F. Thanies, Helii. Chini. Acfti, 1972, 55, 289.

L. Birkofer and N. Ramadan, J. Orgnnomc~tallicChem., 1972, 44, C41. D. R. M. Walton and F. Waugh, J. Organonietallic Chem., 1972, 37, 45. E. S. Bretschneider and C. W. Allen, J. Organontetallic Cheni., 1972, 38, 43. M . Grielen, P. Baekelmans, and J. Nasielski, J . Orgarionr~tcrllic Chrm., 1972, 34,

lHo9 lnlo

lnl1

329.

M. L. Bullpitt and W. Kitching, J. Organometallic Cheni., 1972, 34, 321. M. Gielen. M. De Clercq, and B. de Poorter, J . Orgnnonietullic Chetn., 1972, 34, 305.

lUl4

129

Nilclear Magnetic Resonance Spectroscopy

M = Ge, Sn, or Ph), R1R2C=CR3CH2CH(GeMe3)C02Et,1H15 and Me,GeCMe(CN)CH,PEt,.1*16 ‘H N.m.r. spectroscopy has been used to show that COzN2reacts with Me,SiSiMe, to yield MeCO,SiMe,SiMe, and not HC0,CH,SiMe,SiMe,.1817 Data have also been reported 1-naphthyl derivatives such as (1-naphthy1)Si,Me,,lHIH Me3PNSi,Me,C1,181e R,PCHSi,Me,, 1

.

Me,P=CH-SiMe,Si-

Me2CH,,1820 Me3SiSiR3,1821(200),1832RGeMe,GeMe,,1823 (201), and CI(CH2)4CH=CPhOSiMe3.1824

SiMe2SiMe3

CI-

CH,SiMe, (2ocv

(CF3)aC=C(CN)2and (CF,)(CF,CI)C=C(CN), undergo reactions with a wide variety of organometallic compounds by a 1,4-addition. lH and

19F n.m.r. data have been reported for compounds such as Me,MNCC(CN)C(CF,),SMe (M = Si or Sn) and BU”,G~NCC(CN)C(CF,),NM~,.~~~~ ‘ H N.m.r. data have also been reported for hydrazines substituted with SiMe, or GeMe3.1H2B The observation of two methyl signals for (Me,Si),NCRO or Me,SiOCR=NSiMe, could be due to either restricted rotation or fluxional inequivalence. The observation of lJ(15N-lH) = 77.5 Hz for Me,%NHCOMe provides extra evidence for the structure being Me,SiOCR=NSiMe3.1a2, The lH n.m.r. spectra of But,C=NSiMe,C1,-, show only one But signal even at low temperature. This is in contrast to But,C=NH, which shows two But signals at -60 oC.1H28lH N.m.r. spectroscopy has been used to determine the ratio of isomers for (202) and (203).1829l H N.m.r. spectroscopic investigations of the silyltriazene PhN=NN(SiMe,), show hindered rotation of the amino-group about the N-N single bond U. Shiillkopf, B. Banhidai, and H.-U. Scholz, Atitiulen, 1972, 761, 137. J . Sat& C. Couret, and J . Escudie, J . Orgarronietallic Chetn., 1972, 34, 83. 181i R . T. Conlin. P. P. Gaspar, R. H . Levin, and M . Jones, jun., J . Amer. Chetti. So(.., 1972, 94, 7165. C . G . Pitt, R . N. Carey, and E. C. Toren, jun., J . Anier. Chem. Soc., 1972, 94, 3806. l8lUI { . Schmiclbaur and W. Vornberger, Chent. Ber., 1972, 105, 3187. l N 2 0 H . Schmidbaur and W. Vornberger, Chetn. Ber., 1972, 105, 3173. I n 2 l A . Hosomi and H . Sakurai, Bull. Chern. Soc. Japan, 1972, 45, 248. 1H22 14. Sakurai, S. Tasaka, and M. Kira, J . Anier. Cheni. SOC.,1972, 94, 9285. ln2:’ K. Yamamoto and M . Kumada, J . Organornetallic Chem., 1972, 35, 297. IRZ4 K . Itoh, S. Kato, and Y . Ishii, J . Orgatiometallic Chem., 1972, 34, 293. l n Z 6E. W. Abel, J. P. Crow. and J. N. Wingfield, J.C.S. Dulton, 1972, 787. 1H2e L. K. Peterson and K. I. The, Cunud. J . Chem., 1972, 50, 553. 1827 C. H . Yoder and D. Bonelli, Inorg. Nuclear Chent. Letters, 1972, 8, 1027. l K zJ. 8 B. Farmer, R . Snaith, and K . Wade, J.C.S. Dalfon, 1972, 1501. lnZB K . Itoh, T. Katsuurn, I . Matsuda, and Y . Ishii,J. Orgarionietcillic Chetn., 1972, 34, 6 3 . 1*15

l8le

130


similar to that shown for the alkyltriazene PhN=NNMe2.1830 lH and ,lP n.m.r. data, including J(31P-31P),have been reported for compounds such as SPC12N=PC12N=PC12N= PC12NHSiMe3.1831 Data have also been 1833 Me,SiNHR, Me,SiOR,lE3' (204),1835(205),183s reported for Me3SiX,1832~ Me,Ge

\p - C f

Ph

NMe

I

0-SiMe, (202)

0-SiMe,

o=c/\

NHSiMe,

(W

/o Me3%

(203)

OSiMe,

/

H-c\

NSiMe, (205)

Me3SiNRBFB,1837 (206),1838R1N=NNR2SiMe,,lB3@Me,SiN=NN(SiMe,)]2,1842 PhNNHSiMe3,1B40 Me,SiN= S(O)= NSi Me3,1eq1 [Me2SNSiMe3 =C(OGeMe,)NMeGeMe,,1843Me,SnNR,, Me2SN(MeN,Me)2,1844 (207),1846 Me,SnNSO, and Me2Si(NS0)2.1846 The lH n.m.r. spectrum of Me,PbNCS, with 2J(207Pb-C-1H)= 79.5 Hz, is consistent with a five-co-ordinate species where the methyl group is 1830

iaai ins2

1834

183s 1836 1857

iaaa 1859

1840 1841 1841 1843

1844 184s

1.946

N. Wiberg and H. J. Pracht, Chem. Ber., 1972, 105, 1399. H. W. Roesky, Chem. Ber., 1972, 105, 1439. G. Neumann and W. P . Neumann, J. Organometallic Chem., 1972, 42, 293. S. S. Washburne, W. R. Peterson, jun., and D. A. Berman, J. Org. Chem., 1972, 37, 1738. F. Chen and C. Ainsworth, J. Amer. Chem. SOC.,1972, 94, 4037. L. Birkofer and P. Sommer, J. Organometallic Chem., 1972, 35, CIS. W. Kantlehner, W. Kugel, and H. Bredereck, Chem. Ber., 1972, 105, 2264. G. Elter, 0. Glemser, and W. Herzog, J. Organometallic Chem., 1972, 36, 257. H. P. Becker and W. P. Neumann, J. Organometallic Chem., 1972, 37, 57. N. Wiberg and H. J. Pracht, Chem. Ber., 1972, 105, 1377. N. Wiberg and W. Uhlenbrock, Chem. Ber., 1972, 105, 63. 0. Glemser, M. F. Feser, S. P. von Halasz, and J. Saran, Znorg. Nuclear Chem. Letters, 1972, 8, 321. R. Appel, I. Ruppert, and F. Knoll, Chem. Ber., 1972, 105, 2492. K. Itoh, I. Matsuda, T. Katsuura, S. Kato, and Y. Ishii, J. Organometallic Chem., 1972, 34, 75. J. Hollaender, W. P. Neumann, and G. Alester, Chem. Ber., 1972, 105, 1540. S. Kozima, T. Itano, N. Mihara, K. Sisido, and T. Isida, J. Organometallic Chem., 1972, 44, 117. D. A. Armitage and A. W. Sinden, J. Organometallic Chem., 1972, 44, C43.

Nirclear Magnetic Resoiiaiice Spectroscopy

131

equatorial and the NCS and solvent are axial.lSd7 For the compounds Me,MPHPh (M = C, Si, Ge, or Sn), the magnitude of lJ(BIP-lH) has been explained using the Fermi contact e q ~ a t i 0 n . l ~ ~ ~ 'H and 29Sichemical shifts in Me,Si(O,CR),-, correlate linearly with the electron-withdrawing ability of the carboxylate. The results were explained without invoking p,-d, bonding.1849If OH groups in organic compounds are converted into Me,SiO groups they can be very readily determined by IH n.m.r. ~ p e c t r o ~ c o p yThis . ~ ~ method ~~ is suitable to detect eluates collected using g.l.c.lS5' If flavanoids are converted into SiMe, ethers and the 'H n.m.r. spectra measured in CCI, or CeHe, both the Me0 and Me,Si groups show diagnostic benzene-induced The shifts and coupling constants of the anomeric protons of 30 pertrimethylsilyloligosaccharideshave been measured and a method has been presented for the determination of the configuration of the glycosidic bond in oligoThe 13Cchemical shifts of compounds such as (norborny1)OSiMe, are useful in conformational Correlation of the chemical shift, 8, of the silicon-attached methyl groups in p-XC6H,0SiMe, with the resonance constants OR was unsatisfactory, but the equation

8

= 15.18

+ 4.270~

was MOSiMe, (M = Li, Na, or K) forms 1:l complexes (tetramers) with Me3P0.1M56Data have also been reported for Me,SiOR,1*57-18e3Me,SiO(sugar),lBs4 R1R2C=C(OSiMe3)2,18e5Me,Si( p o l y p h e n o l ~ ) , ~(208),lae7 ~~~ EtCH=CHC(OSi Me3)=CHEt,lBs8 Me,% N. Bertazzi, G. Alonzo, A. Silvestri, and G. Consiglio, J. Organornetallic Chem., 1972, 37, 28 1. P. G. Harrison, S. E. Ulrich, and J. J. Zuckerman, Inorg. Chem., 1972, 1 1 , 25. lXo0 W. McFarlane and J. M. Sealy, J.C.S. Perkin I I , 1972, 1561. lBL A. 0 Hase and T. Hase, Analyst, 1972, 97, 998. lSG1 G. M. Bebault, J. M. Berry, G. G. S. Dutton, and K. B. Gibney, Analyt. Letters, 1972, 5, 413. lnL9 E. Rodriguez, N. J. Carman, and T. J. Mabry, Phytochemistry, 1972, 11, 409. lUh3 J. P. Kamerling, M.J. A. de Bie, and J. F. G. Vliegenthart, Tetrahedron, 1972, 28, 3037. lnG4 H.-J. Schneider, J. Amer. Chem. SOC.,1972, 94, 3636. 1n56 A. P. Kreshkov, V. F. Andronov, and V. A. Drozdov, Zhur.fiz. Khim., 1972,46,992. lWKo H. Schmidbaur and J. Adlkofer, Chem. Ber., 1972, 105, 1956. l n G 7G. G. S. Dutton, N. Funnell, and K. B. Gibney, Canad. J. Chenr., 1972, 50, 39 3. l n S B H . R. Kricheldorf, Chem. Ber., 1972, 105, 3958. 1158 P. Bajaj, R. C. Mehrotra, J. C. Maire, and R. Ouaki, J . Organometallic Chem., 972, 40, 301. l n U oT. Murakawa, K. Fujii, S. Murai, and S . Tsutsumi, Bull. Chem. Soc. Japan, 972, 45, 2520. A. P. Kurtz and C. R. Dawson, J. Org. Chem., 1972, 37,2767. H. R. Kricheldorf, Annalen, 1972, 763, 17. lXo3 G. Neumann and W. P. Neumann, J . Organometallic Chem., 1972, 42, 277. lHa4 J. Lehmann and H. Schafer, Chem. Ber., 1972, 105, 3503. lna5 C. Ainsworth and Y.-N. Kup, J. Organometallic Chent., 1972, 46, 73. l X eA a. Sato, T. Kitamura, and T. Higuchi, Mokuzai Gakkaishi, 1972, 18, 253. lnE7 P. Cazeau and F. Frainnet, Bull. SOC.chim. France, 1972, 1658. 1n6H K. Ruhlmann, B. Fichte, T. Kiriakidis, C. Michael, G. Michael, and E.Grundemann, J. Organornetallic Cheni., 1972, 34, 41. 1H47

ln4"

132


ON02,1869(209),1870Me3SiOCHPhSiR1R2R3,1871 F2PE1E2SiMe,(El, E2 = 0 or S),lB7,Me,MOCOCH,CH,COPEt, (M = Si, Ge, or Sn),ln7,Me,NNHCE,MMe, ( M = Si or Ge; E = 0 or S),la7, Me,Pb(NO,), ll, 1 H7 6 and

(208)

(209)

(4-R1C6H4)2C(OSnR23)C(OSnR23)(C6H4R3-4)2.1876 13CN.m.r. spectroscopy

has been used to assess the charge distribution in PhSMMe, (M = C , Si, Ge, Sn, or Pb) and compared with ESCA measurements on the sulphur. A linear correlation was found between the ESCA data and the 13C-S chemical shift.1877lH N.m.r. spectroscopy has been used to show that Me,SnSCH,CO,SnMe, slowly disproportionates to give Me,Sn and Me,Sn(SCH,C0,)2.1878 lH N.m.r. data have also been reported for PhC(O)SeMMe, (M = Ge or Sn).1879 lH N.m.r. data for R,SnX,-, (R = Me or Et; X = halogen) have been measured. J(Sn-H) correlates with the electronegativity of the substituents. The Fermi contact mechanism was assumed and a correlation with tin s-character was drawn.lH80 lH and 29Si n.m.r. spectroscopy have been used to demonstrate the stereochemistry of (210) and related compounds.18a113C and 29Sin.m.r. spectra, including 1J(13C-29Si), have been reported for (21 1).1882Data have also been reported for (212; M = Si, Ge, Sn, or Pb; R = Me or Ph),18HY Me(Ph)(l-naphthyl)SiR,f884s188G (213; X = H, C1, or Me),1X86(214),lHE7 (215),18*8 (21 6),1889 Me(Ph)( l-naphthyl)SiCHX2,18go(217),lng1 (21 8),lHg2 L. Birkofer and M. Franz, Chem. Ber., 1972, 105, 470. J. J. Bloomfield, R. A. Martin, and J. M. Nelke, J.C.S. Chem. Cotnm., 1972, 96. ln71 H . Watanabe, T. Kogure, and Y. Nagdi, J. Organometallic Chem., 1972, 43, 285. In7* R. G . Cavell, R. D. Leary, and A. J. Tomlinson, Inorg. Chem., 1972, 11, 2573. 1n78 C. Couret, J. Escudie, and J. Satge, Rec. Tral;. chirn., 1972, 91, 429. L. K. Peterson and K. I. The, Canad. J. Chem., 1972, 50, 562. l n i 6 K. C. Williams and D. W. Imhoff, J. Orgnriornetallic Chenr., 1972, 42, 107. ln70 H . Hillgiirtner, B. Schroeder, and W. P. Neumann, J. Orgnnometallic Chem., 1972, 42, C83. I n i 7 S. Pignatoro, L. Lunazzi, C. A. Boicelli, R. I l i Marino, A. Ricci, A. Mangini, and lno9

R. Danieli, Tetrahedron Letters, 1972, 5341. M. Wada, S.-I. Sato, M. Aritomi, M. Harakawa, and R. Okawara, J. Orgrinotnetullic Chem., 1972, 39, 99. lniU H. Ishihara and S. Kato, Tetrahedron Letters, 1972, 3751. 1n80 G . Barbieri and F. Taddei, J.C.S. Perhin 11, 1972, 1327. lHR G. 1 Fritz and M. Hiihnke, Z.arrorg. Chem., 1972, 390, 137. InR2 R. L. Lambert,jun. and D. Seyferth, J. Amer. Chem. Soc., 1972, 94, 9246. I n n s J. Y . Corey, M. Dueber, and M. Malaidza, J. Organometallic Chem., 1972, 36, 49. l X n 4 R. J. P. Corriu and J. P. R. Masse, J. Organometallic Chem., 1972, 34, 221. Inns R . J. P. Corriu and G. Royo, Bull. Sue. chin?. France, 1972, 1497. lnno L. Birkofer a n d H. Haddad, Chem. Ber., 1972, 105, 2101. Ina7 R . A. Felix and W. P. Weber, J. Org. Chem., 1972, 37, 2323. laan C. L. Frye and J. M. Klosowski, J. Amer. Chem. SOC.,1972, 94, 7186. 18n9 T. J. Barton, J. L. Witiak, and C. L. McIntosh, J. Amer. Chem. Soc., 1972, 94, 6229. l a g o L. H. Sommer, L. A. Ulland, and G. A. Parker, J. Amer. Chem. SOC., 1972, 94, 3469. Ing1 W. Adcock, S. Q. A. Rizvi, and W. Kitching, J. Amer. Chem. SOC.,1972, 94, 3657. lngz T. J. Barton, A. J. Nelson, and J. Clardy, J. Org. Chem., 1972, 37, 895.

Inin

133

Nirclcar Magnetic Resonance Spectroscopy 1

I

Me,SiCH,SiMe,CH= CHSiMe,CH, and 44 related C O M ~ O U ~ ~ S(2,1 ~9)* (including 2RSin.m.r. data) and related C O M ~ O U ~ (220),189fi ~ S , ~ ~ ~Me,Si~ (CHBSiMeHCH2)2SiMe2,1896MeSi(CH,SiMe,),CH,1807 and Me(Ph)(1 -naphthyI)gernia~ie.~*~~ Mc,

-

Me,

Mc,

fSI Y si’iSiMe,

Me,Si -7i

~ ~

\

/

M

MC

Me 1

Me,,

OR‘

R2

R3

R1

Me,

G . Fritz and M. Hahnke, Z . atiurg. Chem., 1972, 390, 104. G . Fritz and M . HAmke, 2. anorg. Chetn., 1972, 390 ,157. I H g 5 H . Okinoshima, K . Yamamoto, and M. Kumada, J . Amer. Chem. Soc., 1972. 94, 9263. 1306 G . Fritz and M. HBhnke, Z.anorg. Cheni., 1972, 390, 185. lHR7 G. Fritz and M. Hghnke, Z . anurg. Chem., 1972, 390, 191. l R e 8 R. 5. P. Corriu and J. I. E. Moreau, J. Organornetallic Chem., 1972, 40, 55.

lWRj

lHg4

I 34

Spectroscopic Properties of Iirorganic and Organornetallic Conipoiiiicls

The 'H n.m.r. spectra of some vinyl derivatives of germanium, e.g. Me,Ge(C,H,),, have been analysed using LAOCN3.'s99 The 'H n.m.r. spectrum of (1 -naphthyl)(Ph)Sn(Me)CH(Me)C=CH shows the presence of two species in ~ o l u t i o n .The ~~~ inequivalence ~ of the methyl groups in RMe,SnCHMeY has been examined as a function of R, solvent, and t e m p e r a t ~ r e . ' ~ ~Data ' have also been reported for (221),lDo2(222),leoa Me,,Ge,,1n04

(EtO)zSi(CH,)3NSiMe,(OEt),190~ MeRSi(NSiRMeCI),I

1

SiMeR,lQosMe,SiXSiMe,NPrSi Me,SiMe,NPrSiMe,X (X = NMe or O),lQo7 ~ ~ (223), Me,S(=NSnMe,),, and [ - N N = S M ~ , = N - S ~ M ~ , - ] ] , . ~ ~For

2J(Pb-C-H) = 177 Hz, which is the highest such coupling reported for a Me2Pb"' group.1DoQ 'H N.m.r. spectroscopy has been used to analyse the cyclotetrasiloxanes formed from treatment of cis- or trans-Me,Ph,Si,O, with KOH.lnlo TI Measurements have been carried out on polysiloxanes and related to the effect of substituents on segmental motion.1911 For Me,SnClO,CR, 2J(119Sn-C-1H) is cn. 75 Hz in CHCI,, indicating five co-ordination, and l'ue

R. C. Job and M . D. Curtis, Inorg. Nirclear Chem. Letters, 1972, 8, 251.

A . Jean and M. Lequan, J. Organonietallic Chem., 1972, 36, C9. M . Gielen, M. R. Barthels, M. de Clercq, C. Dehouck, and G. Mayence, J. Orgcinometallic Chem., 1972, 34, 315. D. N . Roark a n d G. J. D. Peddle, J. Amer. Chem. Soc., 1972, 94, 5837. lUo3 R. West and A. Indriksons, J. Amer. Chem. Soc., 1972, 94, 6110. l U oE. 4 Carberry. B. D. Dombek, and S. C. Cohen, J. OrganometaNic Chrtn., 1072, 36, 61. 1"u5 T.-T. Tsai and C. J. Marshall, jun., J. Orgnnornetallic Chem., 1972, 37, 5%. lRo8 L. W. Breed and J. C. Wiley, jun., Znorg. Chem., 1972, 11, 1634. l R oU 7. Wailnagat and S. Meier, %. anorg. Chem., 1972, 392, 179. lnon D. Hanssgcn and R. Appel, Chem. Ber., 1972, 105, 3271. l R o QF. Di Bianco, E. Rivarola. G . C. Stocco, and R. Barbieri, %. crrrorg. Chem., 1972, 387, 126. l a l o D. Harber, A . Holt, and A. W. P. Jarvie, J. Organornetallic Chenr., 1972, 38, 255. l a l l J. A. Barrie, M. J. Fredrickson, and R. Sheppard, Polymer, 1972, 13, 431. leoU

leol

Nuclear Magnetic Resonance Spectroscopy 135 is co. 90 Hz in (CD&CO, indicating six c o - o r d i n a t i ~ n .The ~ ~ ~observation ~ of 132 Hz for 2J(Pb-C-H) in Me2Pb(OMe), has been taken as evidence for octahedral co-ordination, whereas 93.5 Hz for ,J(PbCH) in Me,Pb(OBut), indicates tetrahedral c o - o r d i n a t i ~ n . ~For ~ ~ ~ Me,Pb(acac),, 2J(PbCH) is larger than for Me,Pb. This has been attributed to the accommodation of some positive charge on the central lead afom.lgl4 Data have also been reported for (NCCH2CH2SiMe2)20,1g16 PhEtCHOSi MeCl,, lgl6 (RO)MeSi( CH 2)2CHMe,m7 Me(N,)SnOSn Me20Me,1g18and (224; R = Me or Ph).lgl* The lH n.m.r. spectrum of (225) in liquid SO2 is sharp but in CDCI, it vanishes and this has been attributed to radical formation.1g20The lH n.m.r. spectrum of (226) shows two methyl resonances at room temperature, owing to restricted rotation about the carbon-nitrogen bond.1e21 Data

rn

have also been reported for C12SiCH2CH2CH2 m2 and (227).IB2, MeHN,

C

,NHMe

II

0

0

II

/ c , NHMe MeHN

C. S.-C. Wang and J. M. Shreeve, J. Organometallic Chem., 1972, 38, 287. R. J. Puddephatt and G. H. Thistlethwaite, J.C.S. Dalton, 1972, 570. M. Aritomi, Y. Kawasaki, and R. Okawara, Inorg. Nuclear Chem. Letters, 1972, 8, 69. l0l6 E. S. Brown, E. A. Rick, and F. D. Mendicino, J. Organometallic Chem., 1972, 38, 37. l o l a K . Yamamoto, T. Hayashi, and M. Kumada, J. Organometallic Chem., 1972, 46, C65. lU1’ J. Dubac, P. Mazerolles, and B. Serres, Tetrahedron Letters, 1972, 525. l P l 8 H. Matsuda, F. Mori, A. Kashiwa, S. Matsuda, N. Kasai, and K . Jitsumori, J. Organometallic Chem., 1972, 34, 341. 1919 R . H. Abu-Samn and H. Latscha, Chem.-Ztg., 1972, 96, 222. l e Z o Y. Takaya, G. Matsubayashi, and T. Tanaka, Inorg. Chim. Acta, 1972, 6, 339. lg21 K. Tanaka and T. Tanaka, Bull. Chem. SOC.Japan, 1972, 45, 489. lUz5 R. Damrauer, R. A. Davis, M. T . Burke, R. A . Karn, and G. T. Goodman, J. Organometallic Chem., 1972, 43, 121. loZs N. M. Sergeyev, G. I. Avramenko, V. A . Korenevsky, and Yu. A. Ustynyuk, Org. Magti. Resonance, 1972, 4, 39.

lola

l9lS

1 36

Spectroscopic Properties of hiorganic und Organometallic C'ompouncls

The 'H chcmical shifts of Et,M (M = Si, Ge, or Sn) in 13 solvents have been reported and found similar to those reported for Et,Hg. The effccts did not correlate with electronegativity.1922'I9F Chemical shifts have been reported for (F-aryl)CH,MPh, ( M = Si, Ge, Sn, or Pb): i t was concludcd that hyperconjugation The n.ni.r. spectra of Ph,MX ( M = C , Si, Ge, Sn, or Pb; X = Ph, vinyl, or N3) have been fully analysed. An electronegativity order was proposed using nteta coupling constants.1u2" The acceptor properties of some alkynyl-lead compounds have bccn investigated by 'H n.m.r. spectroscopy. 4J(MeC==CPb) appears to reflect qualitatively the s-character of the lead-carbon bond. The coupling constant decreases when another ligand c o - ~ r d i n a t e s . The ~ ~ ~lH ~ n.ni.r. spectra of (228) and (229) (X = 0 or S ) have been measured and the coupling constants derived. The relative signs of the long-range J(Pb--H ) appear to be the same and are thought to arise from the Fernii contact

I

m e c h a n i ~ n i . Data ~ ~ ~ ~have also been reported for R1R2MCH,S(0)CH2-

CH,kH, ( M = C, Si, or Ge),1929(230),1930[Ph3SiCH,CH(Me)-]l,,'!1:i1

(228) (229) (230) Et3SiC=CC=CH,lg3?p-Et3Ge(CH2)2C,H4COMe,1g33 R3GeCH= CH Ph,'O:;* Et3GeCHFCF3,1g35Ph3SnCH2CH,CH,Cl,1936and (ne0phy1)~PhSn.l~~~ The 'H n.ni.r. spectra of p-substituted phenoxysilanes and phenoxygermanes have been interpreted as showing that in these compounds thc silicon-oxygen bond has more pn-dn character than the germanium-oxygen bond, but that pn-clv bonding is not negligible in phenoxygermanes.15':'H A melt of Et3SnOH shows resonances due to (Et,Sn),O and H,O. Thc same happens on other attempts to observe the lH n.m.r. spectrum of V. S. Petrosyan, N. S. Yashina, and 0. A . Reutov, Izcest. Ahnd. Narrh S .S .S .R . , Ser. hhitn., 1972, 5, 1018. leal W. Kitching, A. J. Smith, W. Adcock, and S. Q. A. Rizvi, J . Organometallic Chot,i, 1972, 42, 373. leZ6 P. N. Preston, L. H. Sutcliffe, and B. Taylor, Spectrochim. Acta, 1972, 28A, 197. l e Z 7 R . J . Puddephatt and G . H. Thistlethwaite, J. Organometallic Chcm., 1972, 40, 141. lgZ8 G . Barbieri and F. Taddei, J.C.S. Perkin I I , 1972, 262. lnZe J. Dubac, P. Mazerolles, M. Joly, W. Kitching, C. W. Fong, and W. H . Atwcll, J . Organometallic Chem., 1972, 34, 17. l e 3 0 R . Corriu and J . Masse, J . Organometallic Chon.. 1972, 35, 51. A . W. P. Jarvie, A . J . Bourne, and R . J . Rowley, J . Orgnnometallic Chem., 1972, 39. 0.i. 1e32 R. Eastmond, T. R. Johnson, and D. R. M . Walton, Tetrahedron, 1972, 28, 4601. 1033 P. Mazerolles and H . Coussc. Bull. SOC.chiin. France, 1972, 1361. l e S p R . J. P. Corriu and J. J . E. Moreau, J . Orgnnomefallic Chetn., 1972, 40,73. l B 3 & B. I . Petrov, 0. A . Kruglaya, N. S. Vyazankin, B. I . Martynov, S. R. Sterlin, ;ind B. L. Dyatkin, J . Organometallic Chent., 1972, 34, 299. l B 3 O M. Gielen and J. Topart, Bull. SOC.chim. helges, 1971, 80, 655. lg3' H.-J. Giitze, Chem. Ber., 1972, 105, 1775. 1038 J. R. Chipperfield, D. F. Ewing, and G . E. Gould, J. Organortietallic Chem., 1072. 46, 263. lgZ4

137

Nuclear Mrignctic Resoniritce Spectrosrop-v

Et3SnOH.1Q3BData have also been reported for ArN= "(SIR,),, l!'lll Ph:,SnNCNSnPh,,1Q41 (PhCH,)(Ph,C)NCNSnBrph,,'B12 Ph,Si(OMc)C H ,D,l B 4 R,Ge 0N Ph( CH Ph), Et ,GeO ,SA r , B uilgSn 0C R R 2N= CPh2,1046 ( t ~ ~ y l ) , S n O , S A rand , ~ ~ArPb(0,CMe),.194H ~~ From 'H n.m.r. investigations it has been concluded that SiF, rcacts with allene to yield H,C=C=CHSiF,SiF,CH,CH=CH, and HC=CCH,Si F2CH2CH=CH2.1g4* The I*F i1.m.r. spectra of CF3CF2SiF,Xare second order and have been coniputer The X-ray structure of (23 I) shows that for (a) the F-Si-F angle is 106.1" and ?J(F-F) is 56 H z a nd for (b) the F-Si- F angle is 104" and ,J(F- F) is 31 Hz. Therefore there is no simple relationship between J ( F F) and bond angle.1Qs1The i1.m.r. spectrum of (C,H,)SnX shows no tin coupling. I t was thereforc suggested

c, c-:;; SiF,

1

~i~,(a) (23 I )

SiF2

(232)

that there is rapid cyclopentadienyl The neophyl nlethylene resonance in Bu"Ph(neophy1)SnI is AB with tin satellites J(Sn-lH) = 55 and 35 Hz. Hence the correlation between ,J(Sn-'H) and percentagc s-character is i i i a c c ~ r a t e .Data ~ ~ ~ ~have also been reported for (232),1054 !diF,SiF,CH,CH= CHkH,,lgS5PhSi MeX,,1s56( F,SiCH,),Si F2,1Q57 p-CI:,Si( CH2)3C6H4CH2C1,1BsH and f l u o r o ~ i n y l s i l a n e s . ~ ~ ~ ~ J. M . Brown, A. C. Chapman, R. Harper, D. J. Mowthorpe, A . G. Davies, anti P. J.

Smith, J.C.S. Dalton, 1972, 338. N. Wiberg and H. J. Pracht, J. Orgnnornetcillic Chern., 1972, 40, 289. R. A. Cardona and E. J. Kupchik, J . Organotiretallic Chent., 1972, 34, 129. R. A. Cardona and E. J. Kupchik, J. Organornetcrllic~Chetn., 1972, 43, 163. P. Boudjouk, J. R. Roberts, C. M. Golino, and L. H. Somrncr, J . Ariirr. C ' h c / i ~ .S n c . , 1972, 94, 7926. J . Satge, M . Lesbre, P. Riviere, and S. Richelme, J. Orgtinornetnllic- Chein., 1972, 34, C18.

E. Lindner and K. Schardt, J . Orgnriornetallic- Chctn., 1972, 44, 1 1 1. P. G . Harrison, J.C.S. Perkin I, 1972, 130. U . Kunze, E. Lindnrr. and J. Koola, J. Orgnrrornctmllic Chent., 1972. 40, 327. D. de VOS and J. Wolters, J . Orgrirrometnllir Chetn., 1972, 39, C63. C. S. Liu and J . C. Thompson, J . Organornetrillic~Clrcni.. 1972, 38, 240. K . G . Sharp and T. D. Coyle. Inorg. Chem., 1972, I f , 1259. C. S. Liu, S. C. Nyburg, J. T. Szymanski, and J . C. Thompson, J.C.S. DnltoJi. 1972, 1129. K. D. Bos, E. J. Bulten, and J. G. Noltcs, J . Or,rrcinotiretnllir C ' h e m . , 1972, 39, CS2. C. E. Molloway, S . A . Kandil, and I. M. Wnlkcr. J . Atiier. Choir. Sot., IQ73, 93. 4027. C. S. Liu, J. I-. Margrave, J . C. Thompson. a n d P. L. 'T'immc, Ctiitcrtl. J . Chc/)r..1072, 50, 459. J. C. Thompson and J. L. Margrave, 1nor.g. Clict)r., 1072, 11, 913. P. Hencsei. J . Reffy, 0. Mestyanek, T. Veszpremi. and J. N a g y . Periorlicw Po!\'tc,c,h.. 1972, 16, 101. G. Fritz, M . Berndt, and R. Huber, Z . arrorg. Chctir.. 1972, 391, 219. W. Pnrr and K . Grohmann. Angew). Cheni. Ititernat. Edtr., 1972, 11, 314. A . Orlando. c'. S. Liu. and J. C. Thompson, J. Flirorine Chctn., 1972. 2 , 103.

1 30

Spectroscopic Properties of Inorganic atid Organonretullic Compoirnds

A solution of SnCl, in Me,NCHO shows 'H n.m.r. signals for bound and free Me,NCHO, and the formation of [SnCl,( Me,NCHO)]+ and [Sn,CI,,]has been suggested.leao Data have also been reported for (Et,N),SnCI,,2HCl,1e61[ S n ( a c a ~ ) X , ] - ,(~B~u~~ O ) , S ~ ( S Hand ) ~ , ~[Sn(S2CsH3Me),I2~~~ 8 Compounds of Group V Information concerning complexes of these elements can be found at the 135 (Me0)2PH0,135p ASH,,^, Cr(cO),( Me,Asfollowing sources : P4,1349 m m C= CCF,CF,AsMe,), M,(CO),( Me,AsC= CCF,CF,AsMe,) ( M = M n or Re),257 Cr(CO)4(Me2AsCR1R2CR3R4AsMe,),156 {M(CO),},L [M = Cr, Mo, or W; L = (Me,Sb),CH, or (Ph,Sb),CH2],225 (C6H5)Mo(CO),(EPh,)SnMe, (E = As or Sb),274(C,H,)Mo(CO),(CN)(Me,AsCH,CM=CH2),27R(OC),WEMe,XEMe,W(CO), (E = P or As; X = 0, S, NMe, or PPh),312 Fe3(CO)6(Ph2AsC2CF3)2(P(OMe),},,460 RuCI,(CO),(Ph,AsCH2Ph2),,"0 RhX{As(o-~inyl-C~H,)~),8U~ R X ( A S P ~ ) , ( R N C ) , ~lrI3,~~ (AsP~,),(S,COE~),~~~ IrH,X{(p-t~lyl)NC)(AsPh,),,~~~ trans-PtCI(0,SPh)(ASE~,),,~ ~~ P~(AsP~,),(O,CCF,)(CR=CRCR=CRH),~~~ (Me,N),BEEt, (E = As or Sb),laS5 HN,, R,AS(N,),I~~[N,P,M~,]+[MO(CO),I]-,~~~ ( a c a ~ ) R ~ S b ,R,lnX,5SbMe,,1714 ~~ Me,BCH2A~Me,,1e5s H , S ~ A S R , , ~ ~ ~ ~ R , G ~ A S M ~ , , ~ ~[F,P~PN=SN(~OS~~)M~,]+,~~~~ ~' S=PC12N= PC12N=PC12N=PCI,NHSiMeS,1831 PBr3,l3'*165 and [Et4N]+[E(S2CeH3Me),] (E = As, Sb, or Bi).Iea4 The use of spectroscopic techniques to investigate phosphorus-fluorine chalcogen compounds has been reviewed.1s65A review on recent advances in phosphonitrilic chemistry contains a survey of the use of 19F and n.m.r. spectroscopy to investigate these systems.106s+ Iga7 The application of high-resolution n.m.r. spectroscopy to phosphorus compounds loasand the structure determination of nitrogen compounds with the aid of n.q.r., n,m.r., and ESCA have been reviewed.lg6O On The 13Cn.m.r. spectra of R1,PCH=CR2R3 have been dilution, the IH n.m.r. spectrum of R4P2 broadens: the presencc of aggregates was 'H N.1n.r. spectroscopy has been used to show that in CF,C02H, (233) protonates in the 5 - p o ~ i t i o n .The ~ ~ ~l3C' ~ n.rn,r. spectrum of Ph,Sb showed three resonances, but the carbon attached W. G. Movius, J . Inorg. Nuclear Chem., 1972, 34, 3571. G. E. Manoussakis and J. A. Tossidis, J . Inorg. Nuclear Chem., 1972, 34, 2449. lw2 D. W. Thompson, J. F. Lefelhocz, and K. S. Wong, Znorg. Chem., 1972, 11, 1139. 1963 W. Wojnowski and M . Wojnowska, Z . anorg. Chem., 1972, 389, 302. lDo4 E. Gagliardi and A. Durst, Monatsh., 1972, 103, 292. l g e 0 H.-G. Horn, Chem.-Ztg., 1972, 96, 666. 1e66 H. R. Allcock, Chem. Reu., 1972, 72, 315. Io6' D. €3. Denney, Analyt. Chem. Phosphorus Compounds, 1972, 61 1. I 9 w J . R. Van Wazer and T. Glonek, Analyt. Chem. Phosphorus Compounds, 1972, 1 5 1 . logo H. G. Fitzky, D. Wendisch, and R. Holm, Angew. Chem. Internat. Edn., 1972, 11, 979. M.-P. Simonnin, R.-M. Lequan, and F. W. Wehrli, Tetrahedron Letters, 1972, 1559. I g i 1 H. C. E. McFarlane and W. McFarlane, J.C.S. Chem. Comm., 1972, 1189. lgiz D. Lloyd and M . I. C. Singer, Tetmhedron, 1972, 28, 353. lgeo

lS6l

Nuclear Magnetic Resonance Spectroscopy 139 to antimony was not detected. The 'H n.ii1.r. spectrum of (3,4,5-trideuteriophenyl),Sb showed only a single resonance down to - 142 "C, although there was significant broadening below - 1 0 0 0C.1873A general correlation has been found between chemical shift, electronegativity, and the principal quantum number of the valence electron for ( P - M ~ ~ N C ~ H ~(M ) ~= M P, X~ As, or Sb).1g74Data have also been reported for Me,POMe,1876Me,PF,1B76 [PhCH2(NH2)P(CaH4)2P(NH2)CH2Ph]2+C1-2,1D77 [PRF],,,'~~~(234),lD7'

'"'-6; Ph

Ph

AsPh,

i'h

phnph Ph

(233) (234)

As

(235)

Ph

Pll-

AS I

K

(236)

Me2AsC=C(AsMe2)(CF2),CF2,1Dao (235),lDa1(236),lee2~ 19*3 As(u-C,H,),,CH,lga4 Ph3Sb, PhsSbCl2,lss5 Ph(Me)RSb,laa6 Ph2EtSb,lBR7MeOC,H,SbMe,,108aand (C6F5)3Bi.1eeB It is interesting that for (CF,)2CFN= S=NC(CF,),N=(CF,),, 10J(18F-1nF)= 1.5 Hz. It was suggested that the coupling is through s p a ~ elggl . ~lH ~ N.m.r. ~ ~ ~ spectroscopy has been used to demonstrate adduct formation between S4N, and 0 1 e f i n s . ~Data ~ ~ ~ have also been reported for [(CF3)2C=NS]2,1893 CF~CICF~N=S=NMC,'~~* (FaCS)(CIF,CS)NHCSHpN,lBB5 and FN=CFN=NCF=NF.lBB6 1073

I. R. Reattie, K. M. S. Livingston, G. A. Ozin, and R. Sabine, J.C.S. Dalton, 1972, 784.

J. M. Keck and G. Klar, Z. Narurforsch., 1972, 27b, 591. H. Schmidbaur and H. Stiihler, Angew. Chem. Internat. Edn., 1972, 11, 145. I n 7H. ~ Schmidbaur, K.-H. Mitschke, and J. Weidlein, Angew. Chem. Ititernat. E h . , 1972, IR7&

11, 144. S. E. Frazier and H. H. Sisler, Inorg. Chem., 1972, 11, 1431. H. G. Ang, M. E. Redwood, and B. 0. W'est. Austral. J. Chern., 1972, 25, 493. 1n79 G. MBrkl, J. Advena, and H. Hauptmann, Tetrahedron Letters, 1972, 3961. lORo L. S. Chia and W. R. Cullen, Cunad. J. Chem., 1972, 50, 1421. lnnl G. Miirk!, H. Hauptmann, and J. Advena, Angew. Chem. Internat. Edn., 1972, 11, 441. la** G. Mark1 and H. Hauptmann, Angew. Chem. Internat. Edn., 1972, 11, 439. lnS3 G. Mark1 and H. Hauptmann, Angew. Chem. Internat. Edn., 1972. 11. 441. lPB4 H. Vermeer, P. C. J. Kevenaar, and F. Bickelhaupt, Annalen, 1972, 763, 155. lns6 D. L. Venezky, C. W. Sink, B. A. Nevett, and W. F. Fortescue, J. Organome~allic Chem., 1972, 35, 131. l Q a a S. Sato, Y. Matsumura, and R. Okawara, J. Organometallic Chem., 1972, 43, 333. InZI7 S. Sato, Y.Matsumura, and R. Okawara, Znorg. Nuclear Chem. Letters, 1973, 8 , 837. lonR G. G. de Paoli, B. Zarli, and L. Volponi, Synth. Znorg. Metal-org. Chern., 1972, 2 , 77. lr'nQ G. B. Deacon and I. K. Johnson, Inorg. Nuclear Chem. Letters, 1972, 8, 27 I . 1n80 R. F. Swindell and J. M. Shreeve, J. Amer. Cheni. SOC.,1972, 94, 5713. 1081 R. R. Swindell and J. M. Shreeve, Inorg. Nirclear Chem. Letters, 1972, 8, 759. l B u a M. R. Brinkman and C. W. Allen, J. Amer. Chern. SOC.,1972, 94, 1550. l R Q 3S. G. Metcalf and J. M. Shreeve, Inorg. Chem., 1972, 11, 1631. lnBp R. Mews and 0. Glemser, Inorg. Chem., 1972, 11, 2521. lnQ6 A. Haas and R. Lorenz, Chem. Ber., 1972, 105, 3161. *sa6 J. B. Hyne, T. E. Austin, and L. A. Bigelow, Znorg. Chem., 1972, 11, 418. I Q 7 ~

I 40

Spectroscopic Proper1ii.s of Inorganic and Orgnnometallic. Coniporrrrt/.y

The 31P n.m.r. spectrum of R(Me,N)P(O)OP(O)(NMe,R) shows the presence of two species, presumably the meso and racemic forms. The influence of R on the separation of the two resonances was exarnined.lUU7 Variable-temperature l9F n.m.r. measurements have been carried out on hexafluoroacetone adducts of a series of 1-substituted phosphetans, in order to obtain data on the relative apicophilicities of different groups. The data were interpreted in terms of electronegativity and back-bonding Similarly, lQFn.m.r. measurements on N,P,F,,_,Ar (n = 3 8 ; Ar = C,F, or FC,H,) have been used to determine (JI and q t . 3 9 9 9 The ' H n.1ii.r. spectrum of P(NMeNMe),P shows a virtual triplet pattern, but the methyl resonance for CIP(NMeNMe),PCI is only a doublet; however, the methyl resonance of CI,P(NMeNMe)PC'I, is a virtual triplet.2o00 The magnitude of 4J(P-H) for HCIC=CCIN=PCl, is temperature dcpendent and this behaviour has been attributed to the position of the equilibrium changing.?Oo1 13C N.ni.r. data, including 'J(P-N C), have been reported for Me,NPPhX.2002'H N.m.r. spectroscopy provides a quick and specific way of assaying sodium cacodylate Data have also been reported for P,N,F,(N (23 CI,P= N PCI,= NS0,C1,2'107 (238),,0°8 R12NR2PC=CPR2NR12,2009 RzAsNEt2,2n10 [R,AsNMe,]'CI and (239).,012 The 3J(13Ccoupling constants in some 1 ,3,2-dioxaphosphorinan2-ones have been shown to be dependent on the POCC dihedral angle and the orientation of the phosphorus-oxygen bond.2013 The or-methyl 7),20059

(237) IR3'

M. D . Jocstcn and Y . T. Chen, Inorg. Chem., 1972, 11, 429. R. K. Oram and S. Trippett, J.C.S. Chetn. Cotntn., 1972, 554. T . Chivers and N. L. Paddock, Inorg. Chetn., 1972, 11, 848. M. D. Havlicck and J. W. Gilje, Inorg. Chem.. 1972, 1 1 , 1624. E. Fluck and W. Steck, Z . anorg. Chem., 1972. 387, 349. M.-P. Simonnin. R.-M. Lequan, and F. W. Wehrli, J.C.S. Chetn. Cuttiui., 1972, 1204. W. Holak, J. Pharin. Sci., 1972, 61, 1635. E. Niecke, H. Thamm, and D. Bohler, Inorg. Nuclear Chem. 1,erter.Y. 1972, 8, 261. R . Appel, R . Kleinstiick, anc K.-D. Ziehn, Chern. Eer., 1972, 105, 2476. A . Schmidpcter, J . Ebeling, H . Stary, and C. Weingand. Z.onorg. Chcni.,1972. 394,

lnsR

lunB

2onn 2o01

*OU4

2o06

171.

''on8 2oon 2010

21112

"'I3

W. Haubold and E. Fluck, Z . Nntirrfursch., 1972. 27b, 368. M . Bermann and J . R . Van Wazer, Inorg. Chem., 1972. I ! , 2 5 1 5 . W. Kuchen and K. Koch, Z . nnorg. Chetn.. 1972, 394, 74. L. S. Sagan, R. A . Zingaro, and K . J . Irgolic, J . Orgariornetnllic~ Clwtii., 1072. 39, 301. L. K. Krannich and H . H. Sisler, Znorg. Cheni., 1972, 11, 1226. 0. J. Scherer and R. Wies, Angew. CJietn. Intrrnnt. Edn., 1972, 1 1 , 592. A . A . Borisenko, N . M . Sergeyev, E. Yc. Nifant'cv. and Yu. A . U s t y n y u k , J . C . S . Chcni. Cumni., 1972, 406.

141 2J(31P-13C) in 2,2,3,4,4-pentamethylphosphetans is stereospecific with respect to the exocyclic phosphorus substituent. The coupling is large (27-37 Hz) when the methyl group is trans and small (@-5 Hz) when the methyl group is cis to the exocyclic phosphorus ~ u b s t i t u e n t .This ~ ~ ~sort ~ of behaviour appears to be frequently found in a very wide range of phosphorus-containing four-membered heterocyclic 201e lH 19F, and 31P n.m.r. spectroscopy have been used to show the presence of two conformers for (240)at - 100 0C.2017However, the lH n.m.r. spectrum of (241)is temperature invariant.2018The lgFn.m.r. spectrum of R1PF3(OR2) is almost independent of R2.2019The lH n.m.r. spectrum of (CF3),P02H


9

MC

does not show phosphorus coupling even at - 100 “C, implying rapid exchange. The I9F and 31P n.m.r. spectra of (CF,),P(S)OP(S)(CF,), are of the AA’XaX’a spin type.2020Data have also been reported for F2C1CSN=CC1S2CC1F2,2021 R2P(02CCF3),2022 Me(HOCH2)P02H,2023 (Et0,POCH=CHOR,2024Ph,-,(PhC=C),P=S,2025 Me,PEMe (E = 0 or S),202eand RPHF0.2027 The n.m.r. spectra of (242)have been measured and used to estimate the anisotropic diamagnetic susceptibility of the arsenic-oxygen and arsenicchlorine bonds.2028For Cl,R,-,Sb(acac) (R = Me or Ph) and EtC1,Sb(acac), if &CH) and 6(CH3) are plotted against for the substituents, a linear relationship is obtained. The stereochemistry was assigned by signal multiplicity and isomers were In order to explain the ‘H chemical G. A. Gray and S. E. Cremer, J.C.S. Chem. Comm., 1972, 367. G. A. Gray and S. E. Cremer, J . Org. Chem., 1972, 37, 3458. 2 0 1 e G. A. Gray and S. E. Cremer, J . Org. Chern., 1972, 37,3470. m7 N . J. De’Ath, D. Z . Denney, and D. B. Denney, J.C.S. Chem. Cotnm., 1972, 272. 2018 N. J. De’Ath and D. B. Denney, J.C.S. Chem. Comtn., 1972, 395. 201B D. U . Robert, G. N . Flatau, C. Demay, and J . G . Riess, J.C.S. Chem. Comm., 1972, 1 127. 8 0 2 0 A. A. Pinkerton and R. G . Cavell, J . Amer. Chem. Soc., 1972, 94, 1870. z o z l P. Gielow and A. Haas, 2. ariorg. Chem., 1972, 394, 53. P. Sartori and M. Thomzik, Z . cinorg. Chetn., 1972, 394, 157. 2u23 L. Maier, 2. anorg. Chem., 1972, 394, 117. 2 u 2 4 L. Maier, 2. anorg. Chem., 1972, 394, 1 1 1. 2 0 2 s E. Fluck and N. Seng, 2. anorg. Chem., 1972, 393, 126. 2u20 F. Seel, W. Gombler, and K.-D. Velleman, Annalen, 1972, 756, 181. 2 0 2 7 U. Ahrens and H. Falius, Chetn. Ber., 1972, 105, 3317. 2028 G. Kamai. N. A. Chadaeva, I. I. Saidashev, and N. K. Tazeeva, Vop. Stereokhim., 1971, 1, 127. 202B H. A. Meinema, A. Mackor, and J. G. Noltes, J . Organometallic Chent., 1972, 37, 285.

2u14

901b

142

Spectroscopic Properties of Inorganic und Organometallic Conipounds

shifts in (243) it was necessary to postulate that the phenyl group is perpendicular to the acetylacetonate C-H axis. This postulate was confirmed by an X-ray structure determination.2030Ph,SbCl,(dpm) has two t-butyl and two CH resonances in the ‘H n.m.r. spectrum, due to (244) and (245). When a freshly prepared solution in C,D, is examined, only Me

\

R3 (242)

Me

,

But

BU‘

( 244)

(245)

one isomer is observed but, slowly (24 h), the second species appears.2o3* For Me3Sb(02CR),, a plot of methyl chemical shift against pK, of the acid produces a straight Data have also been reported for R1,NCO,CH2CHR2XMMe, ( M = As or Sb) 2033 and P h , B i X ( ~ x a l a t e ) . ~ ~ ~ ~ The 19F n.m.r. spectrum of H2NPF4shows two leF resonances of equal intensity. The axial fluorines and the amino-protons form an AA’XX’ spin system and J(15N--lH) = 90.3 Hz. This has been taken to indicate that the nitrogen is sp2 hybridized.2035lSFand 31Pn.m.r. spectra have been reported for F2PN3, F2PON3, and FPO(N3)2. Such work appears to be dangerous and expensive as F2PN3detonated, destroying the phosphorus probe.2o36‘H, 19F,and 31Pn.m.r. spectroscopy have been used to show that I

I

FPNMeCH,CH,NMe binds to BH, via phosphorus. With BF3, species such as (246) are formed.203731P N.m.r. spectroscopy has been used to show that PCI,, BCI,, and NHICl react to form [Cl(Cl,P=N),PC13]+.203a 31P N.m.r. spectroscopy has been used to assist characterization of mixedsubstituent poly(aminophosphazenes).203g The l0F n.m.r. spectra of a *030 2031 9032

2033 *OS4 5035 2038

z037

2038

*Om

J. Kroon, J. B. Hulscher, and A. F. Peerdeman, J. Organometallic Chem., 1972, 37, 297. H. A. Meinema and J. G. Noltes, J. Organometallic Chem., 1972, 37, C31. R . G. Goel and D. R. Ridley, J. Organometallic Chem., 1972, 38, 83. J. Kokctsu, S. Kokjma, and Y. Ishii, J . Organometallic Chem., 1972, 38, 69. G . Faragalia, E. Rivarola, and F. Di Bianca, J. Organometallic Chem., 1972, 38, 91. A. H. Cowley and J. R. Schweiger, J.C.S. Chetrr. Comm., 1972, 560. S. R. O’Neill and J. M. Shreeve, Inorg. Chem., 1972, 11, 1629. S. Fleming, M. K. Lupton, and K. Jekot, Inorg. Chem., 1972, 11, 2534. K . Niedenzu, I. A. Boenig, and E. B. Bradley, Z. anorg. Chem., 1972, 393. 88. H. R. Allcock, W. J . Cook, and D. P. Mack, Inorg. Chem., 1972, 11, 2584.


I43

series of complexes such as (247) have been measured. The results were discussed in terms of molecular conformation and of intramolecular exchange.2040The ‘*F n.m.r. resonances for (248) are not equivalent and an ABX n.m.r. spectrum is observed.2041Data have also been reported for PF2N3,2042(249),2049{C12P(S)}2NR,2044RSPF,C12-,=NPX20,2045 S02(NPC1NEt2),NMe,2046{CI(Me,N)P(O)},NMe and many similar comp o u n d ~ ,F2PN=C=NPF2,20P8 ~~~~ (250),2049(251),2060[-N=PF2-]l,,2061 OPF, I

Mc

I N,

I //N S

(247)

o=P

/ N ‘’

CF3CH,0

20p0

20‘1 2042

2043 204*

2045 2046 2047

2048

2040 2060

zo6f

,P(ocH,cF,),

(25 1 )

‘I‘ CI,P,\

N

ii ,pa,

(252)

R. K. Harris, J. R. Woplin, R. E. Dunmur, M. Murray, and R. Schmutzler, Ber. Bunsengesellschaft phys. Chem., 1972, 76, 44. H. W. Roesky and L. F. Grimm, Angew. Chem. Internat. Edn., 1972, 11, 642. E. L. Lines and L. F. Centofanti, Inorg. Chem., 1972, 11, 2269. S. E. Frazier and H. H. Sisler, Inorg. Chem., 1972, 11, 1223. R. Keat, J.C.S. Dalton, 1972, 2189. H. W. Roesky, B. H. Kuhtz, and L. F. Grimm, Z. anorg. Chem., 1972, 389, 167. U. Klingebiel and 0. Glemser, Chem. Ber., 1972, 105, 1510. I. Irvine and R. Keat, J.C.S. Dalton, 1972. 17. D. W. H. Rankin, J.C.S. Dalton, 1972, 869. M. Bermann and J. R. Van Wazer, Inorg. Chenr., 1972, 11, 209. H. R. Allcock and E. J. Walsh, J . Amer. Chern. SOC.,1972, 94, 119. H. R. Allcock, It. L. Kugef, and E. G. Stroh, Inorg. Chem., 1972, 11, 1120.

144

Spectroscopic Properties of Inorganic and Organometallic Cornpounds

(252),2052 [MeNPF,],, [(MeN),P,F,]*[PF,]-,2053 P3N3F,-nCIn,2054 N4P4C1,-

(NCS)n,z"55 P4N,CI,. ,,(NMe,)n,2056 and Sb(NMe2)2(NR,).2057 For MeO,SNSOF, and OE(NSOF,), (E = S or Se) the fluorine atoms are inequivalent, giving rise to an AB The CF, fluorines in CF,SO(NH)CF,CF, are also i n e q ~ i v a l e n t . ~ Data ~ ~ ~ have also been reported for C1 FSCN(SCCI,-, F,1)2,2060 O= PF,N= SF2= NPF20,20s1 and F2S= NC(0)NC0.206p The 31Pn.m.r. spectra of some cyclic metaphosphates have been reported. I t was found that the order of 31Pchemical shifts to high field for [HP03], is 3 < n < 8 < 4 < 5 < 6 < 7 in tetramethylurea as solvent. Other orders are found in water and as a function of pH. The order was discussed in terms of conformers.2os331P N.m.r. spectroscopy has been used to assist the identification of products such as H3P0, from the reaction of phosphorus compounds, e.g. P4O10 or P203F4, with H202.2064 The 31P n.m.r. spectra of polymetaphosphates have been measured in order to determine the ratio of middle: end groups and hence to determine the amount of Spin-lattice relaxation times of 'H, 2H, 19F, and 31P in solutions of NaPF, and NaP0,F in H 2 0 and D20 have been measured. 19F and 31P spin-relaxation times occur mainly by spin-rotation and dipole-dipole interactions.2066lH, 19F, and 31P n.m.r. spectra have been used to examine FP03H2,FzP0,H2, F3P0, PF3,phosphonic acid, phosphinic acid, pyrophosphoric acid, and polyphosphoric acid with FS03H or FS0,H--SbF5 in order to determine the amount of p r ~ t o n a t i o n .The ~~~~ 19F and 31Pt1.ni.r. spectra of (RFP(S)),S have been analysed to obtain 2J(P-S-P) for the racemic and rneso-forms.2068The 31P n.m.r. spectrum of P4S3shows a quartet and a doublet which is consistent with the structure (253).2069 Data have also been reported for (254),2070 and Et0,PClNCCl,. ,07 H. W. Roesky, Angew. Cherti. Internut. Edn., 1972, 11, 642. K . Utvary and W . Czysch, Motiatsh., 1972, 103, 1048. 2 0 G 4 P. Clare, D. B. Sowerby, and B. Green, J . C . S . Dalton, 1972, 2374. 2 0 b 5 K. L. Dicck and T. Moeller, Itrorg. Nuclear Chern. Letters, 1972, 8, 763. 2 0 5 6 D. Millington and I>. B. Sowerby, J.C.S. Dalton, 1972, 2035. 2057 A . Kiennemann, C i . Levy, and C. 'I'anielian, J. Organometallic Chem., 1972, 46, 305. 2 0 5 8 A. Roland, K. Seppelt, and W. Sundermeyer, Z. anorg. Chem., 1972, 393, 141. "ObD D.T. Sriucr and J . M . Shreeve, Inorg. Chetn., 1972, 11, 238. 2 o a " A. Haas and R . Lorenz, Clienr. Ber., 1972, 105, 237. zuu(iL 0. Glemscr. J . Wegener, and K. Hiifer, Clrem. Ber., 1972, 105, 474. 2 o a L ' A. I . Clifford, J . S. Harman, and C. A . McAuliffe, Inorg. Nucleur Chetn. Letters, 1972, 8, 567. "Oe3 T. Glonek, J. R . V a n Wazer, M. Mudgctt, and T. C. Myers, Inorg. Chem., 1972, 11, 567. "Oa4 E. Fluck and W. Steck, Z. onorg. C h e w . , 1972, 388, 53. "Oa6 K . C. Mehrotra, P. C. Vyas, and C. K. Oza, IndianJ. Chem., 1972, 10, 726. 2ooBe M. F. Froix and E. Price, J . Chem. Phys., 1972, 56, 6050. "Oa7 G. A. Olah and C. W. McFarland, Inorg. ('hem., 1972, 11, 845. 2 ~ K 8 . K . 14arris, J. R . Woplin, M. Murray, and R. Schmutzler, J.C.S. Dalton, 1972, 1590. 2ua8 L. Kolditz and E. Wahner, Z. Chem., 1972, 12, 389. 2 0 7 0 W. G . Bentrude, W. D. Johnson, and W. A. Kahn, J. Amer. Chern. SOC., 1972, 94, 3058. ? 0 7 * W. Haubold and E. Fluck, Z. onorg. Chenr., 1972, 392, 59. 2(1b2

2ub3

Niiclear Magnetic Resorinrrce Spectroscopy 145 The IH n.m.r. spectrum of ( 2 5 5 ) has been analysed as AA'XsX13 and J(AA) used to determine which isomer is cis and which is 15N N.m.r. spectroscopy has been used to show two isomers for (256) and (257).2073

(257)

13CN.ni.r. data have been reported for [PhMeI]+[SbF,]-.20741°F, lBISb, and lZsSbn.m.r. spectra have been observed for [SbF6]-. The O ' F n.m.r. spectra show 1J(10F-121Sb)= 1934 Hz and 1J(10F-123Sb)= 1047 H z . ~ ~ ~ Data have also been reported for MePXY.2076 9 Compounds of Groups VI and VII and of Xenon Information concerning complexes of these elements can be found at the following sources: TeCpHp,1779TeC,H,Cr(CO),, TeC4H4Fe2(CO)s,241 R1R2C2SeFe2(CO)s,408 [Fe(CO),SeMe,],,477 rruns-PtCl(SO,Ph)(EEt,), (E = Se or Te),*24trans-PtC1(O2SPh)(EEt2),(E = Se or Te),825[Me,NCSe,C2H4]+,1021 H,Ru,(CO),E (E = S, Se, or Te),347(H,M),E, (F,P),E (M = Si or Ge; E = 0, S, Se, or Te),lP3H3SiSeMe,1745 OSe(NSOF,),,2058R3PSe,142 HOF,"' HCI,"' [ClF6]f,70and [IFG]'.~~ A book has appeared which lists nuclear magnetic resonance data of sulphur compounds. The lH n.m.r. spectra of (258; E = 0, S, Se, or Te) have been analysed and solvent effects examined.2o78The 1 7 0 n.m.r. spectrum of C F 3 0 0 0 C F 3 shows resonances at - 321 p.p.m. (intensity 2) and - 479 p.p.m. (intensity 1 ) relative to H2170. OFz reacts with C170F, to give the resonance at -321 p.p.m. and 170F2reacts with COF, to give the resonance at 2073

2074

zo70

2Uf7

:Oin

6

D. W. Aksnes and 0. Vikane, Acta Chern. Scand., 1972, 26, 835. P. Stilbs, Tetrahedron Letters, 1972, 227. G. A. Olah and E. G. Melby, J. Amer. Chem. Soc., 1972, 94, 6220. R. G. Kidd and R. W. Matthews, Inorg. Chent., 1972, 11, 1156. H. W. Schiller and R. W. Rudolph, Inorg. Chem., 1972, 11, 187. N. F. Chamberlain and J. J. R. Reed, in 'The Analytical Chemistry of Sulphur and its Compounds, Part III', ed. J. H. Karchmer, 'Nuclear Magnetic Resonance Data of Sulphur Compounds', Wiley-Interscience, New York, 1971. P. Faller and J. Weber, BI4/[. Soc. chini. France, 1972, 3193.

146

Spectt oscopic Pr0perlic.r of Itiorgunic and Orgarionic allic Compounds

- 479 p . ~ . r n , ~ O let; ~~ N.m.r. data have also been reported for CFBOOF20Ho and (CFs00)2C0.2081 l9F Chemical shifts have been measured for compounds of the type FC6H4SOX. The effects of substituents, X, at sulphur have been analysed by use of the polar and resonance substituent parameters 01 and og.208a Data have also been reported for [HCS(SH)],,2083[HCS(SR)],,20B4 [HCS2]-,2085HCOSH,2086F3CSCC12SSCF,C13-, (including n.m.r. data),2087E1C(E2Me),(El, E2 = S or Se),2088 and (259).208Q

(L,

(260)

The 'H n.ni.r. spectra of benzo(b)selenophen and benzo(b)tellurophen have been fully analysed; long-range coupling between the rings is o b ~ e r v e d . ~ ~The ~ O structures of complexes between selenane and bromine or iodine have been determined in solution. By analysis of the coupling constants in the ring for the selenane-bromine complex it was possible to show trigonal-bipyramidal stereochernistry.20Q1 lH N.m.r. spectroscopy has been used to show axial preference of the substituent in (260).2092Data have also been reported for R1R2SeCXY,20sSpoly-(3,3-dimethyl~ e l e n e t a n ) ,ArECl, ~ ~ ~ ~ (E = Se or Te),20Q5RN=C=Se,2096 PhSeX,2097 ArSeMe,20s8(261),20s9 PhCOSeH,2100(262),2101 (263),2102 (PhSe),CHMe, 207s

.Onl 2on2 "OB3

L'0s4 "u86 '.OX6

.Ons "OnU

2LLuo

"OU1

2'J83 "Og3

20!'4

"Oe5

2op6

a097 "OU8

20@B 2100 2101

?Io4

I. J. Solomon, A. J. Kacmarek, W. K. Sumida, and J. K. Raney, Inorg. Chetn., 1972, 11, 195. D. D. DesMarteau, Inorg. Chem., 1972, 11, 193. D. Pilopovich, C. J. Schack, and R. D. Wilson, Inorg. Chem., 1972, 11, 2531. W. A. Sheppard and R. W. Taft, J . Atner. Chem. Soc., 1972, 94, 1919. R. Engler and G. Gattow, 2. anorg. Chem., 1972, 389, 145. R. Engler, G. Gattow, and M. Drager, Z. anorg. Chem., 1972, 390, 64. R. Engler, G. Gattow, and M. Driiger, 2. anorg. Chem., 1972, 388, 229. R. Engler and G. Gattow, Z. anorg. Chem., 1972, 388, 78. A. Haas, W. Klug, and H. Marsmann, Chrm. Ber., 1972, 105, 820. M. DrBger and G. Gattow, Spectrochini. Acta, 1972, 28A,425. A. Tadino, L. Christiaens, M. Renson, and P. Cagniant, Bill/. Soc. chitn. helgrs, 1972, 81, 595. G. Llabrks, M. Baiwir, J. Denoel, J. L. Piette, and L. Christiaens, Terrahedron Letters, 1972, 3177. J. B. Lambert, D. H. Johnson, R. G. Keske, and C. E. Mixan, J . Atner. Chem. Soc-., 1972, 94, 8172. J. B. Lambert, C. E. Mixan, and D. H. Johnson, Tetrahedron Letters, 1972, 4335. N. N. Magdesieva, R. A. Kandgetcyan, and A. A. Ibragimov, J. Organometallic Chem., 1972, 42, 399. E. J. Goethals, E. Schacht, and D. Tack, J. Polymer Sci.,Part A - I , Polymer Chetri., 1972, 10, 533. K. J. Wynne, A. J. Clark, and M. Ber, J.C.S. Dalton, 1972, 2370. N. Sonoda, G. Yamamoto, and S . Tsutsumi, Bull. Chem. SOC.Japan, 1972, 45, 2937. K. J. Wynne and P. S. Pearson, Inorg. Chem., 1972, 11, 1196. F. Mantovani, L. Christiaens, and P. Faller, Bull. SOC.chim. France, 1972, 1595. C . Dragnet and M. Renson, Bull. SOC.chim. beiges, 1972, 81, 295. K. A. Jensen, L. Bprje, and L. Hendriksen, A d a Chem. Scand., 1972, 26, 1465. L. Fitjer and W. Luttke, Chem. Ber., 1972, 105, 919. L. Fitjer and W. Luttke, Chetn. Ber., 1972. 105, 907.

-

147

Nuclear Magnefic Resonance Spectroscopy

CH,C(5Ph),C(SePh),,2103(264),2104(265),,lo5 benzo[b]selenophens,z106-2108 PhTeOAc,2108 o-C,H,(CH(OEt)2}(TeCH,CH(OEt)2},2110 o-C,H,(TeBr)(COCH=CHPh),2111(266),2112and l-(tellurophen-2-yl)ethyl acetate.2113

(265)

(266)

The lSF n.m.r. spectra of ArO,SF, and (ArO),S(O)F, show resonances for equatorial and axial f l u ~ r i n e s The . ~ ~19F ~ ~n.m.r. spectrum of HOSeF, Cation dependence is found is of the AB, type with selenium for the O ' F n.m.r. spectrum of [SeOF,]-.2116 XeF, reacts with HOSeF, to give Xe(OSeF,), and FXe(OSeF,), which give AB4 'OF n.m.r. spectra with "Se and 12BXe [C6H5NH]+[TeF50]-and SeF,CI also give AB, l8F n.m.r. spectra.211e~ 2118 Data have also been reported for S3N3Fg,2120 F,SeOS0,0S02F,2121R1R2P(OH)Se,2122 and F,TeOR.2123 Nuclear spin relaxation and molecular motion in liquid HBr and HCl have been examined.2124The lH shielding of [CIHCII-, [BrHBrj-, and [HIHI- has been derived and a deshielding of ca. 13 p.p.m. found with D. Seebach and N. Peleties, Chem. Ber., 1972, 105, 51 1. B. Decroix, I. Morel, C. Paulmer, and P. Pastour, Bull. SOC.chim. France, 1972, 1848. 2 1 u G F. Terrier, A.-P. Chatrousse, R. Schaal, C. Paulmier, and P. Pastour, Tetrahedron Letters, 1972, 1961. ?lot) T. Q. Mink, L. Christiaens, and M. Renson. Tetrahedron, 1972, 28, 5397. * I o 7 T. Q. Mink, P. Thibaut, L. Christiaens, and M. Renson, Tetrahedron, 1972, 28, 5393. N. N. Magdesieva and V. A. Vdovin, Khim. geterotsikl. Soedinenii, 1972, 15. *I0@ B. C. Pant, Tetrahedron Letters, 1972, 4779. J.-L. Piette, R. Lysy, and M. Renson, Bull. SOC.chim. France, 1972, 3559. 2 1 1 1 J -L. Piette and M. Renson, Bull. SOC.chim. belges, 1971, 80, 669. P'. Fringuelli and A. Taticchi, J.C.S. Perkin I, 1972, 199. 2113 F. Fringuelli, G. Marino, and A. Taticchi, Gazzetra, 1972, 102, 534. 2114 D. S. Ross and D. W. A. Sharp, J.C.S. Dalton, 1972, 34. 2116 K. Seppelt, Angew. Chem. Internat. Edn., 1972, 11, 630. 2116 K. Seppelt, Chem. Ber., 1972, 105, 2431. 2117 K. Seppelt, Angew. Chem. Internat. Edn., 1972, 11, 723. "llR G. W. Fraser and J. B. Millar, J.C.S. Chem. Comm., 1972, 1 1 13. yllQ C. J . Schack, R. D. Wilson, and J. F. Hon, Inorg. Chem., 1972, 11, 208. N. I. Maraschin and R. L. Lagow, J. Amer. Chem. SOC.,1972, 94, 8601. 21z1 K. Seppelt, Chem. Ber., 1972, 105, 3131. s 1 2 2 M. Mikolajczyk and J. tuczak, Tetrahedron, 1972, 28, 541 1. 212s F. Sladky and H. Kropshofer, Inorg. Nuclear Chem. Letters, 1972, 8, 195. 2103

21u4

I48

Spectroscopic Proptvties of Inorganic and Orgoitotnetollic Conlporrrrdv

respect to the solvatcd hydrogen halide. The equilibrium constants arc ill the order consistent with a simple electrostatic model of ion-moleculc association.2125The shielding constants were shown to be dominated by hydrogen charge-density, which is less than for the corresponding molecule. This is the charge shift predicted by a simple electrostatic model but not by the independent-electron molecular orbital model.2126 The lBFn.m.r. spectrum of [ClF2]+has been reported for the first time.2127 The lVFn.rt1.r. spectrum of CIF,O has been measured as a neat liquid and as a gas; no extra resonances were found on From lVFn.m.r. spectra, the presence of I(SO,F), in mixtures of I2 and S,O,F, has been suggested.2129 The 19F n.1n.r. spectrum of CF,IF, is A3X, at room temperature.2130 The 19F n.m.r. spectrum of [F5Xe]+shows the presence of two types of fluorine of intensity one, lJ(lavXe-lvF)= 170 Hz, and intensity four, 1J(129Xe-1vF)= 1377 Hz?~' I n SbF5, OXeF4,2SbF, and XeOzF,,2SbF, have the structures [XeOF,] ' [Sb,F,,] and [XeO,F] '[Sb,F,,]- respecti

10 Bibliography

The following is a list of those references obtainable via the Chemical Society's n.m.r. Macroprofile (UKCIS) which are in journals not abstracted from the main text and omitted from Volume 5 of this S.P.R. The Chemicd Abstracts reference number is given in brackets. Chemical Absfracts, 1972, Volume 76. A . G. Yurchenko and S. D. Isaev. 'H n.m.r. spectra of adamantanone and adamantanone oxime in the presence of europium tris(dipivaloy1methanate). Zhur. org. Khitii., 197 1. 7 , 2628 (CA 71 918). M. Karras and E. Rahkamaa. Determination of moisture in pulp by the n.m.r. method. Pap. Puu, 1971, 53, 653 ( C A 73 963). J. R. Campbell. Lanthanide chemical shift reagents. A/dric,hitiiica Ac,fa, 1971, 4, 5 5 ( C A 78 585). H. Pfeiffer. N.m.r. and relaxation of adsorbed niolecules. Paramagn. Rezonnns IY44 1969, Vses. Yubileinaya Konf. 1969, 1971, 255 ( C A 78 987). L. Tomic, Z. Majerski, M. Tomic, and D. E. Sunko. Tris(dipivaloylmethanato)holmiuminduced n.m.r. shifts. Croat. Chem. Acta, 1971, 43, 267 (CA 79 097). Yu. V. Belov, Yu. L. Kleiman, N. V. Morkovin, and Yu. Yu. Samitov. Observation of double resonance in the rya-2307 n.m.r. spectrometer. Prib. Tekh. Eksp., 1971, 186 (CA 79239). V. Niculescu, S. Mandache, and I. Pop. Device for temperature regulation in n.m.r. measurements. Stud. Cercet. Fiz., 1971, 23, 1123 ( C A 79 248). -

2124

s12B

*I1' 2128

212e

21:'1 :':I2

K. Krynicki and J. G. Powles, J. Magti. Resonance, 1972, 6 , 539. F. Y. Fujiwara and J. S. Martin, J. Chem. Phys., 1972, 56, 4091. J. S. Martin and F. Y. Fujiwara, J. Chem. Phys., 1972, 56, 4098. M. Brownstein and J. Shamir, Cunad. J. Chem., 1972, 50, 3409. D. Pilopovich, C. B. Lindahl, C. J. Schack, R. D. Wilson, and K. 0. Christe, Znorg. Chem., 1972, 11, 2189. C. Chung and G. H. Cady, Znorg. Chem., 1972, 11, 2528. 0. R. Chambers, G. Oates, and J. M. Winfield, J.C.S. Chem. Comm., 1972, 839. D. D. Desmarteau and M. Eisenberg, Inorg. Chem., 1972, 11, 2641. R . J. Gillespie, B. Landa, and G. J. Schrobilgen, J.C.S. Chem. Comm., 1972, 607.

Nuclear Magnetic Resoriance Spectrmcopy

149

Yu. D. Gavrilov and V. F. Bystrov. Suppression of a hcteronuclear spin-spin interaction in n.m.r. spectra using a spin generator. Prib. Tekh. Eksp., 1971, 140 ( C A 79 250). S . A. Al'tshuler and M. A. Teplov. N.m.r. of paramagnetic ions in singlet electronic states. Paramngn. Rezonnns 1944-1 969, Vses. Y'iibilrinaya Konf. 1969, I97 I , 166 ( C A 92 181). I. A. Nuretdinov and E. I. Loginova. Phosphorus-31 and selenium-77 spin-spin interaction constants and structure of chlorophosphine selenides. Izlvst. Akad. Nnuk S.S.S.R., Ser. khinr., 1971, 2360 (CA 92662). A. N. Gil'manov, S. I. Berezina, G . S. Vozdvizhenskii. and V. D. Lapshin. Proton magnetic relaxation study of the state of hydrogen adsorbed by palladium and platinum cathodes. Elektrokhinriya, 1971, 7 , 1336 ( C A 92 663). T. Kanashiro, T. Ohno, T. Taki, and M. Satoh. Acoustic excitation of n.m.r. in sodium chlorate. Bull. Fac. Eng., Tokushima Unir:., 1971, 8, 19 ( C A 92 664). I. A . Nuretdinov, V. V. Negrebetskii, A. Z. Yankelevich, A. V. Kessenikh, L. K . Nikonorova, and E. I. Loginova. Proton n.m.r., phosphorus-3 1 n.m.r., and proton-phos= phorus-31 INDOR-!"P spectra of compounds containing the =PX-N=E-PY group. Izoest. Akad. Nauk S.S.S.R., Ser. khim., 1971, 2589 ( C A 92 667). V. S. Lyubimov and S. P. Ionov. Electronic structure and n.m.r. spectra of boron compounds. Izoest. Akad. Narik S.S.S.R., Ser. khirn., 1971, 2584 ( C A 92 679). V. I. Chizhik and Yu. A. Ermakov. Quadrupole relaxation of the nuclei of lithium and sodium ions in aqueous solutions of electrolytes. Yad. Mngn. Rezonans, 1971, 60 ( C A 92 697). H. Yokoyama, S. Chiba, and N. Ichinose. N.m.r. and magnetic propertics of cobalt chromium sulphide (CoCr,S,) and its solid solution. Ferrites, Proc. Internnt. Conf. 1970, 1971, 611 ( C A 92 710). S. Albert, H. S. Gutowsky, and J. A. Ripmcester. Spin-lattice relaxation time study of molecular motion and phase transitions in the tetramethylammonium halides. U.S. Not. Tech. Itform. Sent., A D Rep., 1971, 22 ( C A 92 721). V. K. Voronov. Paramagnetic shifts in complexes of nickel with some derivatives of the five-membered N-heterocyles. Izcest. Sibirsk. Otdel. Aknd. Naitk S.S.S.R., Ser. khinr. Nnuk, 1971, 62 ( C A 92 723). Yu. N. Molin, R. Z. Sagdeev, E. V. Dvornikuv, and V. A. Grigor'ev. N.m.r. of 'other' nuclei in paramagnetic complexes. Paramngn. Rezonnns 1944-1969, Vses. Yuhileinoya Konf. 1969, 1971, 246 ( C A 92 734). Z . Kecki. Proton magnetic resonance of electrolyte solutions in methanol and water. Paramagn. Rezonans 1944-1969, Vses. Yuhileinoya Konf. 1969, 1971, 234 ( C A 92 742). R. S. Borden. Fluorine-I9 n.m.r. study of some bromofluorotitanate complexes and hydrolysis of some titanium tetrafluoride complexes. IJ.S. Not. Tech. Inform. Sera., A D Rep., 1971, 40 ( C A 92 756). F. I. Bashirov, Yu. L. Popov, K. S. Saikin, and R . A. Dautov. Apparatus for studying nuclear magnetic relaxation in the laboratory and rotating frames. Prib. Tekh. Eksp., 1971, 137 ( C A 92917). V. R. Nagibarov. Inertial spin-lattice relaxation. Partrnrogrr. Rezonans 1944-1969, Vses. Yubileinnya Konj:, 1969, 1971, 250 ( C A 92 183). V. V. Frolov. Theory of the effect of internal rotation on the spin-lattice relaxation rate. Yad. Mogn. Rezonans, 1971, 18 ( C A 92 682). R. R. Fraser, T. Durst, M. R. McClory, R. Viau, and Y . Y. Wigfield. Comparison of the effects of solvents and Eu(dpm), on proton shieldings in sulphoxides. Internat. J . Sulfur Chem. ( A ) , 1971, 1, 133 ( C A 98 577). M. L. Filleux-Blanchard and A. Durand. Hindered rotation around the carbon-nitrogen bond in thioureas and selenoureas. Conrpr., rend. 1971, 273, C , 1770 (CA 98 585). N. N. Magdesieva. V. A. Vdovin, and N. M. Sergeev. Chemistry of benzo[b]selenophen: lH n.m.r. spectra o f deuterio-derivatives of the benzo[h]selenophen series. Khinr. geterotsikl. Soedinenii, 1971, 1382 ( C A 98 610). P. M. Borodin and Yu. I. Mitchenko. Complexing in organophosphorus compounds studied by n.m.r. Paramngn. Rezonons 1944-1969, P'SPS. Yubileinayn Kotrf. 1969, I97 1, 180 ( C A 98 923). M. Noshiro and Y. Jitsugiri. Determination of boron in glass by fluorine-19 n.m.r. Asnhi Gnrosit Kerikyrt Hokokrr, 1971, 21, 47 ( C A 103 200). F. J. C. Rossotti. Hydration and structure of copper(^^) complexes in solution. PIWC.. ConJ Co-ordinotiotr Chetti.. 3rd. 1971, 283 ( C A 104 560).

1 50

Spectroscopic Properties of Inorganic and Orgnnometnllic Compounds

P. M. Borodin, K. Z. Nguyen, and P. P. Andreev. Structure of aqueous solutions of Li,SiF, studied by the fluorine-19 n.m.r. method. Yud. Magn. Rezonuns, 1971, 103 (CA 104 624). R. F. Snider. Boltzmann equation and gaseous n.m.r. Kinetic Equations, Papers of 1969 Meeting, 1971, 129 ( C A 105 656). D. Demco and V. Ceausescu. N.m.r. lineshape governed by a time-dependent Hamiltonian. Rev. Roumaine Phys., 1971, 16, 1093 (CA 105 666). A. P. Potemskaya, G. P. Aleeva, V. Z. Kuprii, and V. A. Lunenok-Brumakina. Structure and decomposition reactions of vanadium peroxide compounds. Teor. i eksp. Khim., 1971, 7 , 757 (CA 106 089). A. S. Tarasevich and Yu. P. Egorov. Determination of P=N bond order in phosphazodrivatives by a phosphorus-31 n.m.r. method. Teor. i eksp. Khim., 1971, 7 , 828 ( C A 106 144). E. I. Angerer and P. M. Borodin. Proton magnetic relaxation in alcohol solutions of antimony trichloride. Yud. Magn. Rezonans, 1971, 72 (CA 106 168). Yu. S. Chernyshev and Yu. A. Ignat’ev. Frequency dependence of the spin-lattice relaxation time of benzene on a potassium chloride surface. Yud. Magn. Rezonanr, 1971, 66 (CA 106 169). P. M. Borodin and G. P. Kondratenkov. Antimony trichloride solutions in isoalipathtc alcohols studied by an n.m.r. method. Yud. Mugn. Rezonuns, 1971, 77 ( CA 106 170). S. Maricic, M. Cervinka, G. Pifat, and J. Brnjas-Kraljevic. Proton magnetic relaxation studies on haemoproteins in crystals and in concentrated salt solutions. Europenn Biophys. Congr., Proc., Zst, 1971, 1, 77 (CA 109400). G. Pifat and S. Maricic. Proton magnetic relaxation study of human ferrihaemoglobin and horse myoglobin in dilute salt solutions. European Biophys. Congr., Proc., I s t , 1971, 1, 81 (CA 109401). Y. Kurimura, E. Tsuchida, and M. Kaneko. Preparations and properties of some watersoluble cobalt(iii)-poly-(4-~inylpyridine)complexes. J . Polymer Sci., Port A - I , Pofyriier Chem., 1971, 9, 3511 (CA 113 592). S. Tanaka, S. Toda, J. Saito, T. Mitsuishi, C. Nagata, K. Kanohta, S. Hashimoto, Y. Shimizu, and H. Kitazawa. Graphic representation of carbon-13 n.m.r. chemical shifts: master chart. Bunseki Kagaku, 1971, 20, 1573 (CA 119 147). A. A. Tyshchenko, K. H. A. Aslanov, V. B. Leont’ev, and A. S. Sadykov. Correlation between interaction constants in n.m.r. and e.p.r. spectra. Doklady Akad. Nauk UAb. S.S.S.R., 1971, 28, 37 (CA 119204). V. A. Atsarkin, M. E. Zhabotinskii, A. F. Mefed, S . K. Morshnev, and M. I. Podak, Role of a spin-spin reservoir in paramagnetic resonance and in the dynamic polarization of nuclei. Paramagn. Rezonans 1944-1969, P’ses. Yubileinaya Konf. 1969, 1971, 38 (CA 119 596). P. M. Borodin. Kinematic relativism in n.m.r. Yad. Mugn. Rezonans, 1971, 5 (CA 119 636). L. L. Buishvili. Effect of saturation of the magnetic chromium-53 nuclei resonance on the magnetic aluminium-27 resonance in ruby. Izoest. V.U.Z., Rudiofiz., 1971, 14, 1364 (CA 119 637). H. Lechert and H. J. Hennig. Influence of hydrogen sulphide (adsorption) on the behaviour of proton and sodium-23 resonances in faujasite-type zeolites. Z. phys. Chem. (Frankfurt), 1971, 76, 319 ( C A 119 655). T. G. Pinter. Crystalline electric fields in some thulium-aluminium compounds. Report, 1971, 126 ( C A 131 710). P. M. Borodin and M. I. Volodicheva. Effect of ions of normal aliphatic alcohols in the SbC1,-ROH system on a chemical shift in an n.m.r. proton signal. Yad. Magn. Rezonuns, 1971, 38 (CA 132210). J. W. Neely. Oxygen-17 n.m.r. studies of the first hydration sphere of diamagnetic metal ions in aqueous solution. Report, 1971, 72 ( C A 132258). H. Pfeifer. Spin echoes: means for high-resolution n.m.r. in solid bodies. Wiss. Z. Karl-Marx-Univ. Leipzig., Math.-Naturwiss. Reihe, 1971, 20, 549 (CA 133 532). V. D. Doroshev, N. M. Kovtun, E. E. Solov’ev, A. Y. A. Chervonenkis, and A. A. Shemyakov. N.m.r. study of spin reorientation in thulium ferrate single crystals. Pis’mu Zhur. Eksp. i teor. Fiz.,1971, 14, 501 (CA 133 900). N . S. Biradar and M. A. Punjar. Linkage isomerism in cobalt(ii1) amine complexcc. Proc. Cherti. $,nip., Ziicl. 1971, 1, 209 ( C A 133 916).

Nriclenr Magnetic Resonance Spectroscopy

151

A. Vertes and F. Parak. Relation between the spin relaxation and other properties of paramagnetic iron(ii1) salts. Kem. Kozlem., 1971, 36, 429 ( C A 133 871). D. F. Gaines and J. Borlin. Internal exchange in new Group 111 metalloborane derivatives: Me,AlB,H, and Me,GaB,H,. U.S. Not. Tech. Inform. Sero., A D Rep., 1971, 15 ( C A 127 059). Z. Michalska and Z. Lasocki. Determination of relative acidities of some substituted phenylsilanetriols by n.m.r. and i.r. spectroscopy. Bull. Acad. polon. Sci., SPr. Sci. chitn., 1971, 19, 757 ( C A 139 817). L. 1. Zakharkin, B. A. Kvasov, and V. N. Lebedev. Synthesis and study of fluorine-19 n.m.r. spectra of 1-fluoromethyl-o-carbaboranesand 2-substituted l-fluoromethyl-ocarbaboranes. Zhur. obschchei Khim., 1971, 41, 2694 (CA 140 936). P. Salvador Salvador. Applications of n.m.r. in mineralogy. Bol. Geol. Minero, 1971, 82, 543 ( C A 143 295). W. Mueller-Warmuth and F. Kraemer. N.m.r. studies on motional processes in glasses. Znternat. Congr. Glass, Sci. Tech. Comm., 9th, 1971, 1, 303 (CA 144296). G. K. N. Reddy and E. G. Leelamani. Carbonyl hydrides of iridium with tertiary arsines. Proc. Chem. Synip., 2nd, 1971, 1, 247 (CA 146 924). N. K. Skvortsov, A. V. Dogadina, G. F. Tereshchenko, N. V. Morkovin, B. I. Ionin, and A. A. Petrov. Protonation of phosphine oxides studied by proton and phosphorus-31 n.m.r. Zhur. obshchei Khitn., 1971, 41, 2807 ( C A 152 761). N. N. Magdesieva and V. A. Vdovin. Chemistry of benzo[6-b]seleiiophen : derivatives of selenoindoxyl. Khim. geterotsikl. Soedittenii, 1971, 1640 ( C A 153 554). C . Rhee and P. J. Bray. N.m.r. studies of the structure of caesium borate glasses and crystalline compounds. Phys. and Chem. Glasses, 1971, 12. 165 ( C A 157 564). C. Rhee and P. J. Bray. Effect of ionic motion on the caesium-133 n.m.r. in glassy and crystalline caesium borates. Phys. and Chem. Glasses, 1971, 12, 156 ( C A 157 565). R. D. Green and S. P. Sinha. Lanthanide shift reagents: acetylacetone complex of ytterbium(1Ii) ion. Spectroscopy Letters, 1971, 4, 41 1 ( C A 160 521). K. Sugimoto, A. Mizobuchi, K. Matuda, and T . Minamisono. Hyperfine Inferactions of Excited Nuclei, Proc. Conf., 1971, 1, 167 ( C A 160 569). D. Spanjaard, R. A. Fox, I. R. Williams, and N. J. Stone. Nuclear spin-lattice relaxation measurements below 0.1 K by nuclear orientation. Hyperfine Interactions of Excited Nuclei, Prof. Conf., 1971, 1, 345 (CA 160570). H. S. Gutowsky and D. F. S. Natusch. Influence of paramagnetic species on the internuclear Overhauser effect. U.S. Not. Tech. Itform. Seru., A D Rep., 1971, 55 ( C A 160 582).

Chemical Abstracts, 1972, Volume 77. R. T. Ogata and H. M. McConnell. Binding of a spin-labelled triphosphate to haemaglobin. Cold Spring Harbor Symp. Quant. Biol., 1971, 36, 325 ( C A 2158). A. G . Redfield and R. K. Gupta, Pulsed n.m.r. study of the structure of cytochrome. Cold Spring Harbor Synip. Quant. Biol., 1971, 36, 405 ( C A 2159). J. Reuben. Gadolinium(m) as a paramagnetic probe for magnetic resonance studies of biological macromolecules. Proc. Rare Earth Res. Cong., 9rh, 1971, 2, 514 ( C A 2462). A. N. Nesmeyanov, 0. V. Nogina, V. A. Dubovitskii, B. A. Kvasov, P. V. Petrovskii, and N. A. Lazareva. Transmission of the electronic effects of ligands in mono- and his-cyclopentadienyl derivatives of titanium in various solvents. Izvest. Akad. Nauk S.S.S.R., Ser. khim., 1971, 2729 ( C A 4724). Yu. S . Stark. Nuclear magnetic resonance. Metody Ispyt., Kontr. Issled. Mashinostroit. Mater., 1971, 1, 512 ( C A 1 1 534). S. P. Sinha and R. D. Green. N.m.r. studies of lanthanide(rii) complexes: high-field shifts in complexes of l,10-phenanthroline. Spectroscopy Letters, 1971, 4, 399 ( C A 12 077). B. Matic and A. Brumnic. Time-mode system for measuring nuclear resonance. Automatika, 1971, 12, 381 ( C A 12 185). D. G. Davis, S. Charache, and C. Ho. N.m.r. studies of hnemoglobins. Genet., Funct., Phys. Stud. Haemuglobins, Proc. Inter-Amer. 1969, 1971, 280 ( C A 15 792). V. V. Kosovtsev, T. N. Timofeeva, B. I. Ionin, and V. N. Chistokletov. 'H n.m.r. spectra of alkenylphosphines and derivatives of nlkenylpho v4, comparison with isoelectronic SOF2 and normalco-ordinate analyses both suggest that it is correct. The order of S02-Xinteraction in the series XSO; (X = F, Cl, Br, or I), viz. F > C1 < Br < I, determined by normal-co-ordinate analysis, is supported by the relative intensities of the electronic transition^.'^^ The vapours of both SOF2 and S02Fa have been studied by i.r. absorption at moderate resolution. A notable feature is the extensive satellite absorption associated with upperstate transitions (established by their temperature dependence and by intensity calculations). Hot band sequences were found to originate from : vAul) 385 cm-l torsion, v5(a2) 389 cm-l deformation for S02F2, and v4(u’) 377.8 and v6(a”)392.5 cm-l deformations for SOF2.13’ The assignments below are reported for aqueous solutions of KXOB salts (X = C1, Br, or I). v2 has the following wavenumbers/crn-l for the isotopic variants shown: Br160; 418, Br1e0160, 414, Br1s021s0-407, and BrlBO; 401 cm-l.13*

c10,

BrO; 10,

Vl(aJ

vz(a1)

vde)

vde)

933 805 805

608 418 358

977 805 775

477

358 320

In molten KClO, and NaClO, the anion frequencies (Raman) are close to those found in solutions and there is no lifting of degeneracy;139in contrast, in a similar Raman experiment with alkali-metal carbonates the ‘forbidden’ v 2 ( a 3 mode was observed at ca. 880 cm-l and v,(e’) ~ p 1 i t . l ~ ~ The new compound BrNCO shows i.r. absorption (solid) at 3440, 2256, 21 64, 21 20, 1289, 690, 566, and 473 cm-l.lP1 Penta-atomic Species.-The accumulation of more complete and accurate frequencies for tetrahedral species AB4 continues, with emphasis on new Raman data. Use of isotopic substitution coupled with force-field calculations is much in evidence, both in regular and in substituted entities. Raman and i.r. frequencies have been listed for liquid and crystalline samples of SiH4-SiD4 mixtures.142SiH4 shows a transition at 63.75 K but no crystallographic data are available on either phase. Spectra of phase I are similar to those of the liquid and presumably arise from orientationally 137

138 I4O

A. J. Sumodi and E. L. Pace, Spettrochim. Acta, 1972, 28A, 1129. D. J. Gardiner, R. B. Girling, and R. E. Hester, J . M o f . Structure, 1972, 13, 105. A. B. Lece, A. J. Kale, and K. Sathianandan, High Temp. Sci., 1972, 4, 231. J. B. Bates, M . H. Brooker, A. S. Quist, and G . E. Boyd, J . Phys. Chem., 1972,76, 1565. W. Gottardi, Monarsch., 1972, 103, 1150. R. P. Fournier, R. Savoie, N. D. The, R . Belzile, and A. Cabana, Canad. J . C‘hetn., 1972, 50, 35.

21 1

Vibrational Spectra

disordered molecules, but those of phase I1 are highly complex and compatible with a structure having one of the following factor groups: S,, C4,c4, (tetragonal); C,,, D3, DSd (trigonal); C3h,c6, C6, (hexagonal). have been High-resolution spectra of the v3 bands of *%iH4143 and GeH, analysed, as have v2 and v, of GeH,.14," Table 9

Vibrational wavenumberslcm-l for tetrahalogeno-species a

Species

vl(a1)

PCli TiF,(g) BeFiGeCI, SnCl, GeBr, SnBr, TiCI, TiBr, Ti I, ZrC1, ZrBr, ZrI, HfCI, Hf Br, HfI, COCI, cocI$ CrCl; ZnClfCdBrfCdIi-

458 71 2 547 --

vz(e)

v3(t2)

178 185 255 (147p ( 1 00)!'

662 793 800 463

-

-

-

_ -

389 23 1.5 162 377 225.5 158 382 235.5 158 -

-

164 120

114 68.5 51 98 60 43 101.5 63 55 -

___ -

..~

324 279 498 393 323 418 315 254 39 0 27 3 224 304, 290

182 146

Ref. 148 124 I49

i;i

86 136' 88 67 113 72 55 112 71

>

I.r., solutions

145

t

Raman, gas phase

150

151

l.r., phenH+ salts

152

1.r. and Raman, R,N+ salts

153

"Further frequencies (not new) are listed in references 154 and 155 for Group IV tetrahalides. * From combinations.

Assorted vibrational data for tetrahalogeno-species of Td symmetry are gathered in Table 9 and require little comment. Full details have now been published of the vapour-phase Raman spectra of 21 Group IV tetrahalides MX, (M = C to Sn or Ti to Hf; X = F, C1, Br, or I).163a Fine structure A. Cabana, L. Lambert, and C. Pepin, J. Mol. Spectroscopy, 1972, 43, 429. H. W. Kattenberg, W. Gabes, and A. Oskam, J . Mol. Spectroscopy, 1972, 44, 425. 144 R. J. Coricejun., K. Fox, and W. H. Fletcher, J . Mol. Spectroscopy, 1972, 41, 95. Id4" A. V. Pleshkov, Optika i Spektroskopiya, 1972, 32, 819. I p s T. E. Thomas and W. J. Orville-Thomas,J . Inorg. Nuclear Chem., 1972, 34, 839. 148 R. A. Work and M. L. Good, Spectrochim. Acta, 1972, 28A, 1537. lo' W. Gabes, K. Olie, and H. Gerding, Rer. Trau. chim., 1972, 91, 1367. P. Van Huong and B. Desbat, Bull. SOC.chim. France, 1972, 2631. A. S. Quist, J. B. Bates, and G. E. Boyd, J . Phys. Chem., 1972, 76, 78. lKD R. J. H. Clark, B. K. Hunter, and D. M. Rippon, Inorg. Chern., 1972, 11, 56. 161 R. M. Clipsham and M. A. Whitehead, Canad. J . Chem., 1972, 50, 7 5 . lsa S. N. Ghosh, J . Inorg. Nuclear Chem., 1972, 34, 1456. 15s S. D. Ross, I. W. Siddiqi, and H. J. V. Tyrrell, J.C.S. Dalton, 1972, 1611. 16ya R. J. H. Clark and D. M. Rippon, J . Mol. Spectroscopy, 1972, 44, 479. 143

2 I2

Spectroscopic Properties of' Inorganic arid Orgariometcillic Compoutdy

shown in the Raman spectra of MCl, ( M = C, Si, Ti, or Sn) and MBr, ( M = C or Sn) at - 196 "C has been discussed 144a but adds little to similar work reported last year. Values of v1 and v3 for ACl, (A = C, Ge, or S n ) and ABr, (A = Ge or Sn) have been plotted against various measures of electronegativity and used to support those of Gordy and of Orville-Thomas but not Allred and Rochow's. It is further concluded that Si, Ge, and Sn do not use d-orbitals for n-bonding in these tetra halide^.',^ Some distortion from tetrahedral accompanies ion-pair formation (in benzene solution) between GaCI, or GaBr, and long-chain tertiary or quaternary ammonium cations: the extent of the disturbance revealed by the spectra is dependent upon the particular cation and the concentration. Typically, for [aliquat 336][GaC14] v3 = 377 and v4 = 151 cm-l(7;), but when the cation is [(C,H,,),NH]+ C,, rules apply: v1 362, v2 339, v3 160, v4 383, and The Ranian spectrum of solid PBr,Cl shows that it is to be 151 regarded as PBriC1-, isomorphous with PBr, : the fundamental frequencies of the cation are considerably split by site and correlation effects but are comparable with those reported earlier for PBr, and PBr7.14' Although not always providing new vibrational data, several other studies of tetrahalides have deepened our understanding of the spectra of these molecules. It is confirmed that there is no variation of the depolarization ratio for v,(a,) of the 35Cl and 37Clvariants of MCll ( M = C, Si, Ge, or Sn); it further appears that the value (0,003) is independent of the central atom.154 The depolarization ratios obtained by others 155 for the series of liquids MC14 (M = Si, Sn, or Te) are apparently a little larger (ca. 0.05) than Griffiths'; however, the contribution is valuable in listing also the absolute Raman intensities, spectral linewidths, mean-square amplitudes, and force constants. The crucial F34stretch-bend interaction force constant of CCll was estimated from a matrix-isolation investigation of the isotopic splitting pattern in the v4 ~ e g i 0 n . lAn ~ ~exact force field has been obtained for llaSnCl4and 12,SnC1, using new data from an i.r. study of the vapour spectra. From this, frequencies for 11eSn35C1337CI, 11sSn35C1,37C12, and 116Sn35C137C13 were estimated and used to account for the observed band contours of v3 for ll6SnC1, and 124SnC14.167 A similar exercise has been conducted for a selection of isotopic variants of SiCl, using previously published matrix-isolation data.15* Reaction of bromine and TIC1 yields a material formulated as T11[T1111C12Br2]. Its i.r. spectrum shows several more bands than previously reported for that anion, although this is not necessarily incompatible with the structure claimed. 1.r. bands are at 325w, 293s, 273s, 239m, 221s, 21 2s, J. E. Griffiths, Spectrochim. Acra, 1972, 28A, 1029. V. S. Demova, I. F. Kovalev, and M. G. Voronkov, Dokludy Phys. Chem., 1972, 202,

Ih4 156

Is6

15n

66. I. W. Levin and W. C. Harris, J . Chem. Phys., 1972, 57, 2715. A. Miiller, F. Koniger, K. Nakamoto, and N. Ohkaku, Spectrochini. A d a , 1972, 281% 1933. N. Mohan and A. Miiller, J . Mol. Spectroscopj,, 1972, 42, 203.

Vibrationnl Spectra 21 3 and 198s cm-l.lK9 ICl; (NO+ salt) has Raman bands at 284 [v,(a,,)], 265 [v,(b,,)], and 127.5 cm-l [~,(b,,)].l~~ A consideration of the v1 : v3 ratios of tetrahedral oxoanions led Baran to estimate v1 of XeO, at 800 cm-l,lsl but events appear to have overtaken him.lB2 The data are shown in Table 10. The force field for XeO, differs

Table 10 Species RiPO,

RU'~O, XeIBO, Xe**O, M no: FeO: RuOiCrOi[VS413[ N bS,I3[TaS4I3[ M oS,I2[WS412[ VSe4I3[ N bSe4I3[Ta Se,I3-[ M oSe,l2[ W Se.,I2a

Vibrational wavenumbers/cm-l for some MA, species Vl(Ql)

vde)

885.3 834.9 775.7 732.9 812 832 840 834 375 408 424 460 485 232 239 249 255 28 1

319k2 303 & 2 267 k 5 -

325 3 40 33 1 260 I

-

-_

-

-

__ _ _

v3(f2)

92 1 878.8 879.2 838.0 820 790 804 8 60 460 42 1 399 480 465 365 316 277 3 40 309

V40d

336 320.9305.9 291.4, 332 322 336 324 , -

Ref. 164 162 163 a

165 a

--

-

Raman data for aqueous solutions.

significantly from those of RuO, and OsO,; in particular, the negative value of F, emphasizes the differences in bonding (basically sp3 in XeO, but d 3 s in the others). A considerable collection of Raman and i.r. data for RuO;, MO!- ( M = Mn, Fe, or Ru), MOi- (M = Cr, Mn, Re, or Fe), and M04p- ( M = Ti, V, Cr, Mo, W, Fe, or Co), as Lit, K+, Cs+, Mg2+,or Ba2+ salts, has been analysed and MVFF constants have been tabulated. Some of the data shown in Table 10 were from solutions but the bulk came from solid samples (most of the salts are unstable in water or are insoluble): consequently various site- and factor-group split modes were observed. From knowledge of the symmetry correlations, values of the affected fundamentals were estimated and used in calculations. Combining the new observations with earlier data, trends in metal-oxygen force constants (MVFF) were demonstrated: (i) F(M-0) drops with oxidation state for a 160 161 *W

lRr'

R. P. Rastogi, B. L. Dubey, and N. K. Pandey, J . Iirorg. Nuclear Chent., 1972, 34, 831. J. P. Huvenne and P. Legrand, Compt. rend., 1972, 274, C, 2073. E. J. Baran, Z . Nururforsch., 1972, 27a, 1000. R. S. McDowell and L. B. Asprey, J . Chem. Phys., 1972, 57, 3062. F. Gonzalez-Vilchez and W. P. Griffith, J.C.S. Dalfon, 1972, 1416. R . S. McDowell, L. B. Asprey, and L. C. Hoskins, J . Chem. Phys., 1972, 56, 5712. A. Miiller, N. Weinstock, N. Mohan. C. W. Schlapfer, and K. Nakamoto, Z.NuturJ m c h . , 1972, 27a, 542.

2 14

Spectroscopic Properties of Inorganic and Orgairometallic Compounds

given metal (e.g. Ru""' > Ru"" > Ru") and (ii) a similar progression occurs within an isoelectronic series (0sv"' > Rev" > W"', Crv* > Vv > Ti"). An explanation is given in terms of varying extents of 0-and r-bonding.lB3 Wavenumbers for tetra-thio- and -seleno-anions are also in Table 10; further material appears in Chapter 6, Tables 8 and 18. Sundry data for substituted tetrahedral entities are shown in Tables 11 and 12. Table 11

Vibrational wat.enumberslcm--l for some substituted tetrahedral entities MAB3 of C,, symmetry

Species

e 1

I

V1

VOFS(i3) VOCl,(g) VOBr, TcO,CI(I) ReO,CI(I) MOS:-

w0s;-

MoOSei WOSei-

v2

1-'3

v(M B3)s 8(MB3)s v(MA) 720.5 256.0 1055 409.5 163.0 1042.5 272.0 118.5 1029.0 445 299 948 1002 43 3 303 468 858 460 869 293 120 858 292 (120) 878

>

I

v4

v5

v6

v( M B3)a 6( M B3)a Rock 80 1 204.0 503 124.5 401 .O 82.0 213.0 932 340 962 345 __ __ 490, 474 --_ __ 477 188 355 120 312 194 ( I 20)

I

Ref

169 166 167 a 168 Ir

Average of i.r. and Raman frequencies for Cs+ salts. * Raman, aqueous solutions. Further data for MOS:- species are quoted in Tables 7 and Raman solution values. 8 of Chapter 6 and for SP0:- and S,P03- in Table 37 of Chapter 5.

Table 12

Vibrational wavenumberslcm-' M02X2,of C,,symmetry a V02Fa 970 664 330 -

962 295 63 1 295 170a

for substituted

@2Mo02Si819 473 307 199.5 267 801 96 1 246 232 506 435 267 232 170 170b

V02CI, 972 ca. 453 316

M00, Si 815 470 305 199 267 793 246 499 267 170

loo

tetrahedral species Mo0,Seg836 359 280 799 -_ 342 114 168

W0,Se;863 335 283 -

808 -315 119 168

Further data on MO,S, types are in Chapter 6, Table 8 and PO&- is dealt with in Chapter 1.r. spectra of NH: salts. Raman spectra of NH: salts. 5 , Table 37. laaaA.Muller, K. H. Schmidt, K. A. Tytko, J. Bouwma, and F. Jellinek, Spectrochirn. Acta, 1972, 28A, 381. laa A. Guest, H. E. Howard-Lock, and C. J. L. Lock, J. Mol. Spectroscopy, 1972,43,273. A. Miiller, N. Weinstock, and H. Schulze, Spectrochim. Acta, 1972, 28A, 1075. Isa K. H. Schmidt and A. Muller, Spectrochim. Acta, 1972, 28A, 1829. R. J. H. Clark and P. D. Mitchell, J.C.S. Dalton, 1972, 2429. 1 7 0 A. Miiller, N. Weinstock, K. H. Schmidt, K. Nakamoto, and C. W. Schliipfer, Spectrochim. Acta, 1972, 28A, 2289. 170a E. Ahlborn, E. Diemann, and A. Miiller, J.C.S. Chem. Comm., 1972, 378. 170DE.Ahlborn, E. Diemann, and A. Muller, Z. anarg. Chem., 1972, 394, I .

-

[BKFI2291 1125 1081 2380 1177 802

-

[BDsFj1673 824 1059 1748 92 1 597 2285 1135 890 2179 2350 1197 872 335

P'B HsCN] -

Parentheses indicate a tentative assignment.

W3H3)s v(B-X) v(CN) e v(BH3)a 8(BH3)a pr(BH3) ~(BCN)

a1 v(BH,)s

[llBH,NC]2290 1105 760 2070 2350 1175 645 330

Table 13 Vibrational wauenumberslcm-l for BH3X- 174 [lOBH,CN]2290 1145 (910) a 2365 (1205) (880) 355

[11BD3CN]1661 906 800 2180 1761 870 675 330

P1BD3NC]1640 940 665 2075 1745 855 525 300

[l0BD3CN] 1671 926

2 I6

Spectroscopic Properties of Iriorgattic tirid Orgnnometallic Conipoutich

Further data for Cr0,X- species are in Chapter 6. At very low temperatures the spectra of Tc0,CI and Re0,Cl become more complex, possibly owing to a phase change.IF6 From a Raman vapour-phase study of VOCI, (and VOF,) it was possible to resolve the existing contradiction regarding the lowest fundamental, 125 cm-I: it is a n e-mode. Mixing VOCI, and VOBr, results in immediate redistribution at room temperature. The molecules VOC1,Br and VOCIBr, were accordingly identified by their Raman spectra and most fundamentals assigned.lBg Oriented polycrystalline films of Me1 were studied down to 10 K. Significantly, the first harmonics have the order of their symmetry species inverted with respect to those of the fundamentals, in discord with Davydov's theory as applied to molecular Wavenumbers/cm-' are :

(3: A1

B,

1'1

"2

2934.5 2933

1238.5 1235

21'2 9454.2 2455.2

1'3

21*:t

524.2 519.2

1037.9 1039.1

The v p fundamental (v,, = 2296.46 cm *) of CD3Br has been studied at high v(S-H) is at 2435 and 8(SH) a t cn. 1110cm-' in [R;N][HSO,] New data for salts of BH,X - (Table 13) have been analysed using the hybrid-orbital force field, together with earlier work on BH, , BH,CO, BH3,PF3,and BH,,PH3. The order of magnitude of 13-X force constants was found to be: X = F- > C N - > N C - > H - > CO > PF, > PH,.174 The v4 + v8 - v 8 band of "BH,CO at M . 700 cm ' has been a n a 1 ~ s e d . l ~ ~ ~ Molecules with stereochemically active lone pairs have been further investigated. Assignments for matrix-isolated SeF, and TeF, (i.r.) (Table 14), as well as vapour- and solid-phase data, have been analysed to show that Table 14 I.r. absorptiort waceniimherslcm-' for SeF, atid TeF, in rritrogerr mntrices

Mode v1 v, a, v3 a, v4 01

175

%eF, 742.6 588.5 405.5 -

TeF, 695.0 572 293.3 -

Mode v6 h, v7 b, v8 6 , vg b,

Se F,

"

598.0 364.0 725.2 254.0

Te F, 588.9, 587.9, 586.9 333.2 082.2 -

the axial bonds are weaker than the equatorial bonds. Oligomers formed upon diffusion, or in more concentrated matrices, appear to be bridged viu axial fluorines SeF, has been studied in all three phases by Raman li2

174

171n li5

J . Aubard and G . G . Dumas, Cotnpr. rend., 1972, 275, B, 419. R . W. Peterson and T. H . Edwards, J . Mol. Spectroscopy, 1972, 41, 137. R . Maylor, J. B. Gill, and D. C. Goodall, J.C.S. Dalton, 1972, 2001. J . R. Bcrschicd, jun. and K . F. Purcell, Inorg. Cheni., 1972, 11, 930. L. Lambert, C . Pepin, and A . Cabana, J . Mol. Spertroscopj-, 1972. 44, 578 C. J. Adams and A . J. Down% Specfro(hilf1.Acts, 1972, 284, 1841.

21 7

Vibrational Spectra

Table 15

Correlation of' the fuiidamentai modes of vibration of SeF, arid SF, with those of AsF, and BrF, HrF,

;2.lotle

Assignnieiitlcm- l

b, (trandation)

a2

(rotation)

-

I5

a1

b, (rotation)

226

3 53 Symmetry co-ordinatcs are used to describe approximately the fundamental modes. Coupling will be serious, notably for the two e' modes of AsF,.

spectroscopy (using a sapphire cell) and by i.r.(g). correlated with those of BrF, and AsF,, are shown complete assignments of i.r. and Raman data C102Fi,177and C10,F; (2) 17* (Table CIF:,O I;"

li7

I,''

The final assignments, in Table 15.lZ4 Rather have been made for 16) and for XNSF,

K . 0. Christc and E. C. Curtis, Inorg. Cherii., 1972, 11, 2196. K . 0. Christc, Irtorg. Nirclecir Chew. Letters, 1972, 8, 453. K. 0.Christe and F . C. Curtis, Iiiorg. Cheni.. 1972, 11, 35. I 10 cm-l. Internal modes of H 2 0 having large TO-LO splittings exhibit 2aa

2R3

X* 2R6

J. P. Coignac and M . Debeau, Contpf. rend., 1972, 275, B, 211. J. P. Huvenne, P. Legrand, and F. Wallart, Compr. rend., 1972, 275, C , 83. P. Barbier, G . Mairesse, F. Wallart, and J. P. Wignacourt, Cornpr. rend., 1972, 275, C . 475. J. A. McGinnety, J . Amer. Chent. SOC.,1972, 94. 8406. S. L. Chodos, J . Chem. Phys., 1972, 57, 2712. G . L. Cessac, R. K. Khanna, E. R . Lippincott, and A . R . Bandy, Spectrochim. A ( , l t i , 1972,28A, 917.

Vibrational Spectra 235 small correlation field splittings. The partial results shown in Table 31 are quoted as typical. Table 31

4 E A, E A,

E

Values (cm-l) of TO and LO for internal H 2 0 modes in Na2ZnCl,,3H20 and Na,ZnC1,,D20 Na2ZnC1,,3 D 2 0 TO LO 2609 2604 2537 2537 2525 263 287

Na2ZnCI,,3H20 TO LO 3505 3519 3516 3503 3458 3458 3442 3436 27 1 265 299 287

Raman spectra for eight oriented crystals M’,[FeC15(H20)] and M’2[InCIs(H,0)] showed a number of bands due to anion internal modes comparable with that predicted by factor-group analysis of the tetramolecular cell, Dii. Fewer than the predicted number of lattice modes were observed. Assignments are summarized in Table 32. The most unusual feature is that n(MC1,) modes apparently come above a(MC1,) modes. A mechanism involving cancellation of polarizabilities within the unit cell is proposed to account for the exceeding weakness of the B,, modes.287

Table 32 Raman wavenumbers/cm-’ and assignments for [MC1s(H20)]2-267 Mode

K2[FeC&(H20)]

C,,

Cs,[InCI,(H,O)I 280 27 1 280 256 215 187 162 149 124 310

Oxoanion-containing Crystals.-Since the ordered perovskites Ba,MB+M6+08(M = Mo, W, or Te) contain one (Ms+O,,) group per primitive cell and none of the oxygens are shared with other (MO,) groups, the i.r. and Raman spectra are both simple and can be assigned on the basis of Ohlabels for an isolated octahedron.2ss Typically, for Ba,MgWO,, Raman

& Vl

817 aRS 18b

v2

680

v6

444

I.r.

r v3

622

v4 388

‘External’ 319cm-l

D. M.Adams and D. C. Newton, J.C.S. Dalton, 1972, 681. A. F. Corsmit, H. E. Hoefdraad, and G. Blasse,J. Inorg. Nuclear Chern., 1972,34,3401.

236

Spectroscopic Properties of Itiorgcitiic mid Osganornetallic C o t ~ i p m ~ n d ~

The Raman shifts of Table 33 have been assigned to phonons (as well as some electronic Raman shifts) for the spinels and garnets shown.

Table 33

Raman wauenumhers/cm- and assignments jur YIG gnr-rrets 20D and norrnal spinels 269n

; ;IT2" YIG

2 74 315 347 380

Spinels

a

7

420 E, 447

E, + A,, T,, Eg

T2g

+ T,, + A19

593 507 A T2s l, 698 Al, 740 A,,

Theory: 3A1, I-SE,+ 14T,.

+ E,,

Ag2Mo04 88

Co2Ge0, ZnAl,04 -

302

242

757 347 869

643 757

65 5

-_

T.

v 2 for Raman-active modes.276 There is also considerable interaction between internal anion bending modes and external translatory From computed polariton dispersion curves for CaWO, it is shown that even modes due to anion internal vibrations have considerable disper~ion."~Vibrational spectra of powdered Ag,CrO, (orthorhombic) have vl and v3 some 20 40 cm-l lower than in K,Cr04; this has been interpreted in terms of appreciable Ag-0 Vihrariotial Spectru

Complex Cationic Salts.---The NH: librational mode in NH4Re0, was noted above. The Ranian spectrum of NH4CI shows a band at ca. 93 cm-' which behaves in a curious way on passing through an order/disorder transition at 242.8 K. At the transition temperature it splits into two: this is said to be due to short-range NH,Br has a phase transition at 234.5 K (5). Above fi Raman scatter at ca. 56 cm-l is anomalous i n the sense that it is associated with a zone-boundary TA phonon. Below 5 the tetragonal distortion halves the size of the Brillouin zone, relocating the above phonon to the zone centre, where it becomes Raman-active and shows unusual thermal dependence, increasing in intensity on cooling below c. It is accompanied by an intensity-decreasing mode (not predicted by group theory) attributed, as for NH,Cl, to short-range ordering. The evolution of long-range order governs the temperature behaviour of these bands.27e A phase change occurs at 10&-110 K in NH4C104(detected by i.r.): an assignment of i.r. and Raman data has been made for NH,C104 and its deuteriate.2H0 An especially interesting single-crystal Raman and i.r. study is reported for [M(en),]CI, ( M = Cr, Co, or Rh) using both racemic ( d l ) and optically active ( d ) The d-forms have symmetry Ds, 2 = 4, but it is not stated how they were handled experimentally in polarized light ; dl-forms have trigonal symnietry D i d , 2 = 4, and show much simpler spectra. Assignment of the MN, A,, breathing mode is clear-cut and shows strong R. A. Johnson, M . T. Rogers, and G. E. Leroi, J . Chem. Phys., 1972, 56, 789. P. Tarte and M. Liegeois-Duyckaerts, Specrrochint. Acfa, 1972, 28A, 2029. 27R M. Liegeois-Duyckacrts and P. Tarte, Specfrochitti. Acra, 1972, 28A, 2037. 2 7 7 V. C . Sahni and G . Venkataraman, Proceedings of the 15th Symposium o n Nuclear Physics and Solid State Physics, 1970, Vol. 3, p. 447. ma R. L. Carter, Spectroscopy Letters, 1972, 5 , 401. 'LiB C. H. Wang and R. B. Wright, J . Cheni. Phys., 1972, 56, 2124. L 7 B C . H . Wang and R. B. Wright, J. Chem. Phys., 1972, 57, 4401. D . J. I. Van Rensburg and C. J. H. Schutte, J . Mol. Structure, 1972, 1 1 , 229. J. Gouteron-Vaissermann, Conipt. rend., 1972, 275, B, 149. 2iJ

277.5

238

Spectroscopic Properties of Inorganic and Organome fallic Compounds

dependence upon the metal cation in accord with the order of LFSE. Thus, for the dl-forms the values obtained were: 547 (Rh), 527 (Co), and 494 (Cr) cm-I. Although symmetry species have been assigned, some doubt exists as to which bands are due principally to MN6 and which to (en) modes, if, indeed, such distinction can be made. Some results are shown in Table 34. A separate report has appeared dealing with the differences between spectra of the dl- and d-forms of these materials, and of some related tris-oxalates, in the region below 200 cm-1.282 Table 34

Vibrational

wuuenumbers/cm--'

dl-[M(en),]CI, 281

and

assignments

M = CO M = Rh M = Cr &&& I.r. 578 E, 544 A,,

Rarnan 582 E,

495 E,, 468 Azu 438 E, 368 E,

501 E,

a

527 A l ,

441 E, 372 E, 338 A l ,

I.r. 574 E, 542 A,,

498 E, 452 A,, 445 ? 354 E,,

Rarnan 576 E,

547 A l , 507 E, 447 E, 356 E, 329 A l ,

Raman

I.r. 550 E,, 517 A,,

for

Assignment

a

494

FIY-N) v(M-N),

442

}&ring) v(M-N), E,

A1 I

480 E, 450 Aau

01,labels used in this column; all other labels refer to unit-cell symmetry D d .

Complex Anionic Salts.-The Raman-active modes of Ca(OH)2 and its deuteriate have been assigned by single-crystal methods; all predicted The assignment, Table 35, is in complete discord modes were with an earlier one due to Krishmarthi, upon which others have based calculations. Inelastic neutron scattering data for Ca(OH), 284 are shown for comparison. In a Raman study of TO phonons in NaNO, (2@-250 " C )it was found that the ferroelectric phase obeys the rules of Cit. In the paraelectric phase six (not three as expected) extra resonances were observed. This Table 35

Vibrational wauenumbers/cm-l and assignments for Ca(OH),

A , , v(OH) A l , translatory E, translatory

E, rotatory 2n2 283 es4

Ca(OH), 3610 357 254 680

283

Ca(OD), 2664 350 252 475

283

5:zg) +

Ca(OH),

2a4

310

ca. 250 ca. 100

R of types E,, E, T R of types A l p , Aru, E u T(acoustic) T(acoustic)

+ T(E,)

J.-P. Mathieu and J. Gouteron-Vaissermann, Compt. rend., 1972, 274, B, 880. P. Dawson, Solid State Comm., 1972, 10, 41. A. Bajorek, J. A . Janik, J. M. Janik, I. Natkaniec, T. Stanek, and T. Wasiutynski, Acta Phys. Poion. ( A ) , 1971, 40,431.

Vibrational Spectra

239

anomaly is accounted for by recognizing the effect of NO; disordering along the 6-axis. The nitrogen atom jumps between two equivalent sites by the flipping of NO; about the a-axis: temperature-dependent coupling between normal modes precipitates this Iqbal continues his courageous studies on solid azides. In a singlecrystal study2ss of KN, (400--5000cm-') the technical quality of the spectra was higher than in an earlier investigation (by Bryant). The very considerable fine structure associated with the main absorption regions was interpreted in terms of internal -t external mode combinations, including those from critical points and symmetry lines in the Brillouin zone. This work forms a good basis for elucidation of the optical phonon frequencies determined by neutron spectroscopy, which must be completed before the lattice dynamics of the solid are fully understood. 1.r. and Raman singlecrystal methods have been applied to a study of the phase transition in T1N3.287Below the transition temperature the low-frequency spectrum becomes very complex and a non-centrosymmetric structure may be formed. At 90 K internal modes have wavenumbers/cm-l:

4

A,,

622

E,

628

vl{

4,

-

A,,

1323

1995 cm-I

v3 E,

whereas at 298 K librational lattice modes are at 178 (&,) and 47 cm-l (E,), and a translational mode is at 33cm-l(Eg). About half the number of internaZ modes of KNCS predicted by factor-group analysis were observed in a single-crystal i.r. (to 400 cm-l) and Raman study. However, the main interest lies in the lattice-mode study. Analysis of the v 3 + lattice mode complex, Figure 2, yielded values of mode energies at points away from k 0. This is possible because conservation of momentum in a twomode process is satisfied if component modes have non-zero equal and opposite wave vectors, k and -k. Thus, k values can range throughout the Brillouin zone, although only regions of high density of states will make significant contributions. Typically, for the 11 c i.r. experiment :288

-

39 T ( A ) along I;, A, A 69 B,, B,, at I? 94 B,, B3, along Z, A, A

+ +

109 T(B,,) along Z, A, A 126 R(B,, B3,) at I' 142 T(B,,) at X, Y, Z

+

The assignment of Table 36 was deduced from i.r. and Raman work with single-crystal LiI03, C:. The dielectric constant determined by the LST relation does not reveal any large contribution by lattice dynamics to the low-frequency dielectric response.28QRaman spectra of NaClO, and KClO, DM

zn6 288

C. M. Hartwig, E. Wiener-Avnear, and S. P. S. Porto, Phys. Rev. ( B ) , 1972, 5 , 79. Z. Iqbal, J . Chem. Phys., 1972, 57, 2422. Z. Iqbal and M. L. Malhotra, J . Chem. Phys., 1972, 57, 2637. Z. Iqbal, L. H . Sarma, and K. D. Moller, J . Chem. Phys., 1972, 57, 4728. W. Otaguro, E. Wiener-Avnear, C. A. Arguello, and S. P. S. Porto, Phys. Reo. (B), 1971, 4, 4542.

240

Spectroscopic Properties of Itrorgnnic atid Organometallic Conipourrds

2200

2000

1800

W a v e n u m b e r I cm-’

Figure 2 1.r. absorption of single-crystal KCNS in the v 3 2 external mode region: parallel to c, dotted line: perpendictrlar to c, full line. (Reproduced by permission from J . Chem. Phys., 1972, 57, 4728)

Table 36 Raman wai:enrrrnberslcm-‘ and assignments for LiI03, C:

TO 358 795

148 238

LO 468 817

Predicted: 4A, + 5B, (inactive) are due to ‘external’ modes.

288

TO

98 200 330 340 332 ----_ 3____.._....__._________ 70 460 347 769 848 765

LO

180

+ 4E1+ 5E2. Frequencies

above the lines

before and after X-ray treatment showed that new lines appeared ca. 680 and 980 cm-l: these are attributed to O;, formed by loss of Cl from the anions.2Bo S. Radhakrishna and A . M . Karguppikar, Proc. Itrdian Acad. Sci. ( A ) , 1972, 75, 132

24 1 Single-crystal Raman spectra reported for CsNO, 291 complete the assignment of all alkali-metal nitrates. In the disordered phase of CsNO, the discrete lattice spectrum is replaced by a broad band at cu. 90cm-l superimposed on an anisotropic wing. The internal vibrations retain their polarization characteristics in the high-temperature phase, and the melt spectra are very similar to those of the disordered crystal at elevated temperatures. For the room-temperature structure (C,), (wavenumbers/cm-l) Vibrutioital Spectra

A,

E

29, 39,

50, 113 116

715 704

1051 1048

1383 1345

1396 1420

1.r. spectra of NO; isolated in K X and NaX matrices show that the site symmetry is C3G.Harmonic frequencies were shifted to higher values as the lattice constant of the matrix decreased. In KI, bands due to The vibrational v(interna1) 2 localized lattice modes were spectrum of Na,S03 has been assigned, from powder data, on the basis of unit-cell symmetry. Anomalous results previously reported for its i.r. spectrum in aqueous solution are shown to be due to a reaction with AgCl cell CaCO, I11 is a phase formed by compression of calcite below 200-300 "C. The Raman spectrum at 77 K is reported but interpretation is difficult in the absence of structural information. The large number of bands indicates low I3C substitution has been used to determine coupling constants for v2 (ca. 850 cm-l) of C o t - in some compounds with the aragonite structure ( M = Ca, Sr, Ba, Eu, or Pb) and in Li,CO, and NazCO3,H20. A relationship found between the value of the coupling constant and the fifth power of the anion distances shows that the coupling is governed by short-range repulsive forces, not by dipole-dipole Bzu and BSu modes in azurite, 2CuCO,,Cu(OH),, were distinguished with the aid of a normal-co-ordinate analysis.2gs BeS04,4H,0, a uniaxial piezoelectric crystal, has been studied by singlecrystal Raman technique in the v, SO:- region.2g7The new values (cm-l) are: B,(T) E(T) E(T)

1081 1124 1084

E(L) E(L)

1110 1162

A full Raman single-crystal assignment for K,SO, is available.298 1.r. spectra confirm the presence of a continuous solid solution between D. W. James and J. P. Devlin, J . Chem. Phys., 1972, 56, 4688. M. Tsuboi and I. C. Hisatsune, J . Chem. Phys., 1972, 57, 2087. J. D. Brown and B. P. Straughan, J.C.S. Dalton, 1972, 1750. M . Nicol and W. D. Ellenson, J . Chem. Phys., 1972, 56, 677. W. Sterzel and W.-D. Schnee, 2. anorg. Chem., 1972, 392, 173. B. Taravel, G . Chauvet, P. Delorme, and V. Lorenzelli, C b m p r . rend., 1972,274, B, 8 8 2 . R . Unger, Phys. Stat. Solidi ( B ) , 1972, 49, 107. M . Debcau, Reo. Phys. Appl., 1972, 7 , 49.

242


CaS0,,2H20 and anhydrite 2n9 and v1 and v, SO:- frequencies are listed for a series of metastable crystals in the BaS0,-CaSO, A full assignment of the i.r. single-crystal spectra (30-4000 cm-l) of Li2S04,H20 and its deuteriate at ambient and liquid-nitrogen temperatures has been supported by a force-constant calculation. The assignments for external modes of the water are compared with inelastic neutron-scattering data in Table 37.301 Others, also comparing vibrational data with those from i.n.s. for the same compounds, claim that acoustic modes are showing through in the vibrational spectra owing to disorder associated with the water m01ecules.~~~

-

Table 37 External water modes (cm-l) in Li2S04,H20 Z.r.

P. Pu + P+ PT + Po

Translations

I.n.s.

Ha0 600 533 338

D2O 440 269

H2O 769 556 343

196 180 143

194 176 141

235 186 164

Full single-crystal Raman assignments are reported for KH2P04,303* KDaPO4, RbH1P04, and NH4HaP04.303 In addition to the ferroelectricphase modes (at 90 K) observed by Kaminov and Damen, a sharp line at 5 15 cm-l was found in that phase for KH2P04and is related to phosphorusatom movement.304 1.r. absorption data have been listed for FeAsO,, F ~ A s ~ . ~and ~ FeAso.nn6P0,00504,2H20.306 ~ P ~ . ~ ~ ~ ~ ~ , Previous assignments of the vibrations of the formate ion have been confirmed by a single-crystal i.r. and Raman study of Sr(HCOO),. 1.r.active external modes were estimated from combinations but Ramanactive ones were observed directly. Below 250 cm-1 9A + 8B1 + 8B9 + 8B3 modes were found in exact correspondence with predictions for translatory lattice modes. None of the expected 6 ( A + B1 + B2 + B,) rotatory modes were found.306 No evidence is given to justify such a distinction. A qualitative assignment of i.r. and Raman spectra of Cu(HC00),,4H20 has been given.3o7 Raman spectra of oriented crystals and i.r. spectra of thin films of CSH(CF,COO), and KH(CFsC00)2 and their deuteriated 20p

301

307

M. Soustelle, B. Guilhot, and J.-J. Gardet, Compt. rend., 1972, 274, C, 853. 0. Vojtech, J. Moravec, and I. Krivy, J . Inorg. Nuclear Chem., 1972, 34, 3345. S. Meshitsuka, H. Takahashi, and K. Higasi, Bull. Chem. SOC.Japan, 1971, 44, 3255. E. Mikuli, J. M. Janik, G . Pytaz, J. A. Janik, J. Sciesinki, E. Sciesinska, and A . Mazurkiewicz, Insr. Nuclear. Phys., Cracow, Rep., 1972, INP-791/PS, 15pp. E. A. Popova, Izvest. Akad. Nauk. S . S . S . R . , Ser. fiz., 1971, 35, 1812. J. P. Coignac and H. Poulet, J. Phys. (Paris), 1971, 32, 679. F. d'Yvoire, Compt. rend., 1972, 275, C, 949. N. R. McQuaker and K. B. Harvey, Canad. J. Chem., 1972, 50, 1453. R. S. Krishnan and P. S. Ramanujan, Spectrochim. Acta, 1972, 28A,2227.

243 analogues have been fully assigned, the particular interest of this work being modes involving the hydrogen atom of the symmetric hydrogen bond. For the Cs+ salt they are:3o8 Vibrational Spectra

1.r. 1168 cm-l 870 -

1830 1020 940

Raman 1200 cm-l 825 798 -

__

-

COH COH OH0 OH0 OH0 OH0 OH0

6 bend

ybend sym. stretch usym. stretch 6 bend y bend

I35 twist A particularly complete study of oriented crystals (i.r. reflectance and Raman spectra) of Li(CH3C00),2H20 has appeared.s08a Both 6Li/7Li and lH/,H substitution was used. The complete i.r. range 2&-3600 cm-l was covered and a full assignment deduced. In combination with other recent work on hydrates, this forms an important contribution to our knowledge of the lattice dynamics of hydrated salts. 1.r. reflectance from beryl in the region 280-1400 cm-l allowed location of 6Azu 13&, modes of the P6/rncc structure, leaving only 3E1, ~ n d e t e r m i n e d . In ~ ~a~ single-crystal Raman study of K3[Fe(CN),] most of the factor-grouppredicted modes were observed. In particular, the 6(CFeC) bend becomes completely mixed in with the large number of lattice modes present in the range 51-185 cm-l and loses its identity.310

+

Molecular Crystals.-Work on the Raman spectra of solid hydrogen has been reviewed at length,311and the densities of phonon and libron states Vibrational spectra of have been investigated by neutron the solid halogens have been re-a~signed.~'~ An assignment of the i.r. and Raman data for crystalline CIOa (C'i;, 2 = 4) was made by analogy with those of SO,: vl, Al 912-917, A2 939-944; v2, A l 465, A, 456-459; v3, B1, B, 1052-1121 Although the i.r. spectrum of phosphonitrilic chloride trimer, (PNCl,)3, has been rather fully studied, the vibrational assignment has been illfounded for years because of lack of definitive Raman data. Using singlecrystal methods most of the Raman-active modes have been assigned u n a m b i g u ~ u s l y316 . ~ ~ In ~ ~ particular, the long-sought vp(a;) mode was located at 172 cm-l. A full assignment for R u ( ~ T - C ~crystals H ~ ) ~ has been deduced from i.r. and Raman 308 30Ha

308 310

312 313 :Ii4

ylb s16 31i

P. J. Miller, R. A. Butler, and E. R. Lippincott, J. Chem. Phys., 1972, 57, 5451. M. Cadene and A. M . Vergnoux, Spectrochim. Acta, 1972, 28A, 1663. F. Gervais and B. Piriou, Compt. rend., 1972, 274, 8, 252. D. M. Adams and M. A. Hooper, J.C.S. Dalton, 1972, 160. H. L. Welsh, E. J. Allin, and V. Soots, Phys. Solid State, 1969, 343. H. Stein, H. Stiller, and R. Stockmeyer, J . Chem. Phys., 1972, 57, 1726. Y. S. Jain and H. D. Bist, ref. 277, p. 485. J.-L. Pascal, A. Pavia, and J. Potier, J . M o f . Structure, 1972, 13, 381. D. M. Adams and W. S. Fernando, J.C.S. Dalton, 1972, 2503. J. Klosowski and E. Steger, Spectrochim. Acta, 1972, 28A, 2189. D.M. Adams and W. S. Fernando, J.C.S. Dalton, 1972, 2507.

244

Spectroscopic Properties of Inorganic and Organometallic Compouncis

Thiourea undergoes a transition at 202 K to a fcrroelectric phase characterized by a very low-frequency ‘soft mode’ which is strongly temperature-dependent (35 cm-’ at 178 K).318 Assignment of the complicated vibrational spectra of CdCl,(thiourea), and CdCl,(thiourea), has been considerably strengthened by single-crystal i.r. and Raman work.31e Others.-Two studies have been made of single-crystals of Bi,,GeO,, by Raman 321 and one of Bil,Si0,,.321 They are isomorphous, T 3 . The germanium compound shows 36 lines in the range 40 720 cm at 15 K and the silicon crystal 43 in the range 40--850 cni-l; all were classified. The two low-frequency bands of HgCr,Se,, determined at 300 K by i.r. absorption and reflection, are at 289.9, 281.8 (LO), and 286.8, 268.6 (TO) cm-1.322 Pyrargyrite, Ag3AsS3, should show 3A1 + 4E modes: single-crystal Raman experiments located bands at 362 and 186 cm( A , ) and at 332 and 120 cm-l (E). A series of isomorphously substituted samples (Sb replacing As) was also investigated q ~ a l i t a t i v e l y . ~ ~ ~ $‘do

921 3a2

923

J. P. Benoit, M. Deniau, and J. P. Chapelle, Compt. rend., 1972, 275, B, 665. D. M. Adams and M. A. Hooper, J.C.S. Dalton, 1972, 631. B. K. Bairamov, B. P. Zakharchenya, R. V. Pisarev, and Z. M. Khashkhozhev, Fit. tverd. Tela, 1971, 13, 3366. S. Venugopalan and A. K. Ramdas, Phys. Rev. (B), 1972, 5 , 4065. T. H. Lee, T. Coburn, and R. Gluck, Solid State Comm., 1971, 9, 1821. D. K. Arkhipenko, A. A. Godovikov, S . N. Nenasheva, B. G. Nenashcv, B. A . Ovekhov, V. S. Pavlynchenko, and M. G. Serbulenko, Kvanfovaya Efektron (Moscow), 1971, 69.

5

Characteristic Vibrational Frequencies of Corn pou nds containing Main-g roup Elements BY S.

R. STOBART

Divisions within this chapter remain unchanged from those employed in previous volumes of the series, vibrational data for Main-group compounds being divided into eight sections, one devoted to each of the Main Groups of elements in the Periodic Table. Further subdivision within each of these sections has been achieved where this is considered to be useful by dealing with each element of the Group in turn (in order of increasing atomic number) or by collecting together references concerning compounds possessing similar groups of atoms. 1 Group I Elements

Monolithium derivatives of acetonitrile and benzonitrile have been isolated and shown by molecular weight measurements to be respectively tetrameric and dimeric,l lowering in frequency of v(C=N) as well as other evidence suggesting association through Li. CN interaction. Skeletal modes for thc acetonitrile derivative are found (it-.) at 432 and 575 cm-l for 'LiCH,CN, shifting to 455, 605 cm-l for 6LiCH,CN and to 410, 575 cn1-l for 'LiCD,CN. The 432cm-l band is identified as v(Li-C), that at 575 cm-l being attributed to v(Li- O N )between the lithium atom and an adjacent nitrogen atom in the tetramer, on the basis that in the proposed structure a Li-C mode should be sensitive to deuteriation whereas a Li-N mode should not. Similar observations for PhCH(Li)CN give v(Li-C) at 460 and v(Li. - N ) at 575 cm- l. The compounds Me,SiOM1,OPMe, (MI = Li, Na, or K) have been assigned2 the cubane-like structures (1) on the basis of physical measurements, including i.r. data. A

-

-

R. Das and C. A . Wilkie, J . Anrer. Chem. SOC.,1972, 94, 4555. H . Schmidbaur and J. Adlkofer, Chem. Ber., 1972, 105, 1956.

245

246

Spectroscopic Properties cij’ Itiorg-Kniiic and Orgnrroim~tallicC’omporrndy

study of the vibrational spectra of 7LiCH,C00,2H20, sLiCH,C00,2H,0, and 7LiCH3C00,2D20is consistent with the known chain structure which includes Li,04(H20)2units. An analysis of fundamentals expected for such units is related to the observed spectra, placing vw,,(Li-O) at 340 cm-l (i.r.) and vmym(Li-O) modes at 429 (Raman) and 498 (i.r.) cm - I ; bands at 210, 241 cm-l are assigned to Li02 deformation modes. Far4.r. spectra of Li+, NH4+-,and Na+ salts in 4-Mepy have been measured by Handy and P O P O V .Frequencies ~ of ion-solvent vibration bands are 390-350 (Lit), 200 (NH,+), and 175 (Na+)ern l ; the position of the Lit solvent band is strongly affected by 2-substitution of Mepy. Characteristic frequencies observed in the far-i.r. for alkali-metal ions encaged in crown ethers in solution have been reported.5 With dibenzo-18crown-6, there is no frequency-dependence of bands attributed to the (Na+-crown) or (Ki-crown) motions (respectively at 214 and 168 cm-I) on either anion or solvent, allowing calculation of ion-crown forces based on an M106S2aggregate with D6h symmetry. Raman spectra of concentrated aqueous solutions of NaOH and KOH show low-frequency bands (282- 322 cm-l) which have been associated6 with the stretch of an ion pair M+. .OH-. Matrix-isolation Raman spectroscopy has been used to show that cocondensation of an atomic beam of lithium with molecular oxygen at 4.2-15 K affords Li02 [v(O-0) at 1097 cm-’1. In LiCl,nH,O, v(Li-0) is assigned at 520, 456 (n = l), 482 ( n = Z), and 476 cm-l ( n = 3). The vibrational frequencies of alkali-metal cations in their equilibrium positions in various metal-alkali-oxide glasses have been observed as cation-massdependent bands in far4.r. spectra.

2 Group I1 Elements The vibrational spectrum of beryllium borohydride has again received attention. Gaseous and matrix-isolation studies by both i.r. and Raman methods on BeB,H,, BeB,D,, and BeB,HD, are reported,1° and their interpretation emphasizes the structural complexity of this system. Gasphase measurements suggest an equilibrium between two coexisting structures, but only one form appears to be present at 20 K, probably with C3,. symmetry (2). The vibrational spectrum of (Et,Be), has been assigned l1 in terms of D2,, pseudosymmetry; similar data for gaseous and liquid BuiBe are consistent l 2 with the point group D3,,, lower symmetry ( D 9 ) being

lo l1

M. Cadene and A. M. Vergnoux, Spectrochim. Acta, 1972, 28A, 1663. P. R. Handy and A. I. Popov, Spectrochirn. Acta, 1972, 28.4, 1545. A. T. Tsatsas, R. W. Steams, and W. M. Risen, J. Amer. Chem. Soc., 1972,94, 5947. S. K. Sharma and S. C. Kashyap, J. Inorg. Nitclear Chem., 1972, 34, 3623. H. Huber and G. A. Ozin. J . Mal. Spectroscopy, 1972, 41, 595. M. blanewa and H. P. Fritz, Z. nnorg. Chem.. 1972, 392, 227. G. Exarhos and W. M . Risen, Solid State Comm., 1972, 1 1 , 755. J. W, Nibler, J. Amer. Chem. Soc., 1972, 94, 3349. N. Atam, H . Miiller, and K. Dehnicke, J. Organometallic Chem., 1973, 37. I 5 J. Mounier, J. Organometallic Chern., 1972, 38, 7.

Cliarncteristic Vibrational Frequencies of Contpounds

247

(2)

suggested for the solid state. For the first of these compounds v(Be-C) frequencies are given as 925 (Ellu)and 875 cm-l (Ag). The azido-derivatives [BeCI(N3),0Et2I2and [Be(N,),], exhibit i.r. bands at 814, 685, and 824, 710 cm-l attributed l3 to v(Be-N) modes. Dinitratotriberyllium tetra-tbutoxide shows i.r. bands at 1505, 1515 cm-', indicating l4 unidentate are also nitrate co-ordination ; i.r. frequencies for other X2Be3(OB~t)4 listed. The adduct [(Et,Be),SCN]- has a vibrational spectrum which suggests l 2 donation through S: v(SCN), 2100, 740; V ~ ~ ~ , / V ~ , ,865; ~(B~~S), and 8(Be,S), 228 cm-l. Raman spectra of vitreous, polycrystalline, and molten BeF, have been obtained lS in the range 25-630 "C. These data are compared with the i.r. spectrum of vitreous BeF,, and lead to an assignment based on a model isostructural with p-quartz (Table 1). Reaction of BeCI, with nitrosyl chloride affords l6 (N0+),BeC14-, with v(Be-CI) assigned at 610, 584, and 553 cm-l. Table 1 Raman spectrum of vitreous BeF, (Dd lattice structure) Waoenumber/cm-' Assignment 282 (R) a, 8(BeFBe)

Wannagat and his co-workers have reported l7 i.r. frequencies for the compound [(Me3Si),N],Mg; a band at 465 cm-1 is assigned to v,,,,(MgN,). For [Mg(N&)61CI, and [Mg(NDdt~lCb,v3 [v(Mg--N)I and v4 [a(Mg-N)I for the cation are found l a at 363, 198 (NH3 complex) and 343, 185 cm-l (ND3complex). The magnesium nitrate-water system has been examined l9 by Raman spectroscopy, covering the entire range from highly dilute solution to an anhydrous molten salt mixture with NaNO,. In nearsaturated solution, v(Mg-OH2) is observed at 354 cm-'. 1.r. absorptions due to vibrations of the hydroxy-groups have been reported for Sr(OH), and Sr(OD),, and a shift of OH modes to lower frequency between M(OH), (M = Sr or Ba) is discussed in relation to Id Is Ii

N. Wiberg, W.-Ch. Joo, and K. H. Schmid, Z . anorg. Chem., 1972, 394, 197. R . A. Andersen, N. A. Bell, and G. E. Coates, J.C.S. Dalton, 1972, 577. A . S. Quist, J. B. Bates, and G. E. Boyd, Spectrochim. Acta, 1972, B A , 1103. J . MacCordick, Nuturwiss., 1972, 59, 421. U. Wannagat, H. Autzen, H. Kuckertz, and H. J. Wismar, Z . unorg. Chem., 1972, 394, 254.

In IH

R. Plus, Compt. rend., 1972, 275, B, 345. M. Peleg, J . Phys. Chem., 1972, 76, 1019.

248

Spcctl-oscopic Propertic>s of I t w r g m k

utid

Orgrrtionw/ollic Compoirtirl.~

hydrogen-bonding.20 Some related data for Ba(OH), hydrates have also been given.21 In a review 2” the i.r. spectra of Group I 1 dihalides have been critically discussed. Several other papers23-25deal with use of i.r. spectroscopy in investigation of oxide surfaces (Be, Mg, and Zn) and other solid-state properties. 3 Group I11 Elements Compounds containing B-H Bonds. Fluorination of Me,N,BH, with H F affords the new fluoroboranes Me,N,BH,F and Me,N,BHF,, for which unassigned i.r. frequencies have been listed;26 those for Me,N,BF, are identical with literature values. Other borane adducts for which i.r. data have been reported are PF2(N3),BH3,27 XPF,,BH, (X = F, CI, Br, or and diborane d i h ~ d r a t ewhich , ~ ~ at low temperatures shows four bands attributable to B-H stretching modes in agreement with the formulation BH2(H20),+BH4-rather than BH3(H20). In the Raman spectrum of a Et,O adduct of S7NBH2,v(B-H) modes are found 30 at 2419, 2409 cm-* with v(S-N) at 766, 750 cm-l. Unassigned i.r. data have been given31 for (3). 1.r. spectra for M(BH4)4(M = Zr or Hf) are nearly identical, only one v(B-H)termirlal being observed 32 as expected for terdentate BH4 groups, indicating similar structures for the two compounds. Keller has found 33 that reaction of Al(NMe,), with excess diborane in ether gives, Me,N-BH, H2B,/ \,NMe, MeS=BH,

(3)

NMe,

HzB’ ‘Al(BH4)2 “/Me, (4)

in addition to known products, two new compounds for which cyclic structures are proposed on the basis of n.m.r. evidence: for one of these, (4), i.r. bands at 2510, 2420, and 2340 cni-l are assigned to v(B- H) modes whereas a further band at 2120 cm-’ is attributed to v(B-H--1). Reactions of substituted lithium amides with diborane yield new p-aminodiboranes R2NB2H, (R = Prn or Pr’) and RNHB,H, (R = Pr”, H. D. Lutz, R. Heider, and R. A . Becker, Spectrochim. Acto, 1972, 28A, 871. G. M. Habashy and G. A. Kolta, J. Inorg. Nuclear Chem., 1972, 34, 57. I. Eliezer and A. Reger, Co-ordination Chem. Rev., 1972, 9, 189. lJ A. A. Tsyganenko and V. N. Filimonov, Doklady Phys. Chem., 1972, 203, 257. 2 4 L. Genzel and T. P. Martin, Phys. Starus S o l i d (B), 1972, 51, 91. 2 5 A. V. Sofronova and L. V. Kolobova, Ritss. J. lriorg. Cheni., 1971, 16, 794. J. M. Van Paasschen and R . A. Geanangel, J. Atner. Chem. Soc., 1972. 94, 2680. 37 E. L. Lines and L. F. Centofanti. fnorg. Chem., 1972, 11, 2269. 3R R. T . Paine and R. W. Parry, Inorg. Chem., 1972, 11, 1237. t u P. Finn and W. L. Jolly, fnorg. Cheni., 1972, 11. 1941. 3 0 M. A. Mendelsohn and W. L. Jolly, Inorg. Chem., 1972, 11, 1944. 3 1 A. B. Burg, fnorg. C h e t ~ . 1972, , 11, 2283. 32 T. J. Marks and L. A. Shimp, J. Arner. Chern. Sor., 1972, 94, 1542. y3 P. C. Keller, J. Atnet-. Chern. Soc., 1972, 94, 4020. 2‘:

Clinrcrct er.ist ic Vihru t iono / Frc~ y rr enc ies of Comp o ir n ds

249 h i , Bu" Bu', But, or C,H,,) for which i.r. frequencies have been listed.31 B-H fundamentals have been assigned 35 for F,PB,H, and F2ClPB3H,, near 2110 and 1570cm-l. Borlin and Gaines have with V(B-H)l,rjdgc given 36 unassigned gas-phase i.r. data for Me2AIB3H8and Me,GaB3H8, the similarity of the spectra indicating closely related structures ( 5 ) . The i.r. spectra of m-borallyl complexes of transition metals (Ni, Pd, and Pt) show distinctive feature^,^, absorptions attributable to the T-B,H,~ligand being identified as follows: v(B-H), 2493-2288 cm--l (complex contour); also 1897, 1642, and 1577 cm-l (the last of these bands is absent for B,H,- and its metal complexes). Partly assigned i.r. frequencies for XPF2,B4H8(X = F, C1, Br, or I ) have been reported.2H For B,H,Br, the following assignment of observed i.r. bands has been proposed38 (cm-l): 2592, 2502, v(B-H); 2165, 1145, 1018, 8akeletal; 970, BH2 rocking; 870, v ~ ~ ~ ~ ( B2100, H B )v,,,,,(BHB); ; H,

'C \ H,B--N=c-BH,

(6)

BH2 torsion; 693, 683 ? v(B-Br). Reaction of KSEt with diborane in THF affords K[EtS(BH,),], with3, v(B-H) at 2375, 2330, 2295, and 2202 cm-l. Macrocylic cyanoboranes (BH,CN), have been prepared and partially separated, that with n = 5 ( > 90% pure) showing 4 0 i.r. bands at 2469,2441, and 2429 [v(B-H)] and 2295 cm-l [v(C=N)]. The appearance of only one v(C==N)absorption at a relatively high frequency is considered to be consistent with the presence of a single bridging cyano-group as required in a cyclic oligomer (6). In the i.r. spectrum of the salt K i [H,BC(OH)=N(H)CH,COO]- a band at 2280 cm-l is described as typical 4 0 n for boranocarboxylates. Rapid exchange of bridging hydrogen atoms of BsHlo with DC1 has been demonstrated using i.r. spectroscopy,41 attenuation of B-H-B I' ,I' I"

A'

X'

41

L. D. Schwartz and P. C. Keller, J . Amer. Chem. SUC.,1972, 94, 3015. R. T. Paine and R. W. Parry, Zmrg. Chem., 1972, 11, 268. J . Borlin and D. F. Gaines, J . Amer. Chem. Suc., 1972, 94, 1367. L. J . Guggenberger, A. R. Kane, and E. L. Muetterties. J . Amer. Chem. Suc., 1972, 94, 5665. J . Dazord and H . Maigedt, Bull. SUC.chim. France, 1972, 950. J. J . Miclcarek and P. C. Keller, J.C.S. Chem. Cumm., 1972, 1090. B. F. Spielvogel, R. F. Rratton, and C. G. Moreland, J . Anter. Chem. SOC., 1972, 94, 8597. M. J. Zctlmeisl and L. J. Malone, Inorg. Chem., 1972, 1 1 , 1245. H. D. Johnson, V. 'r. Brice, G . L. Brubaker, and S. G . Shore, J . Amer. Chem. Suc., 1972. 94. 67 1 1

250


bands being accompanied by the appearance of v(B-D-B)bri,jge at 1 125 cm-l. Studies on monosubstituted decaboranes have established that the frequencies of v(B- H)tlriae (1 6-1 300 cm-l) and 6(BH) (800- 650 cm-l) are characteristic of the site of decaborane skeleton s ~ b s t i t u t i o n . ~ ~ Controlled hydrolysis of hexadecaborane(20) affords 43 a new stable hydride B14H18 with (i.r.) V(B-H)termiml at 2562, 2595, V(B-H)briae at 1830-1 925 and 1540-1600 cm-l. Reaction of hexaborane(l0) with Fe,(CO), gives p-Fe(C0)4-BB,Hl, in which the iron centre is co-ordinated to the unique basal B-B bond of the b ~ r a n e i.r. ; ~ frequencies ~ for v(B-H) modes are 2578, 2555, 2495 (terminal), and 1935, 1850cm-l (bridge). Bruce and Ostazewski have synthesized 45 a stable copper carbonyl, HB(pyrazolyl),Cu(CO), with v(B-H) at 2465 and v ( C 0 ) at 2083 cm-l. Brown and co-workers have reported 46 identification by i.r. spectroscopy of the first monomeric dialkylboranes. Hydroboronation of tetramethylethylene (tme) yields known trialkyl diboranes, but when the tme/borane i~l ratio reaches 16 : 1 the reaction mixture shows only ~ ( B - H ) t e r ~ l ~at 2470cm-l. Similar reaction in a deuteriated system gives a product with v(B-D)termillal, 1820cm-l. For 2,7-dimethyl-l,6-diboracyclodecane (7), and .-H.. bis-borinan (8), vssm (B:.. .:B H’ 1560 cni-l respectively.

absorptions are observed O7 at 1595 and

Carbaborane chemistry has received considerable attention during 1972 and a number of papers including vibrational data have been published. In the i.r. spectrum of 1,2-dicarba-nido-pentaborane(7),obtained from the reaction of acetylene with B4HI0,two bands at unusually high frequency (3150, 3075 cm-l) for v(C-H) are consistent 48 with a relatively large C-C bond order in the proposed structure (9). Raman spectra of 4,5-dicarbanido-hexaborane(8) and its C-methyl derivatives C2B4H,Meand CzB4HeMez (10) have been measured; assignments made by comparison with remeasured i.r. frequencies are discussed in detail. Tentative separation of

44

4n

F. Hanousek, B. Stibr, S. Heimanek, J. PleSek, A. Vitek, and F. Haruda, Coil. Czech. Chem. Comm., 1972, 37, 3001. S. Hefmanek, K. Fetter, and J. PleSek, Chem. and Ind., 1972, 606. A. Davison, D. D . Traficante, and S. S. Wreford, J.C.S. Chem. Comm., 1972, 1 1 5 5 . M. I. Bruce and A. P. P. Ostazewski, J.C.S. Chem. Comm., 1972, 1124. E. Negishi, J . J . Katz, and H. C. Brown, J . Amer. Chem. SOC.,1972, 94, 4025. E. Negishi, P. L. Burke, and H . C. Brown, J. Amer. Chem. Soc., 1972, 94, 7431. D . A . Franz, V. R . Miller, and R. N. Grimes, J . Amer. Chem. SOC.,1972, 94, 412.

Characteristic Vibratiunul Frequencies uf Cumpoiinds

25 1

H I

H

the cage-modes (450 -850 cni-l region) suggests that the framework bonding in these molecules is not as strong as in cluso-carbaborane analogue~.~@ A novel species, p- l ,2-trimethylene- l ,2-dicarba-cluso-dodecaborane( lo), with proposed structure (1 I ) , has been reported by Hawthorne et ul., and i.r. frequencies for ( l l ) , the derived anion, and for

several sandwich-bonded complexes between the anion and Ni or Co, have been listed.50 PleSek and Hefmanek 51 have reported another new type of carbaborane, tetracarba-di-nidu-docosaborane(22)with v(B-H)termiml at 2590, 2600 (sh) and (B-H)bridge at 1830, 1890 cm-l. The corresponding anion C4BI8Hz2-has also been obtained, and the second member of the C2B,H,+s series, 6,9-dicarba-nido-decaborane( 14) has been c h a r a c t e r i ~ e d . ~ ~ Lewis-base adducts of 1,2-dicarba-closu-dodecaboranesshow 63 a shift in the i.r. to 2000--2220 cm-l for v(B-H). Solvent effects on v(C-H) in the i.r. spectra of B-chlorinated o-carbaboranes have been described.s4 I!' :j0

52 6:'

:j4

R. W. Jotham, J. S. McAvoy, and D. J. Reynolds, J.C.S. Dalton, 1972, 473. T. E. Paxson, M. K. Kaloustian, G. M. Tom, R. J. Wiersema, and M. F. Hawthorne, J . Amer. Chent. Soc., 1972, 94, 4882. J . PleSek and S. HePmanek, Chem. and Ind., 1972, 890. B. Stibr, J. PlcSek, and S. Heimhnek, Chem. and Ind., 1972, 649. J . PleSek. T. Hanslik. F. Hanousek. and S. Hefmanek, Coll. Czech. Chern. Comm., 1972, 37,'3403. L. A. Leites, L. E. Vinogradova, N. A. Ogorodnikova, and L. 1. Zakharkin, Zhirr. priklnd. Spectrmkopii, 1972, 16, 488.

252

Spec fr-oscopic Propertics of Itiorgunic arid Orgnnometallir Cor~ipounds

Novel carbaboranes possessing bridging hetero-atoms have featured in a number of reports. Grimes and co-workers have listed i.r. frequencies (not assigned) for 1-methyl- 1-galla-2,4-dicarba-closo-heptaborane(7)and its indium analogue. The similarity of these spectra suggest that both share the structure ( 12), determined crystallographically for the gallium The structure of p,p'-silylenebis-(2,3-dicarba-nido-hexaboraryl) is thought from n.m.r. studies to be (13); i.r. bands for v(C-H), v(B-H), and v(Si-H) occur56 at 3020, 2590 and 2530, and 2150cm-', respectively. Wavenumbers for i.r. absorptions for 2,3-p-trimethylsilylCC'-dime thyl-4,5-dicar ba-nidu-hexaborane( 8) and re1ated compounds with Me I

H

H

H

Me,Ge, Me2C1Si, or Me,B groups in the 2,3-bridging position have been listed.57 A rather similar iron-bridged structure (14) derived from niduC2B4Hshas 5 8 v(C-H)carbabranul at 3 115 , v(B-H) at 2580, and v ( C 0 ) at 2010, 1965 cm-l. Some metallocarbaboranes for which mainly unassigned i.r. data have been given 58-61 are listed in Table 2. s*j

6R

h7

"" 6o

6L

R. N. Grimes, W. J. Rademaker, M. L. Denniston, R. F. Bryan, and P. T. Grcene, J . Amer. Chem. Soc., 1972, 94, 1865. A. Tabereaux and R. N. Grimes, J . Amer. Chem. SOC., 1972, 94, 4768. C. G . Savory and M . G . H. Wallbridge, J.C.S. Dalton, 1972, 918. L. G. Sneddon and R. N. Grimes, J. Amer. Chrm. Soc., 1972,94, 7161. J. L. Spencer, M. Green, and F. G . A. Stone, J.C.S. Chem. Comm., 1972, 1178. M. K. Kaloustian, R . J. Wiersema, and M . F. Hawthorne, J . Amer. Chem. Sor., 1972, 94, 6679. C. J. Jones, J. N. Francis, and M. F. Hawthorne, J . Amer. Chem. Soc., 1972, 94, 8391.

r

Characteristic Vibrational Freqrrencies of Compounds

253

Table 2 Some metalloc~arbnboranescharacterized by i.r. spectroscopy Conipound (1 ,5-C8H,,)Ni [Me,C,B,H,] (n-c5H6)CO [n-(3)- 1 ,2-B, C, H111 (n-C5H6)Co[n-(3)-l,2-Me2-I,2-B,C2H,] (7T-c,H,)cO[7T-(3)-1 ,2-(CH2),- I ,2-B,C,H9]

(C6H6)CO[n-(2)-6,7-B,C,HQ] (C,H~)CO(~-B,C,HQ) (C5Hb)Co[r-(l)-2,4-B,C,Hiol 1)-2,4-B8C2Hlo}] {~-( Me,N[{r-(3)- 1 , ~ - B Q C , H ~ ~ ) C O (C6H6)Co(n-B7C2Hll) Me,N [{ n-(3)- 1 ,2-B,C2H,,}Co{ n-(2)-1 ,6-B,C2H,)] Me,N [{n-(3)- 1 ,2-B9C,H,,} Co{n-(2)- 1 ,1 0-B7C, H,) J

and related isomeric compounds

Re$ 59

60

61

Compounds containing Al-H or Ga-H Bonds.-Comparison with data for related boranes and alanes has allowed the following i.r. bands to be assigned 6 2 for [Bu*~,N]BH,,AIH,,NM~, : v(B-H), 2390-2140 (5 bands); v(A1-H), 1720; 6(BH), 1075; and 6(AlH), 780 cm-l. The BH4- group in the complex is deduced to be bound to A1 by a single bridging H. Deuteriation-sensitive bands at 1880-1 620 and 800-600 cm-1 in the i.r. spectra of complexes [AlH,,(Et,O),]. ( x = 0.3-3.32) have been attributed 63 to v(A1-H) and 6(AlH) modes. 1.r. spectroscopy suggests6, that the final product of the reaction of AlCI, with LiBH, in benzene is the complex AIH2BH4,C6H6.Observation of an i.r. band at 1785 cm-' identified as v(A1-H) supports the conclusion that a complex between AlH, and ( I 5) is formed by LiAIH4 reduction of the corresponding homocubyl spirophosphonium In a study of the complexes Al'"H,,"NMe, (nz = 1 or 2 ; n = 14 or 15) and also AIH,,NR, and AlD,,NR3 (R = Et, Pr", or Bun),

alane modes have been found66 in the following ranges (wavenumber/ cm-l): v,,,,,(AI-H), 1630--1625; ~asylll(Al-H), 1790-1775; v , (Al-D), ~ ~ 1180-1 182; ~a,ynl(AI-D), 1290-1310; 68y",(AlH), 765-650; 6a,y,,,(AIH), 762-784; 6syIll(Al-D), 555-462; and amYm(Al-D), 559-567. Davies and u2 g3

O4

O6

BE

M. Ehemann, N. Davies, and H. Noth, Z . nnorg. Chem., 1972, 389, 235. K. N . Semenenko, Kh. A. Taisumov, A. P. Savchenkova, and V. N. Surov, Russ. J . Inorg. Chem.. 1971, 16, 1104. V. I. Mikheeva, N. N. Mal'tseva, N. S. Kedrova, and E. T. Makhova, Russ. J . Inorg. Chem., 1971, 16, 798. E. W. Turnblom and D . Hellwinkel, J.C.S. Chem. Comm., 1972, 404. K. N. Semenenko, B. M. Bulychev, and V. B. Polyakova, Russ. J . Inorg. Chem., 1971, 16, 949.

254

Spectroscopic Properties of Inorganic and Organornetnliic Contpouncis

Wallbridge have listed mainly unassigned i.r. data for THF, diethyl ether, and bis(methy1amine) complexes of aluminium hydroborate, AI(BH4)3,L. Reactions of LiX (X = H, D, BH,, or Cl) with AI(BH,), to give products with AI-H bonds [v near 1880 cni-’: probably HAI(BH,),,Et,O and 870 H,AIBH,,Et,O] have also been in~estigated,~’ and two other papers are also concerned with aluminium borohydride. Strong i.r. bands are observed at -1700 and 760cm-’ in solutions of LiAlMe,H,, due to v(A1-H) and 6(AIH), respectively.s8 The broadness of an i.r. band centred at 1860 cm-l for the novel compound Al,Me,(NMe,),H, is consistent with bridging Al- H bonds, in agreement with the established eight-membered (Al- H- Al- N- Al- H- Al- N) ring structure ; the corresponding deformation mode is identified 6 g at 876 cm-l. In the related compound Al,Me,(NMe,),H, v(A1-H) is located 6grr at 1796 cm-l. By contrast, for 2(Bu1,Al)-Bu’,AlH, v(A1- H) is found at lower frequency (1 400 cm--l), units. attributed to the presence 70 of bridging Al-H-A1 Synthesis 71 of a series of novel, volatile, cyclogallata-azonianes 67(1t

-

[CH2(CH,),NGaH2], ( x = 1, 2, 3, or 4; n = 2 or 3), by Storr, Thomas, and Penland provides the only i.r. data for gallanes reported during the year. Corresponding boron and aluminium derivatives were also prepared, and M-H stretching frequencies are compared in Table 3.

Table 3

Wavenumberslcm-l for v(M -H)

Compound n CH,CH2N M H,

M = B

modes of [CH,(CH,),NM H21n M = Al

M

= Ga

2430vs, 2390vs, 2320s, 2260s, 2210m

1835s, 1775vs

1885vs, sh, 1855vs 18OOvs, sh

2395vs, 2330s, 2200m

1835vs, 1775vs

1850vs, br, 1800vs, sh

CH,(CH,),NMH,

2400vs, 2330s, 2220m

1835vs, 1780vs

1865vs, br, 1800vs, sh

CH,(CH,),NMH,

(2430s, sh?), 2410vs, 2350s, 2240m

1835vs, ISOOs, sh

1870vs, br, 1800s

m

CH2(CH2),NMH2

m

m

Compounds containing M-C Bonds (M = B, Al, Ga, In, or Tl). -1.r. frequencies for CF2=CHBX2, and cis- and trans-CFCl=CHBX, (X = F or Cl) have been listed,72 and for propynylboron difluoride, MeCSCBF,, N. Davies and M. G . H . Wallbridge, J . C . S . Dalton, 1972, 1421. K. N. Semenenko, 0. V. Kravchenko, and E. B. Lobkovskii, Zhur. strirkt. Khirn., 1972, 13, 540. 1 3 K. ~ ~ N. Semenenko, 0. V. Kravchenko, S. P. Shilkin, and V. B. Polyakova, Doklndy Chem., 1971, 201, 1063. 6H E. C. Ashby and J. Watkins, J.C.S. Chem. Comni., 1972, 998. 6B J. D. Glore, R. E. Hall, and E. P. Schram, Znorg. Chem., 1972, 11, 5 5 0 . J . D. Glore and E. P. Schram, Inorg. Chem., 1972, 11, 1532. 7 v J. J. Eisch and S. G . Rhee, J. Orgonometallic Chem., 1972, 42, C73. 71 A. Storr, B. S. Thomas, and A. D. Penland, J.C.S. Dalton, 1972, 326. 72 J. J. Ritter, T. D. Coyle, and J. M . Bellama, J . Organometallic Chem., 1972, 42, 25. 67

Characteristic Vibrational Frequencies of Compounds

255

all twenty fundamentals have been assigned 7 3 with v(B-C) at 782 cm-l. In C12B(CH2)3BCI,,v,,,,(B-C) is found '* at 920 cm-l, with vasym(BC1,)at 1095 cm-'. A detailed vibrational study has been made of the phenylboron halides Ph,BX and PhBX2 (X = F, Cl, Br, or I) leading to assignments for B-Ph and B-X modes 75 collected in Table 4.

Table 4 Boron-phenyl and boron-halogen vibrations for Ph2BX and PhBX, (wacenurnbers/cm-') v(B-Ph) 1375, 1338 1335, 1222 1261, 1167 1260, 1166

6(B- P h)

I'h,BF Ph,BCl Ph,BBr Ph,BI PhBF, PhBCl, PhBBr, PhBI,

1340 1240 1225 1208

646 640 607 585

671, 582 63 1 , 580 647, 580 633, 571

v(B-X) I348 910 837 81 1 1378 949,910 864,808 717, 691

8(B-X) 696 565 550 43 8

5 70 551 525 500

Assignments for the vibrational spectra of [(Me,Al),N,]- and [Me,AIN,]have been proposed and compared with those for isoelectronic Me3Si species. The symmetric and asymmetric Al-C stretching modes give rise to strong Raman bands near 520 and 610 cm-l, re~pectively.~~ Unassigned i.r. data for Et,IAl,NHMe, and [EtIAINMe,], have been listed.77 Haaland and Weidlein have suggested that the i.r. and Rarnan spectra of solid Et2Al(C6H6)are consistent with the presence of a pentahapto-C,H, ligand. The following assignments (wavenurnber/crn-l) are given :78 vaSy,(A1C,), 690; vSym(AlCZ), 580; 8sym(AlCz), 345; and v(Al-Cp), 210. Renewed interest in organogallium chemistry has resulted in the measurement of v(Ga-C) for a number of compounds, including the frequencies listed in Table 5 for alkylgallium h a l i d e ~ , ~ ~and - ~ lin Table 6 for the bridged species (R2M)204C2(M = G a o r In) (obtaineda2 by reaction of the trialkylgallium with oxalic acid) and [Me,GaO,PX,], (X = F, C1, or Me).83 Bands at 435-446 cm-l in the i.r. spectra of M+(InMe,)- (M = Li--43) are assigned to v(1n-C). The vibrational spectra of alkylindium halides have been examined by two groups of investigators: Poland and Tuck 7n i4

7L 78

77

7n 7Q

no n1 83 n3 84

P. R. Reed and R. W. Lovejoy, J . Chem. Phys., 1972, 56, 183. M . Zeldin and A. Rosen, J . Organometallic Chem., 1972, 34, 259. F. C. Nahm, E. F. Rothergy, and K . Niedenzu, J . Organometallic Chem., 1972, 35,9. F. Weller and K. Dehnicke, J . Organometallic Chem., 1972, 35, 237. K. Gosling and A. L. Bhuiyan, Znorg. Nuclear Chem. Letters, 1972, 8, 329. A. Haaland and J. Weidlein, J . Organometallic Chem., 1972, 40, 29. W. Lind and I. J. Worrall, J . Organometallic Chem., 1972, 40,35. W. Lind and I. J. Worrall, J . Organometallic Chem., 1972, 36, 35. M. J, S. Gynane and I. J. Worrall, J . Organometallic Chem., 1972, 40,C59. H. U . Schwering, H . D. Hausen, and J. Weidlein, 2. anorg. Chem., 1972, 391, 97. B. Schaible and J. Weidlein, J. Organometallic Chem., 1972, 35, C7. K. Hoffmann and E. Weiss, J . Organometallic Chem., 1972, 37, 1.

256

Spectroscopic Properties of Iiiorgcinic aiid Organornetallic Compoirrrds

Table 5 Assignment of Ga--C alkylgallium halides Compound

MeGa,Cl, MeGa,Br, MeGa,I, MeGa,C141 MeGa,Br,T Me,Ga,Br, Et,Ga,Br, Me,G a, I, Et,Ga,I,

[Me,GaO,PF,],

[Me,GaO,PCI,],

[Me,Ca0,PMe2],

stretching modes (wai~eiiumber/cm I ) iir v(Ga--C 1 609

Ref.

79 621, 587, 545 580, 551, 509 612, 575, 538 577, 548, 508

593 61 6 61 4

81

546 553 553

report v(In-C) frequencies as follows 8 5 (wavenumber/cm-l): [Me,In][InI,], 561 (vaRYII1: i.r.), 483 ( v ~ ~ ~R); ~ , :(EtInI,),, 489; (BunlnT,),, 487; whereas Worrall et al. find86**' two bands for (Bulnl,), and also for (PrInI,),, near 485 and 577 cm-l. These workers agree on the ionic formulation [Me,In]+ [InTJ- for the methyl compound, their observations parallelling published data for Me,In+, but for the higher alkyl derivatives the more usual dimeric structure is proposed. In Et,In(OOCMe), vsyIn and v,,,,,(InC,) are found 8 o at 468 and 5 17 cm-I, respectively, and for Me,In(SSCNMe,), MeIn(SSCNMe,),, and EtIn(SSCN Me,),, where v(In-C) modes occur at 51 8 and 482,506 and 486 cm-l, it is suggested that these low frequencies are consistent with strongly bonded dithiocarbamate ligands.oQ For R,In(O,SMe), Rarnan bands at 5 5 2 , 5 10 and 520,474 cm are assigned ~ ~ similar to vS).,,, and vaRYm(In-C) for R = Me or Et, r e s p e c t i ~ e l y ,and bands have been distinguishedQ1 for adducts of MeIn(tdt) (tdt = toluene-3,4-dithiolate). The vibrational spectra of cyclopentadienyl derivatives of indium are consistent with a-bonded Cp rings;02 some assignments are shown in Table 7. Hh

x7 Hn

ne Dl u2

J. S. Poland and D. G. Tuck, J . Organometallic Chem., 1972, 42, 315. M. J. S. Gynane, L. G. Waterworth, and I. J. Worrall, J . Organometallic Chern., 1972, 43, 257. M. J. S. Gynane and I. J. Worrall, inorg. Nuclear Chem. Letters, 1972, 8, 547. H. D. Hausen, J . Organometallic Chem., 1972, 39, C37. T. Maeda and R. Okawara, J . Organonletallic Chern., 1972, 39, 87. H . Olapinski and J. Weidlein, J . Organometallic Chem., 1972, 35, C53. A . F. Berniaz and D. G. Tuck, J . Organometallic Chern., 1972, 46, 243. J, S. Poland and D. G . Tuck, J . Organometallic Cheni., 1972, 42, 307.

Clinracteristic Vibrational Frequencies of Compounds Table 7

257

Wavenumberlcm-l of v(1n-C) modes in Cp,In nnd r.c)lrred specks Compound InCp, In( Cp M e), I nCp,,PPh, JnCp,,bipy InCp,,phen Li [In(indenyl),] Li [In(indenyl),],Et,O

v(In -C) 339, 316 349, 322 321, 303 325, 300 293 371, 352, 340 371, 351, 340

For dimethylthallium diph~sphinite,~, vSy1I1 and vasym(TICz) are at 491 and 532 cm-l, whereas for the corresponding diphosphinate these fundamentals occur at 492 and 541 cm-l. For R(CICH,)TIX (R = Ph, X = C1, OCOMe, or OCOPr'; R = p-MeC,H,, X = C1, OCOMe, or OCOPr'; R = Me, X = OCOMe or OCOPr'; R = OCOMe, X = OCOMe; R = X = OCOPr'), bands assignedo4 to v(T1-C) range from 493 to 537 cni-l, and similarly vaSYrll(TIC2) are at 531---552cm-* for [16; R = Me, 0 II C / \ RZTI-N, ,X C II 0

X = (CH,), or O-C,H,].~~Aromatic ring vibrations for a variety of R,TlY compounds (R = Ph, o-MeC,H,, rn-MeC,H, or p-MeC,H,; Y = electronegative group) are sensitive to the nature of Y.96 Compounds containing M-N Bonds (M = B, Al, or Ga) or B-P Bonds.-In the i.r. spectra of the t-butylmethyleneaminoboranes, But,C=NBX, (X = CI, Ph, or Bu"), the high energy of absorptions due to azomethine stretching modes (respectively at 1839, 1820, and 1821 cm-l) is consistent with their assignment to vaBYr,,of a linear C=N*B ~keleton.~' An examination of the effect on the frequencies of characteristic ring vibrations of varying X in the B-substituted A2-tetrazaborolines (17; X = C1, Br, CN, SCN, or SeCN) has revealed that the five stretching modes are remarkably consistent throughout (at 1410, 1362, 1337, 980, and 906 cm-I for x = C1).9* Partial assignments of observed i.r. and Raman spectra have been given for (Me3Si),NBF2, (Me,Si),NB(F)NHSiMe,, and the related borazines F3B3N3(SiMe,), and F3B3N3H(SiMe3)2,with v(B-N) modes in 93 84 85

w DH

B. Walther, J . Organometallic Chem., 1972, 38, 237. T. Abe and R. Okawara, J. Organometallic Chetn., 1972, 43, 117. B. Walther and C. Rockstroh, J. Organometallic Chem., 1972, 42, 41. T. N. Srivastava, S . K. Tandon, and K. K. Bajpai, Spectrochim. Acta, 1972, 28A, 455. M. R. Collier, M. F. Lappert, R. Snaith, and K. Wade, J.C.S. Dalton, 1972, 370. B. Hessett, J. B. Leach, J. H. Morris, and P. G. Perkins, J.C.S. Dalton, 1972, 131. G . Elter, 0. Glemser, and W. Herzog, Cherrr. Ber., 1972, 105, 115.

258


X I

the expected range (1 250-1480 cm-l). The borazines H2ClB3N3H2Me and H2(Me,N)B,N,H,Me have been partially separated into orrho- and paraisomeric forms, for which the i.r. spectra show some differences in the 950-650 region (BN bending).loO Other B-N bonded compounds (a number of them borazine derivatives) for which i.r. frequencies have been given are listed in Table 8; in some cases assignments including v(B-N) modes have been offered. Table 8 References to compounds wirh B-N spectroscopy

bonds characterized by i.r.

Compound [M%NBH20C(R1)NHR2]+(R1= Me or Ph; R2 = H or Ph) [MQNBH,O-R]+ [R = CHNMe,, C(Me)NMe,, C(Me)N(H)C,H,OEt, C,HNPh, C,H,N, C,H,NMe, or C(Me)NC,H,Cl] [M%NBCI,OC(X)NMe,]+ (X = H or I) [Me3NBH,CNX]+ (X = Me, BH2NMe3, or BH,PM%) RSB3NSM%(R = Ph, Me, or C1: all ten possible compounds) RMeBBsN,Me, (R = Et or Me&,) [MesN,B,Me,l, [M%NsBsMe2]20 (C6H6)SBSN3 (Mec6H4)!3B3N3M%}

]

i 101

102

103

104

105

The vibrational spectra of [(Me3A1),N3]- and [ Me3AlN,]- contain bands due to Al-N stretching at 424 (vBBym) and 302 (vBym), and 420 cm-l respectively, and are consistent with C,symmetry, implying structure (1 8) for the bistrimethylaluminium compound with no evidence for A1 + N n-bonding.'" A band at rather higher frequency (500 cm-l) is attributed lo, 0. T. Beachley, J . Amer. Chem. SOC.,1972, 94, 4223. D. L. Reznicek and N. E. Miller, Znorg. Chem., 1972, 1 1 , 858. l o 2 D. Fenske and H. J. Becher, Chem. Ber., 1972, 105, 2085. l o 3 L. A. Melcher, J. L. Adcock, and J. J. Lugowski, Inorg. Chem., 1972, 11, 1247. lo' B. L. Therrell and E. K. Mellon, Inorg. Chem., 1972, 11, 1137. l o 6 J. Cueilleron and B. Frange, Bull. Soc. chim. France, 1972, 107. l o 6 C. H. Chan and F. P. Olsen, Znorg. Chem., 1972, 11, 2836. loo

lol

Ckarncteristic Vibrationnl Frequencies of Compounds Me,AI,

Me,A1'

259

N-N-N (18)

to v(A1-N) for S,N,,AlCI,, and similar modes are rather doubtfully assigned l3 near 775 cm-l for [AICI,(N,)], and [AlCl(N,),],. Triniethylaluminium-trimethylaminehas been found to decompose at 50 "C to give the cis- and trans-isomers of the trimeric species (Me,AlNHMe), (1 9) ;

N

Me2?' I

Me2" I

'?IMe,

N

'AIMe, I

I

Me -,N, ,N---H H: #e, 'Me (cis-)

(trans-) (19)

strong i.r./Raman bands at 505 (trans-) and 579, 460 cm-l (cis) are thought lo7to arise mainly from (Al-N), ring vibrations. Corresponding ethyl aluminium compounds were obtained similarly. Trimeric cyclopropyl derivatives [(C,H,),M(NC,H,)], (M = A1 or Ga) have also been investigated by i.r. and Raman spectroscopy, the results indicating non-planar ring structures with C2 symmetry.1o8 Schram et al. have given partial i.r. assignments 6gf for the cyclic derivatives Al,Me,(N Me,),H and Al4Me8(NMe2),H2,placing vaaym(Al-N) at 553, v,,(Al-N) at 539 ern-.' for the second of these. 1.r. spectroscopy has been used to confirm that in [R,N]Ga(NCS), (R = Et or Bun) and [(R,N),Ga(NCS),] (R = Me or Bun) the NCS- groups are N-bonded, and bands near 350cm-l for the tetraisothiocyanato-complexes are assigned logto v(Ga-N). Reaction of phosphine or phosphonium iodide with BI, affords H3P,B13, for which v("B-P) is assigned to i.r. absorptions at 487 (n = 11) and 500 cm-1 (n = 10). Fleming and Parry have found that whereas F,PNMe, reacts to form an N-bonded adduct with BF,, [v,,(N-10BF3) at 654 cm-'1 the same base reacts with tetraborane(l0) to give the complex H7B3,F,PNMe,, the i.r. spectrum of which includes features at 592 and 542 cm-l attributable to v(B-P), implying co-ordination through phosphorus.lll The i.r. spectra of the related species F3PB3H, and F2ClPB3H7have also been assigned quite fully,35with v(B-P) at 590 cm-l. A review of spectroscopic aspects of metal-phosphorus bonding includes tabulation and K. J. Alford, K. Gosling, and J. D. Smith, J.C.S. Dalron, 1972, 2203. J. Muller, K. Margiolis, and K. Dehnicke, J . Organornerallic Chem., 1972, 46, 219. L. M. Mikheeva, L. N. Auerman, A. I . Tarasova, and L. N. Komissarova, Russ. J . Inorg. Chem., 1971, 16, 1126. 110 M. Schmidt and H . H . . I. Schroder, 2.anorg. Chem., 1972, 394, 290. S. Fleming and R. W. Parry, Inorg. Chem., 1972, 11, 1 .

lo8

260

Spectroscopic Properties oj'It lor.gunk and 0rganomet cr liic Con1poiirtcl.s

discussion of B- P stretching vibrations in complexes between boranes and phosphorus donors.l12 Compounds containing M - 0 Bonds (M = B, Al, Ga, In, or TI). The alkoxyboranes (ButO),B, (ButO),BMe, and (ButO)BMe, show i.r. absorptions assigned 113 as follows (wavenumber/cm-l) : respectively at 1 347, 1329, and 1346, v(B-0); at 1188, 1183, and 1194, v(C-0); and for the methyl compounds, at 1238, and 1306/1118, v(B-C). Bands attributed to u ( B - 0 - C ) have been observed at 1350-1310 cm--l in the i.r. spectra of some alkylborate derivatives of monosaccharide^.^^^ A number of papers concerning the vibrations of BO, units have appeared.l15In particular,lle the behaviour towards water of B,03 surfaces has been investigated by i.r. techniques, in conjunction with a study of B(OH),, HB02, and Bz03. Structures involving the formation of B309 rings have also been proposed on the basis of vibrational data for a variety of rare-earth borate~.~~~ L80-Labelling has been used in an examination of B(OH)4 . The v : ~ i.r.-active mode was found at 982 cm- (l80compound), compared with 958 cm-l for the lSO compound, whereas v1 was observed in the Raman effect at 744cm-l for both species. The lack of change in v1 leads to the unusual suggestion l l g a that hydrogen-bonding between B(OH),- ions and solvating water molecules is appreciably weaker in the case of 180-labelled ions than for B(1sOH)4-. 1.r. spectra of films of binary borosilicate glasses ranging in composition from SiO, to B203have been discussed in terms of features arising from the presence of Si-0-Si, B-0-Si, or B-0-B bonds, a band at 670 cm-' being assigned to u(B-O-Si).120 Halogen, methyl, amino, and phosI

I

I

'

phine derivatives of O(CH&OB- (1,3,2-dioxaborolan) and S(CH2),SBhave been examined by i.r. spectroscopy.121 References 122-126 contain i.r. data for several other species with B-0 bonds. 112 J. G.Verkade, Co-ordination Chem. Rev., 1972. 9, 1. llS I. Kronawitter and H. Noth, Chem. Ber., 1972, 105, 2423.

V. V. Gertsev and L. A. Frolova, Dokfady Chew., 1971, 200, 834. I. W. Shepherd, Phys. Reo. (B), 1972, 5 , 4524. P. F. Rza-Zade, G. K. Abdullaev, F. R . Sarnedov, and Kh. K . Zeinalova, Russ. J . Inorg. Chem., 1971, 16, 1221. 117 G.Heller and D. A. Marquard, Inorg. Nuclear Chem. Letters, 1972, 8, 663. llU P. Broadhead and G . A. Newman, Spectrochim. Acta, 1972, 28A, 1915. l l @ J. H. Denning and S. D. Ross, Spectrochim. Acta, 1972, 28A, 1775. ilea S. Pinchas and J. Shamir, J . Chern. Phys., 1972, 56,2017. I4O A. S. Tenney and J. Wong, J . Cheni. Phys., 1972, 56,5516. 121 S. G. Shore, J. L. Crist, B. Lockman, J . R. Long, and A . D. Coon, J . C . S . Dalton, 1972, 1123. H. HBni and J. D. Russell, Nature Phj.s. Sci., 1972, 235, 13. 123 J. Frohnecke and G. Heller, J . Inorg. Nuclear Chem., 1972, 34, 69. lZsa H. Gode, 1. Zuika, and G . Adijano, Latv. P S R Zinat. Akad. Vestis, Kim. Ser., 1971, 538. n4 R. Larsson and G . Nunziata, Acta Chem. Srand., 1972, 26, 1503. G . J. Barrett and D. T. Haworth, Inorg. Chim. Acta, 1972, 6,504. A. N . Maitra and D . Sen, J . Inorg. Nuclear Chem., 1972, 34, 3643. 114 116

Cliarncteristic Vibrational Freqirencies of Compounds

26 I

Reaction of AlBr, with a solution of CsNO, in HN03-N205 affords Cs[AI(NO,),] and Cs2[AI(N03)J, characterized by X-ray diffraction patterns and i.r. spectroscopy. The spectra are indicative of covalently bonded NO, groups and differ in the v(Al-0) region (440-500 cm-l) but no firm structural conclusions have been made.127* 128 Partial i.r. assignments for the isopropoxide species AI(Pr*O),, Ga(PriO),, In[A1(PriO),],, and In[Ga(PriO),], include 129 v(Al-0) at 695 and v(Ga-0) near 670 cm-I. The vibrational spectra of the cyclic species [Me,MOOEMe,], (M = Al, Ga, or In; E = P or As) have been assigned, the dimethylphosphinates containing puckered eight-membered (M,O,P,) rings with C2hsymmetry.130 I n a detailed study of [Al(DMS0)J3+ and [Al([2H6]DMSO)6]3+ as AICI,-, AlBr,--, CI-, and Br- salts, v(A1-0) modes are located at 470,496 (DMSO complex) and 440, 472 cm-I ([2H6]DMS0 complex).131 Reaction of tris(dimethy1amino)alane with Fe(CO), yields a carbene complex formulated as [(CO),FeC(NMe,)OAI(NMe,),], ; an i.r. band at 15 12 cm-l is attributed to v(C-0-AI), a relatively high frequency being rationalized in terms of substantial C=O character arising from four-co-ordination at Al. Sat0 has used i.r. spectroscopy in an investigation of the formation of aluminium h y d r o x y - ~ p e c i e s , ~ ~and ~ ~ the frequencies for v1 and v, of Si(Al)04units in Linde-A type synthetic zeolites have been correlated with constituent ion radii.135 The vibrational spectrum of Ga(SO,F), includes a band at 445 cm-l Similarly, for M2GaF,,H,0 (M = tentatively assigned 136 to v(Ga-0). NH4, K, Rb, or Cs), MGaF,,2H20 (M = NH,, Rb, or Cs), and GaF3,3H,O and some deuterio-derivatives, v(Ga-0) modes give rise to i.r. absorptions in the range1,' 431-483 cm-l. The far4.r. spectrum of [Ga,(OH),X,(Me,dpma),]2t(X-)2,H,0 [X = Cl or Br; Me,dpma = methyl-(6-methyl2-pyridylmethyl)-(2-pyridylmethyl)amine]includes a strong band at 530 (X = CI) or 532 cm-l (X = Br) not present for MX,(Me,dpma) (M = In or TI; X = CI or Br) and which is therefore attributed to a v,,,,(Ga-0) vibration.138 The compounds (C6F,),In,(OSMe2)2 and (C6F6),In,oPPh3 show 13Q v(In-0) near 414 crn-'. Some vibrational data for nitroparafin derivatives of T1' have been 1 i ~ t e d . I ~ ~ 127

12H lZ9

lD0

l:I3

lR4

l:I6 l:I7

G. N. Shirokova and V. Ya. Rosolovskii, Russ. J . Inorg. Chem., 1971, 16, 1106. G . N. Shirokova and V. Ya. Rosolovskii, Russ. J . Inorg. Chem., 1971, 16, 808. A. Mehrotra and R. C. Mehrotra, Inorg. Chem., 1972, 11, 2170. H. Olapinski, B. Schaible, and J. Weidlein, J . Organometallic Chem., 1972, 43, 107. J. Meurier and M. T. Forel, Canad. J . Chem., 1972, 50, 1157. W. Petz and G . Schmid, Angew. Chem. Ititernat. Edn., 1972, 11, 934. T. Sato, Z . anorg. Chem., 1972, 391, 69. T. Sato, Z . anorg. Chem., 1972, 391, 167. J. J. P. M . de Kanter, 1. E. Maxwell, and P. J . Trotter, J.C.S. Chem. Cotnrn., 1972, 733. A. Storr, P. A. Yeats, and F. Aubke, Canad. J . Client., 1972, 50, 452.

K . I. Petrov. I . V. Tananaev, and T. B. Vorotilina, Russ.J . Inorg. Chem., 1971, 16, 811.

l:lL) 131)

K. Dymock, C. J. Palenik, and A. J. Carty, J . C . S . Chem. Comnt., 1972, 1218. G. B. Deacon and J. C. Parrott, Austral. J . Chem., 1972, 25, 1169. A. G . Lee, Spectrochim. Acto, 1972, 28A, 133.

262

Specit~osi~opii~ Properties of Itrorganic a n d Organometallic Compounds

Compounds containing M-S Bonds (M = A1 or In) or M-Se Bonds (M = B or Al).-The species [(Me,AI),SCN]-, [Me,AISCN]-, [(Me3Al)2SeCNI-, and [(Me3AI),CN]- have been examined by i.r. and Raman spectroscopy. The results are consistent with AI-S, and AI-Se bonding (Table 9) in the first three complexes, but with the occurrence of Al-CNTable 9 A1-S and Al-Se stretching fundamentals in trimethylaluminiumpseudohalogen complexes v(AI-E)"

Compound [( Me,AI),SCN][(Me, A I)SCN ] -

[(Me, A I),SeCN ]a

E

=

178 ( V W l l l ) 154 (Vsum)

336

3 15 ( ~ a s u n l )

274 (%surd

S or Se.

-Al bridging in the fourth.141 Vibrational bands in the 230--290cm-I region142 for R,InX,SSbMe, (R = Me or Et; X = CI or Br) and MeInCI,,SSbMe,, and at 379 cm-* for Me,In(SSCNMe,), RIn(SSCNMe,), (R = Me or Et)89 have been assigned to v(In-S) modes, the higher wavenumber for the dithiocarbamate complexes being consistent with strong bonding to In. Related data for toluene-3,4-dithiolate complexes derived from trimethylindium have also been reported.91 Unassigned i.r. spectra of amorphous and crystalline B,Se, have been r e ~ 0 r d e d . l ~ ~

Compounds containing M-Halogen Bonds (M = B, Al, Ga, In, or Tl).Novel polyboron and silicon-boron derivatives have been synthesized using the reactive species BF, SiCI,, and SiF,. Products obtained in this way for which unassigned i.r. and Raman frequencies have been re145 are BF2(SiFs), B8Fl2, and (SiCl,),,BCI,,BCO. The reaction ported systems [metal chloride-PC1,-ButC1] (metal = B, Al, or Sn) and [metal chloride-MePC1,-ButC1] (metal = B or Sn) yield solid products characterized as ionic complexes of alkyl chlorophosphonium cations with the species BC14-, AIC14-, and SnC1,-. Observed i.r. bands and assignments for the anions are listed in Table 10. Further similar data have been l d 4 9

Table 10 1.r. wnt:enrrrnbers/cm-lfor BC14- and AIC1,- species Assignment v3

v1 v4 1'2

la1 Ira

146

[ButPC13][AICI,] 49 1vs 349m 183/175s

[ButPCI,][BCI,] 723s (l0B), 696vs ("B) 396mw 275w

196vw, sh (?)

F. Wcllcr and K. Dehnicke, J. Organometallic Chetii., 1972, 36, 23. T. Maeda, G. Yoshida, and R. Okawara, J. Orgattometallic Chem., 1972, 44,237. R. Hillel and J. Cueilleran, Bull. Soc. chim., Fratice, 1972, 98. D. L. Smith, R. Kirk, and P. L. Timms, J.C.S. Chem. Comm., 1972, 295. R. W. Kirk, D. L. Smith, W. Airey, and P. L. Timms, J.C.S. Dalton, 1972, 1392. J. I. Bullock, N. J. Taylor. and F. W. Parrett, J.C.S. Dalton, 1972, 1843.


263 reported for PC14+BC14-,where differences in the Raman (but not i.r.) spectra from those given previously have been due to overlap of v,(cation) with v4, v g , v,(anion), and for several BF4 and also EF, (E = P or Sb) species.147Solutions of Na[BF,OH] in NaBF, (crystalline or molten) show i.r. absorptions at 3641 (2688 on deuteriation) and 767 cm-l, assigned148to v(0H) and v,,,(B-F) of BF30H-. Reaction of molten NaCI-AICl, with As,O, at 170 "C affords a homogeneous metastable oxide solution, up to 6% oxygen being present, but the only species detectable 14# by Raman spectroscopy is AlCI,-. It has been suggested lrj0that melts consisting of gallium trichloridecaesiuni chloride in various mol. ratios contain GaC14-, Ga2C17-, and Ga,CI,. Frequencies of Raman shifts for GaC1,- were close to those reported previously for aqueous solutions (vl, 343; v2, 120; vg, 370; and v4, 153 cm-l); for Ga,Cl,-, bands were detected as follows (wavenumber/ cm-I): 393m, sh(dp), 366vs(p), 3 16w, 140s(dp), and 90s(dp), these resembling known data for AlzC17-. The Raman spectrum of solid InBr, is consistent with the formulation In'(In'"Br,), the e stretching fundamental (v3)for the anion (at 239 cm-l in solution) splitting into three components at 228, 236, and 241 cm-l. By contrast, solid In2Br, appears to exist as (ln+)2(In2Bre2-),a band at 139 cm-l being attributed to stretching of a metal-metal bond in the anion.151 A full assignment for the vibrational spectrum of Cs3Tn2C1,has been proposedlrj2 by analogy with previously reported single-crystal data for Cs,TI,CI,, and the i.r. spectrum for Cs31nBr, has been illustrated lS3in the range 400-30 CM-'. Alkylindium halides have also received some attention as noted earlier;86* some conflicting conclusions have been reached regarding v(1n-I) vibrations, as is shown in Table 11.

14'

K. Niedenza, I. A. Boenig, and E. B. Bradley, Z. anorg. Chem., 1972, 393, 88. V. K. Akimov, A. I. Busev, and D. I. Andzhaparidze, Russ. J. Inorg. Chem., 1971,16, 1427.

5. B. Bates, J. P. Young, M. M. Murray, H. W. Kohn, and G. E. Boyd, J. Inorg. Nuclear Chem., 1972, 34, 2721. 14@ H. Kuhnl and U. Geffarth, 2. anorg. Cheni., 1972, 391, 280. l K 0 H. A. 0 y e and W. Bues, Inorg. Nuclear Chem. Letters, 1972, 8, 31. lS1 L. Waterworth and I. J. Worrall, Inorg. Nuclear Chem. Letters, 1972, 8, 123. lo2 F. J. Brinkman, J. Inorg. Nuclear Chem., 1972, 34, 394. lSs A. G. Dudareva, Yu. E. Bogatov, B. N. Ivanov-Emin, and P. I. Fedorov, Russ. J . Inorg. Chem., 1971, 16, 1378.

264

Spectiwsc-opicPiwperties of Inorganic m d Organonietallic Compounh

The distribution of v(M-X) bands in the vibrational spectra of MX,(terpy) complexes ( M = Al, X = CI or Br; M = Ga or I n , X = CI, Br, or I ; M = TI, X = C1) has been shown to be of limited value as a criterion for distinguishing between alternative structures for these systems : similar patterns were found for trans-octahedral and five-co-ordinate, MX2(terpy)'X-, arrangements.lS4 A shift to lower wavenumber of M. 70- 80 cm-l for v(C0) in complexes of aromatic aldehydes with BF, confirms that co-ordination occurs via the carbonyl oxygen atom.155Other complexes of Group I l l element trihalides for which vibrational data have been given 166-159 are listed in Table 12.

Table 12 References containing uibrcttiorial data for complexes of Group I l l halides Compound

i

tmu,BF, (tmu = tetramethylurea) R1R20,AIX3(Rl, R2 = CH, or CD,; X = Cl or Br) 3(p hen),GaX, (X = Br or C10,) 3(bipy)9GaX3} 2(bipy),GaCI, bipy,GaBr, phen,GaX, (X = C1 or Br)

{GaX,[Ni(salen),]}+GaX,- (X = C1 or Br) and

related Ga"' and In"' halide complexes

Ref: 156 157 158

159

Broadening and splitting of v(T1-CI) fundamentals in the i.r. spectrum of trans-(CoCl,en,)(T1C14) has been discussed in terms of Tl-Cl- H hydrogen bonding.16" A review of the co-ordination chemistry of thallium(1) includes some reference to vibrational spectroscopy.161 4 Group IV Elements

Preparation of thirty-three crystalline adducts of tetra-alkylammonium halides with carbon tetrahalides and with C,Br, and CZI4has been reported by Creighton and Thomas. 1.r. and Raman observations are discussed in terms of site-symmetry for the halogenocarbon molecule ; consideration of results, including bands assigned to lattice vibrations in conjunction with X-ray data, leads to the conclusion that these species should be regarded as 164

166 156

157 168

168

180 181

G . Beran, K . Dymock, H . A. Patel, A. J. Carty, and P. M . Boorman, Inorg. C'hctu., 1972, 11, 896. M. Rabinovitz and A. Grinvald, J . Atner. Chem. Soc., 1972, 94, 2724. J . S. Hartman and G . J . Schrobilgen, Canad. J . C'hem., 1972, 50, 7 1 3 . J. Dcrouault, M . Fouassier, and M. T. Forel, J . Mol. Structure, 1972, 11, 423. F. Ya. Kul'ba, V. L. Stolyarov, and A. P. Zharkov, R i m . J . Znorg. Chem., 1971, 16, 1712. M . D. Hobday and T. D. Smith, J.C.S. Doiton, 1972, 2287. K. Brodersen, J. Rath, and G. Thiele, Z. nnorg. Chem., 1972, 394, 13. A. G . Lee, Coord. Chem. Rel;., 1972, 8, 289.

Clicimcteristic Vibrntiontil FreyicencaicJsoj Conipoiimls

265

donor-acceptor complexes.162 The same authors have suggested I G Jthat the Raman spectra of similar systems in solution in non-hydrogen-bonding solvents show evidence for the existence of 1 : 1 complexes, X ,CBr,*, present as ion-pairs with the cation. It is further proposed, on the basis of changes in vibrational frequencies and depolarization ratios for CBr, on complexation, that in CBr,CI-, the chloride ion is bound to a face rather than an apex or edge of the CBr, tetrahedron. 1.r. and Raman spectra for CSClBr have been recorded, with stretching modes vl, v2, and v : ~at 1130, 764, and 438 cm-I, re~pectively,’~~ and the absolute intensities of i.r. absorptions for the related species CSXz (X = F or Cl) have been measured.165The first report of methyl hydrogen carbonate, MeOCO(OH), includes 166 the i.r. data listed in Table 13.

Virtually complete vibrational assignments for several cyclic fluorocarbon derivatives have been reported: the tetrafluorocyclopropanes C3F4H2,C3F,HD, and C3F4D2possess, respectively, C2?, C,, and C Z 8 symmetry ;lG7 tetrafluoroethylene oxide 168 and 1 -H-trifluorocyclopropene IeO have been the subjects of detailed gas-phase i.r. studies; observed data for perfluorocyclohexane are satisfactorily accounted for 170 o n thc basis of the point group The N-(trichloromethyl)chloroformimidiuni salt CI,CN( H)= CCI 2 i ,SbC1,- and its neutral relative Cl,CN=CCI,,SbCI, have been examined by i.r. and Raman techniques.’’’ Raman spectra of solutions of MeCOCl in HFSOs, HCIS03, HCI04, and HCF3S03 are consistent’72 with the equilibria shown in Scheme 1.

Compounds containing M-H Bonds (M = Si, Ge, or Sn). - The vibrational spectra of phenylsilane and phenyl[’H,]silane have been subjects of a detailed Vapour-phase i.r. measurements suggest that the silyl group can llis

lR4

J. A. Creighton and K. M. Thomas, J.C.S. Dalton, 1972, 403. J. A. Creighton and K. M. Thomas, J.C.S. Dalton, 1972, 2254. J. L. Brema and D. C. Moule, Spectrochim. Acra, 1972, 28A, 809.

M. J. Hopper, J. W. Russell, and J. Overend, Specfrochini. Arlo, 1772, 28A, 1215. G. Gattow and W. Behrendt, Angew. Chew?.Internof. Ed?., 1972, 11, 534. Ini N. C. Craig, G. J. Anderson, E. Cuellar-Fcrreira, J. W. Koepke, and P. 11. M a r t y n , Spectrochim. Acta, 1972, 28A, 1175. lflH N. C. Craig, Spertrorhim. Acta, 1972, 28A, 1195. N. C. Craig and J. W. Koepke, Spectrochirii. A c t o , 1972, 28A, 180. 1 7 0 F. A. Miller and B. M. Harney, Spectrochinr. Acfo, 1972, 28A, 1059. lil A. Schmidt, Chem. Ber., 1972, 105, 3050. li2 R. J. P. Corriu, G. Dabosi, and A. Germain, Bull. Soc. chim. France, 1972, 1617. 173 J. R. Durig, K. L. Hellams, and J. H. Mulligan, Spectrochim. Atfa, 1972, 28A, 1039.

IR6

lER

266


MCC-B I

c1

(B

=

FSO,, CISO,, C10, , or CF,SO,) Scheme 1

rotate freely, leading to an assignment of ring-vibrations in terms of local C2, symmetry, and of Si-H(D) fundamentals in the way shown in Table 14. Si-H stretching wavenumbers for Me,EtSiH, MeEt,SiH, and Et,SiH have been measured and

Table 14

Wavenumberslcm-l of fundamentals of the silyl group in phenylsilane PhSiH,

(ti

21 58

&yrn(Si "H3) p(Si"H3) [O.P.I p(SinH3) [i.p.]

952 928 678 645

= 1)

PhSiD, (n = 2) 1584 1558

671 662 540 507

Co-condensation of SiF2 with diborane affords two thermally very unstable di borane derivatives, tentatively formulated as the novel heterocycles (SiF2),B2Ha(20) on the basis of, as well as other evidence, their

gas-phase i.r. spectra : the latter include bands assigned to V(B-H)terrlrlIlal (near 2600 cm-I) and V(B-H)briae (at 1570 cm-l). Decomposition of these species yields, in addition to known products, the new compounds H3SiSiF3and H,Si(SiF,),, for which gas-phase i.r. absorptions have been measured and assigned. Those given for 1,1,l-trifluorodisilane are sunimarized in Table 15. The authors suggest that the large change in wave17'

I. V. Shevchenko, I. F. Kovalev, V. s. Dernova, M. G. Voronkov, Yu. I. Khudobin, N. A. Andreeva, and N. P. Kharitonov, Izvest. Akad. Nauk. S.S.S.R., Ser. khinr., 1972, 98.

Characteristic Vibrational Frequencies of Conipoirnds 267 Table 15 Infrared spectrum of 1,1,1 -trifiuorodisilnne (wauenurnber/cin-l) Suggested assign nient

vasym(si- H 1 vayni(S i - H ) vasyndsi- F)

H 3SiSiF, 2191 2180

6W3YlXl(SinH3)

v,ym(Si--F) &ym(SinHg) v(Si-Si) &sy m (Si Fa) SSYI11(SiF3)

96 1 826 532 505 306

D3SiSiF3 I601 1568 9 59 774 866 654 51 1 49 3 299

number for vSym(Si--F) observed between H,SiSiF, and D,SiSiF, can be accounted for in terms of strong interaction of this vibration with SSym(SiH3),the corresponding antisymmetric modes not coupling so effectively.l7 1.r. bands for SinH3,NnHPF2(n = 1 or 2) have been recorded and partly assigned. Doubling of N-H stretching and bending modes i n the vapour phase at room temperature is taken to indicate the existence of two different conformers, but solid-phase nieasurenients at 77 K suggest that at this temperature one of these is much the more ~ t a b 1 e . lPartial ~ ~ fluorination with PFBof Si-H bonds in hydrosiloxanes has yielded the following new compounds: SiH,OSiH,F, (SiH,F),O, MeSiHFOSiH,Me, and (MeSiHF),O. Gas-phase i.r. absorptions have been reported and partially assigned for each of Trisilylamine reacts with H2E (E = S or Se) at room temperature to give, in addition to (SiH,),E, solid adducts which have been formulated as NH,+(ESiH,)-, and related salts of the MeNH,+ and Me2NHa+cations have also been prepared.178 Some i.r. frequencies for the silyl anions are listed in Table 16. Reaction of atomic silicon with silanes affords the polysilanes Me,SiHSiH,SiHMe,, MeH,SiSiH,SiH,Me, and n-SiSHI2,for which unassigned i.r. data have been given.179 SiHCI,

Table 16 Assignment of SiH, fundamentals (wat.enuntber/cm-') ,for. salts of silanethiol and silaneselenol Assignment

-

v( Si H) &SiH,) p(SiH,) Y( Si

-E)

R+(SSiH,)R=NH, R=ND, 2100 2100 930 935 635 635 550 5 50

R (SeSiH,)R = NH, R = Me,NH, 2120 2050 930 935 615 430 430

E = S or Se. 17'

D. Solan and A . B. Burg, Inorg. Chern., 1972, 11, 1253. D. E. J. Arnold, E. A. V. Ebsworth, H. F. Jessep. and D. W. H. Rankin, J.C.S. Dalton, 1972, 1681.

E. W. Kifer a n d C. H. Van Dyke, Inorg. Chern., 1972, 11, 404. S. Cradock, E. A. V. Ebsworth, and H. F. Jessep, J.C.S. Dnlton, 1972, 359. P. S. Skell and P. W. Owen, J. Amer. Chem. Soc., 1972, 94, 5434.

368

Spet*~rosc*opic Properties qf' Ittor-gcrrricmid Orgnnometallic Comportncls

and MeSiHCI, and their deuteriated analogues have been identified as products from the reaction of chlorosilylnickel complexes with HCI or DCI in benzene solution through observation of appropriate Si- I-I (Si-D) stretching fundamentals.1so Silylgermylmethane, SiH,CH,GeH,, synthesized in 357; yield by the action of NaGeH, on SiH,CH,CI, and its derivatives GeH,CH,SiH,CI, GeH,CH2SiHCI,, (GeH,CH,SiH2)20, and (SiH,CH,),GeH, have been examined by Van Dyke et a / . Partial assignments of i.r. bands presented in this work include those of Table 17 for the parent compound.18'

Table 17 I.r. data for silylgermylmethane, SiH3CH,GeH, Assignment v(Si- H) v(Ge-H) 6(CH,) 'scissor' 8(CH,) 'wag' 6( Si H3) 8(GeH3) v( Si -C ) v(Ge-C)

WuiTenumber/cni21 50---2210 2056-2095 1362- 1382 1049- 1055 94 1 8 50 75&774 650 (?)

A complete interpretation of the vibrational spectra of p-FCBH,GeH, and p-CIC6H,GeH3 indicates a very low barrier to rotation about the C-Ge bond.la2 The i.r. and Raman spectra of the methylhalogenogermanes MeGenH,X (n = 1 or 2; X = F, C1, Br, or I ) have been the subject of a thorough study by Drake and co-workers, including valence force-constant The authors were able to propose assignments for all fundamentals except the torsion for each molecule on the basis of C , symmetry, including those of Table 18 for GeH, bending niodes.

Table 18

Wavenumbers/cm-l for Ge-H bending modes in methylhctlogenogermanes, MeGeH,X or MeGeD,X v,(d

(GeH, 'bend')

v7(a')

(GeH, 'twist')

H D 721 565 717 544 705 539 694 520

n D 705 565 717 ( ? ) 544(?) 705 (?) 531 694(?) 513

r - - 4 - - 3 - - -

X F

H 11 900 625 875 624 875 622 873 618

c1 Br 1

v,,(a")

(GeH, 'mag')

v17([If')

(GeH, 'rock') H 472 463 456 442

D 379 360 350 336

Identification of the latter was facilitated by refcrence to data obtained through synthesis of additional deuteriated species CD,GeH,X (X = C1 Y. Kiso, K . Tamao, and M. Kumada, J.C.S. Cham. Contm., 1972, 105. C . H. Van Dyke, E. W. Kifer, and G . A . Gibbon, Innrg. Chem., 1972, 11, 408. J. R. Durig and J . B. Turner, J. Phys. Chem., 1972, 76, 1558. G. K. Barker. J . E. Drake, R. T. Hemmings, and B. Rapp, Specrroc,hirn. Acrn, 1971, 28A, 1113.

lH0

l','


269 or Br). Substantial mixing of v7 and u16,indicated by the appearance of the spectra, featured prominently in the calculations. Two strong absorptions of equal intensity attributable to symmetric GeH, deformation modes occur i n the i.r. spectrum of (GeH,),Fe(CO),, at 809 and 835 cm-l. This situation contrasts with that encountered for other digermyl compounds, which show only one such band, but similar spectra have been observed for certain disilyl derivatives.18* References 185-192 give wavenumbers for Si-H or Ge-H vibrations for the compounds collected in Table 19.

Table 19 References to Si-H and Ge andfor Raman spectroscopy

H compounds characterized

Ref.

Conipourid

H2J’Si

184a

m \ S /i H 2

185

I

i.r. Ref.

187 188

GeH,AsMe, (GeH,),AsMe GeH,AsPh,

Me

bji

>

189 190

Me Me(C1)SiHSiH, MeSiH,SiH,CI Me( CI)SiHSiH,CI MeSiCl,SiH, Me(Cl)SiHSiHCI,

]

191 184 186

192

Hydrostannylation of styrene, using R,SnH, (R = Et, Bun, or Ph) or RPhSnH, (R = Et or Bu”),has been followed by monitoring the decrease in intensity of i.r. absorptions due to v(Sn-H), wavenumbers for the latter for each stannane also being listed.lQ3 S. R. Stobart, J.C.S. Dalton, 1972, 2442. B. N. Cyvin, S. J. Cyvin, L. V. Vilkov, and V. S. Mastryukov, Rev. Chim. Mirzhalci, 1971. 8, 877. IHG L. Birkofer and H. Haddad, Chern. Ber., 1972, 105, 2101. C. L. Frye and J. M. Klosowski, J. Amer. Chem. SOC.,1972, 94, 7186. lll6 A. J. Vanderwielen and M. A. Ring, Znorg. Chem., 1972, 11, 246. l a 7 E. Hengge, G . Bauer, and M. Marketz, Z . anorg. Chem., 1972, 394, 93. ln6 T. C . Geisler, C. G . Cooper, and A. D. Norman, Znorg. Chem., 1972, 11, 1710. l R QJ. W. Anderson and J. E. Drake, J.C.S. Dalton, 1972, 951. l B n R. D. George, K. M. Mackay, and S. R. Stobart, J.C.S. Dalton, 1972, 974. lD1 R. D. George, K. M. Mackay, and S. R. Stobart, J.C.S. Dalron, 1972, 1505. J. V. Scibelli and M. D. Curtis, J. Organometallic Chem., 1972, 40,317. lUy L. S. Mel’nichenko, A. N . Rodionov, N. N . Zemlyanskii, and K . A . Kocheshkov, Doklady Chem., 1971, 201, 996. lU4

1H4a

270


Compounds containing M-C Bonds (M = Si, Ge, Sn,or Pb).-1.r. spectroscopy has been used (in the range 400-1 100 cm-l) in a study of S i c singlecrystal films formed by bombardment of crystalline Si with C+ ions.lB4 Flash photolysis of 1,l-dimethyl-1-silacyclobutane(21) at 650 "C, followed by deposition of the pyrolysate at - 196 "C onto an NaCl plate, gives in addition to features due to (21) a new sharp band in the i.r. at 1407 cm-l. Warming to - 120 "C results in non-reversible disappearance of this band, Me, Si=CH, Me'

(22)

(21)

which is tentatively attributed to a fundamental of the species (22), presumably v(Si= CH2).lg5 Co-condensation of tin with carbon monoxide at 20 K in an Ar matrix affords a phase with a large number of i.r. bands in the CO stretching region.lgs At low CO concentration in the matrix, however, a very prominent band appears at 1921 cm-l, thought to be due to the metal-rich species SnCO; a band at 1908 cm-l observed after reaction of Ge under similar conditions is attributed to GeCO. 1.r. and Raman spectra of the ethynyls M(C=CMe), (M = Si, Ge, or Pb) have been discussed on the basis of T, symmetry, v(M-C) modes being assignedlQ7as shown in Table 20. Similar data for tetrabenzylgermane and -stannane and some halogeno-derivatives have also been reand are listed in Table 21. Incidence of more than the predicted Table 20 Metal-carbon stretching wauenumber/cm-l for tetra(methylethynyl) derivatives of Si, Ge, and Pb M Si Ge Pb

dM--C), 384 371 331

Ul

4M-C), 605 440 -

fi

Table 21 Raman bands assigned to Ge-C and Sn-C stretching fundamentals for tetrabenzyl and related derivatives Compound Wavenurnberlcm-' (Ph CH Ge (Ph CH S n (PhCH,),SnCI (PhCH,),SnCI, (PhCH,),SnBr,

615(dP), 5 W P )

572(dP), 583(dP), 589(dP), 587(dP),

558(P) 565(P) 570(P) 5WP)

E. K. Baranova, K. D. Demakov, K. V. Stavinin, L. I. Strel'tsov, and I . B. Khaibullin, Doklady Phys. Chem., 1971, 200, 847. IDS T. J. Barton and C. L. McIntosh, J.C.S. Chem. Comm., 1972, 861. l Q o A. Bos, J.C.S. Chem. Comm., 1972, 26. l g 7 R . E. Sacher, B. C. Pant, F. A. Miller, and F. R. Brown, Spectrochim. Acta, 1972, 2%A,1361. L. Verdonck and Z . Eeckhaut, Spectrochim. Acta, 1972, 28A,433. lu4

Characteristic Vibrational Frequencies of Compounds 27 1 number of features for the latter compounds in the range 600-200 cm-l is thought to arise through hindered rotation about the Ph-C bonds, and for (PhCH,),Hg, also examined, a single polarized band was found at 564cm-l. Vibrational spectra for (Me3SiCH2),M (M = Sn or Pb) and Me,SiCH,Cl have been recorded and discussed as a part of an investigation of the properties of some trimethylsilylmethyl-metal cornpounds.lee Consideration of Raman spectra for R1,Sn(C=CR2)4-. (Rl, R2 = alkyl, CH=CH2, or Ph; n = 1-3) and R,SnC=CSnR, (R as above) have led to 'the proposal that in these species, interactions between separate substituent n-systems are completely inhibited by the tin atoms.200 Shifts and broadening of V(C-H)ethynyl in dioxan and acetone solutions for a series of related ethynyl-tin derivatives have been interpreted in terms of R',SnC=CH OR2hydrogen-bonding.20LUnassigned i.r. frequencies for 203 (23) and (24) have been

-

(23)

M

= Si, Ge, Sn, or Pb; R = Me or Ph

A comprehensive study below 350 cm-l of trimethylchlorosilane by microwave as well as far4.r. and Raman techniques has provided a number of new assignments for this molecule. A value of 3.0 kcal mol-l for the barrier to internal rotation has been derived from frequencies of 233, 208 cm-l [176, 148 cm-l for (CD,),SiCl] for i.r. absorptions attributed to, Some new data have also been given for respectively, e and a, Me,GeF, including normal-co-ordinate calculations.206 The i.r. and Raman spectra of Pr"SnC1, are consistent with the presence in the liquid state of both trans- and gauche-isomers, v(Sn-C) being markedly different (599 as opposed to 523 cm-l) for the two rotamers.206 Investigation of the compounds (p-YC6H,CH,),SnCl,-, (Y = H, F, or C1; n = 2 or 3) has shown that although para-substitution has virtually no effect on v(Sn-Cl), references are collected in Table 22. 190

201

W. Mowat, A. Shortland, G. Yagupsky, N. J . Hill, M. Yagupsky, and G. Wilkinson, J.C.S. Dalton, 1972, 533. 0 . A. Zasyadko, R. G. Mirskov, N. P. Ivanova, and Yu. L. Frolov, Zhur. priklud. Spektroskopii, 1971, 15, 718. 0. A. Zasyadko, Yu. L. Frolov, and R. G . Mirskov, Zhur. priklad. Spektroskopii, 1971, 15, 939.

?O1

204 "OK

so7

J. Y . Corey, M. Dueber, and M. Malaidza, J . Organometallic Chem., 1972, 36, 49. G. Fritz and M. Hlhnke, Z . anorg. Chem., 1972, 390, 104. J. R. Durig, R. 0. Carter, and Y.S. Li, J . Mol. Specrroscopy, 1972, 44, 18. C . Peuker and K. Licht, Z . phys. Chem. (Leiprig), 1971, 248, 103. H . Geissler, Chr. Peuker, R. Heess, and H. Kriegsmann, Z . anorg. Chem., 1972, 393, 230.

L. Verdonck and G. P. van der Kelen, J . Organometallic Chem., 1972, 40,135.

272

Spectrmcopic Properties of Inorganic and Organometallic Compounds

a decrease in v(Sn-C) is evident.207 Unassigned i.r. wavenumbers have been listed for some perfluoro-alkyl and -aryl silanes and germanes;

Table 22

Referertces containing i.r. wavenumbers for perfluoro-alkyl and -uryl silanes and germanes Coritpo und

Ref. 208

209

Normal-co-ordinate calculations for the cyclobutanes (25) have been published.184J" Studies on 1,3,5,7-tetrasila-adamantanes (26) (named carborundanes) include some i.r. data.185a Butadiene reacts with SiFz to give (27) for which partially assigned i.r. bands have been given,21oReactions of tin(ii) halides with dimethylacetylenedicarboxylate afford (28), with v(Sn-C) assigned 211 at 3 9 s - 4 1 5cm-l. A band at 570 cm-l in the i.r. spectrum of Me,Sn(salen) is due to vasyIn(Sn-C), but no feature attributable to v,,,,(Sn-C) could be found, suggesting the structure (29) for this complex, with an approximately linear C-Sn-C Harrison and co-workers have obtained low-frequency i.r. data for several five- and six-co-ordinate methyltin halides which can be interpreted in terms of different stereochemistries : planar SnC, groups (e.g.in Me,SnI,) give rise to a single v(Sn-C) absorption near 550cm-l, but Me,SnX, systems usually show two bands at ca. 570 and 515 cm-l, indicating the presence of both axial and equatorial Sn-C bonds.214 Various other papers contain vibrational information for compounds with M-C bonds, some including assignments for v(M-C) fundamentals (M = Si, Ge, or Sn). These refer to Me,Si(OR),-, (n = 1--3; R = Me 20R

?OU

*I1 213

K . G. Sharp and T. D. Coyle, Inorg. Cheni., 1972, 11, 1259. M. Weidenbruch and N. Wessal, Chern. Ber., 1972, 105, 173. J . C. Thompson and J . L. Margrave, Inorg. Chem., 1972, 11, 913. P. G . Harrison, Inorg. Nuclear Chern. Letters, 1972, 8 , 555. H . Schmidbaur and W . Kapp, Chem. Ber., 1972, 105, 1203. R. Barbieri and R. H. Herber, J . Organomrtalfic Chern., 1972, 42, 65. M . K. Das, J. Buckle, and P. G . Harrison, Inorg. Chim. Acta, 1972, 6. 17.

273 Me I

R

MR

SiF,

kSn

CkiF,

x2

R

(27) (28) X

=

R

x2

C l , B r , o r I ; R = MeO-CO

or Et);?15 Me,Si(ON:CR1R2),-, (n = 0--3; R1, R2 various);216 the silylated ylides Me,SiR,-, [n = 0-3; R = CH=S(0)Me,];212 Et,GeCH(CN)CH2PEt2;217 some organotin esters;21HR2Sn(P02F,), (R = Me, Et, Pr”, Bun, or n-C8H17);21g and the sulphonates 220 Me,Sn(SO,F),, Me,Sn(S03CF3),, Me,SnSO,F, MeSnCI,SO,F, Me,SnCI(SO,F), MeSnCI(SO,F),, and MeSnCI(SO,CF,), for which vnsyIII(Sn-C) [or v(Sn-C)I and vsyIll(Sn-C), respectively, were found within the ranges 576- 585 and 523-535 cm-I. Compounds containing M-M Bonds (M = Si, Ge, or Sn).--Within this category only polysilanes have received significant attention during 1972. 1.r. and Raman spectra for hexafluorodisilane have been recorded and assigned by Hoffler, Hengge, and Waldhor : normal-co-ordinate calculations indicated that a band at 541 cm-l with 56% v(Si-Si) character also involved substantial contributions from both of the other a l , modes ‘?Ib “Is

“17 “IR

”””

N. V. Kozlova, V. P. Bazov, I . F. Kovalev, and M . G . Voronkov, h t v . P S R Zitiat. Akad. Vestis, Kim. Ser., 1971, 604. A. Singh, A. K. Rai, and R. C. Mehrotra, J . C . S . Dalton, 1972, 1911. J. SatgC, C. Couret, and J. Escudie, J . Organometallic Chem., 1972, 34, 83. N. W. G. Debye, D. E. Fenton, and J. J . Zuckerman, J . Inorg. Nucleur Chem., 1972, 34, 352. T. H . Tan, J. R . Dalziel, P. A. Yeats, J. R. Sams, R. C. Thompson, and F. Aubke, Canad. J . Chem., 1972, 50, 1843. P. A. Yeats, J. R . Sams, and F. Aubke, Inorg. Chem., 1972, 11, 2634. 10

274

Spectroscopic Properties of’Inorgnrtic and Orgartontetnllic Compoirrrrls

[vs,,(Si-F) at 910cm-l, and G,,,,,(SiF,) at 220cn1-~], and a value of 2.4 -1- 0.2 mdyn k1for f’j-sj was derived.221 Further work by the same authors on methyl(ch1oro)disilanes 222 and methyl(methoxy)disilanes 233 has suggested similar heavy mixing of v(Si-Si) with other fundamentals. For Me,ClSiSiMe,CI, a polarized Raman band at 398 cm-l is attributed mainly to Si-Si stretching, but for Si,(OMe), (fsi-si = 2.25 mdyn A-l) calculations showed that the same mode contributed substantially to three bands, at 760, 523, and 229 cm-l. 1,1,1-Trifluorosilane has already been ment i ~ n e d , ”and ~ for this compound and its deuteriated counterpart v(Si-Si) were assigned to i.r. absorptions at 532 and 511 cm-l, respectively. Reactions of Me,SiCl, and of MeSiC1, with sodium-potassium alloy in the presence of naphthalene have yielded novel bicyclic and cage polysilanes Si,Me,,, Si,Me,,, Si,,Me,,, and Sil,Mel,. Structures (30)--(32) have been Me

Si

Me, Si”

I Me,Si

‘SiMe,

SIMe2 SiMe, I

\\si

SlMe2

/

Me Me

proposed for three of these on the basis of n.m.r. and U.V. data, and although measured i.r. frequencies have not been assigned it is suggested that bands in the 350-450cm-l region arise from v(Si-Si) modes.224 Further unassigned data have been published, for polysilanes listed earlier in Table 19, and also for Me,SiSiIPh,, Me,SiSi(OMe),Ph, and Me,SiSi(OMe), (ref. 187), and Me,P=N-SiMe,SiMe, and Me,P=N-SiMe,SiMe,-CH=PMe, (ref. 224a). An improved synthesis has been reported for GeBr, which, on reaction with GeBr,, affords Br,GeGeBr,. Observation for this digermane of six Raman-active fundamentals (315, 196, and 78, species A l , ; 339, 111, and y2p

‘‘u 224

24w

F. Hofler, S. Waldhor, and E. Hengge, Specrrochitn. A m , 1972, 28A,29. F. Hofler and E. Hengge, Monarsh., 1972, 103, 1506. F. Hofler and E. Hengge, Monarsh., 1972, 103, 1513. R. West and A, Indriksons, J . Amer. Chein. Soc., 1972, 94, 6110. H . Schmidbaur and W. Vornberger, Chetn. Bey., 1972, 105, 3187.

Characteristic Vibrntionnl Frequencies of Coinpoutids 275 68 cm-l, species E,) together with non-coincident i.r. bands at 327 and 247 cm-l establishes a DSd (staggered) conformation in the solid state. Assignment of an individual band to v(Ge-Ge) was not attempted.2251.r. spectra for the perniethylcyclopolygermanes (Me,Ge), (n = 5 , 6, or 7) have been measured, but only one absorption, at 367 cm-l for the first of these, could be assigned to a Ge-Ge stretching mode.226Similar data for R,SnSnR, ( R = Bur' or Ph) have been reported but no assignments were given.,,?

Compounds containing M-N Bonds (M = Si, Ge, Sn, or Pb), M-P Bonds (M = Si or Sn), or Si-As Bonds.-The compounds Me3NnH[(CI,Si),N] have been prepared by treating bis(trichlorosily1)amine with Me,N. 1.r. bands for these species at 1185, 785 (n = 1) and 1192, 792 cm-l (n = 2) have been assigned to vaaym and v,,,(SiNSi), respectively, and it has been pryposed 228 that the anion possesses a structure corresponding to [CI,Si=N=SiCl,]-. Bis(trimethylsily1)acetamide and monotrimethylacetamide have been shown to have structures (33) and (34) using 16N

PSiMes Me-C\

0

Me-C,

//

NSiMes

NH(SiMe8)

(33)

(34)

substitution, both by n.m.r. and i.r. investigation. The occurrence of small shifts in i.r. bands near 930, 720 cm-l for (33) and 1030, 990 cm-l for (34) between different isotopomers is tentatively ascribed to involvement of v(Si-N) modes.229 Some assignments for Me,SiN(R)BF, (R = Me, Et, Pr, Pr', or Bu) 230 and Me,P=NSi,Me,, Me,P=NSi,Me,N=PMe,, Me,P=NSi,Me,CI, and Me,P=NSi,Me,CH=PMe, have been suggested, including v(Si-- N) near 570 cm-l in the (di~ilary1)phosphineimides.~~~~ The azomethine derivatives But,C=NR (R = SiMe,, SiMe,CI, SiMeCI,, or SiCI,) show v(C=N) at ca. 1735 and v(Si-N) at ca. 960 cm-l, corresponding bands for Ph,C=NR (R = SiMe, or SiMe,Cl) occurring at 1640 and 905 cm-l, Wannagat and Meier have characterized the novel cyclic systems (35)-(38), for which 232 either one or two i.r. bands at 895-950 cm-l are assigned to va8,,(SiNSi) with vsyll, at 530-550 cm-l. 226

2 ~ E 227

m

23L

py2

M. D. Curtis and P. Wolber, Inorg. Chem., 1972, 11, 431. E. Carberry, B. D. Dombek, and S. C. Cohen, J . Organometallic Chem., 1972, 36, 61. H. Prakash and H . H. Sisler, Inorg. Chem., 1972, 11, 2258. H. H . Moretto, P. Schmidt, and U . Wannagat, Z . anorg. Chem., 1972, 394, 125. C. H. Yoder and D. Bonelli, Inorg. Nuclear Chem. Letters, 1972, 8, 1027. G. Elter, 0. Glernser, and W. Herzog, J . Organoinefallic Chem., 1972, 36, 257. J. B. Farmer, R. Snaith. and K. Wade, J.C.S. Dalton, 1972, 1501. U . Wannagat and S. Meier, Z . anorg. Chem., 1972, 392, 179.

276

Spectroscopic Properties of Inorgonic and Organometallic Compoirndy M e2

Me2

o'si\*

NMe \

/

Me, Si

SiMe,

I

PrN,

I

NPr

(SiMe,
vasynl(FeGes). Clod--, PFc, and BF4 Undistinguished i.r. value5 salts. * Identical values for the series X - CI, Br, or I. for v(1nMn) of a trigonal-planar InMn, skeleton. f v(GaGa). undistinguished These and other vibrational data used to identify the compounds as proIj(GaMn). ducts of reaction of Mn,(CO)lo with In or Ga.

''

3 14


Full details have now appeared of the vibrational spectroscopic evidence for assigning a pyrazine-bridged sheet structure, with terminal halogen atoms, to complexes MX,(pyrazine), [M = Co or Ni; X = C1, Br, or ]].I4 v(MX) Modes have also been assigned in the following systems: MCI2(Ph2PO*NMe2), [M = Mg, Ca, Mn, Fe, Co, Ni, Cu, Zn, or Cd];31 MCl,(thiophen-2-aldoxime), [M = Zn, Ni, Cu, or Pd];,, [MX,L]+ salts (M = Co, Ni, Cu, or Zn; X = CI or Br; L = 1,1,4-trimethylpiperazinium cation);33 a large number of complexes of pyridine-?-thiol, pyridine-4-thio1, 2-methylpyridine-6-thio1, or some oxygen analogues with Sn'", Bi'" , or MI1 (M = Co, Ni, Zn, Cd, Hg, or Pt);,, [MC1412 salts (M = Mn, Co, Cu, or Zn) of the 2,4-dimethyl-l H-l,5-benzodiazepinium cation;35 and in dimethoxyethane adducts of MCI, (M = Ti or V ) or Cr CI,. 36 Metal-metal vibrational assignments, of which fewer were noted this year, are collected together in Tables 2 and 3.37-48 Further measurements have also been made on the spectra of M[Co(CO),], species ( M = Zn, Cd, or Hg); metal-metal force constants vary in the order: k(Zn-Co)

2 k(Cd-Co) 2 k(Hg-Co)

and significant coupling across the trinuclear M1M2, unit was found.'* 3 Scandium

1.r. spectroscopy has been used to show that various [Sc(NCS),]- salts (generally hydrated) contained N-bonded NCS- ligands; the values proposed for v( M -OH2) and v( M -NCS) are remarkably high.60 I' :j2

33 34

3H 97

38 X'

bo 41 Oa

44

45

M. W. G . De Bolster and W. L. Groeneveld, Z . Naturforsch., 1972, 27h,759. M. P. Coakley and M . E. Casey, J . Inorg. Nuclear Chem., 1972, 34, 1937. A . S. N. Murthy, J. V. Quagliano, and L. M . Vallarino, Inorg. Chim. Acto, 1972, 6 , 4 9 . B. P. Kennedy and A. B. P. Lever, Canad. J . Chem., 1972, 50, 3488. P. W. W. Hunter and G. A. Webb, J . Inorg. Nuclear Chem., 1972, 34, 151 1 . E. Hengge and H. Zimmermann, Monatsh., 1972, 103, 418. F. A . Cotton and J. G. Norman, J . Amer. Chem. SOC.,1972, 94, 5697. R. D . George, K. M. Mackay, and S. R . Stobart, J.C.S. Dalton, 1972, 1505. R . A. Burnham, F. Glockling, and S. R . Stobart, J.C.S. Dalton, 1972, 1991. C. S. Cundy and M. F. Lappert, J.C.S. Chem. Comm., 1972, 445. S. R. Stobart, J.C.S. Dalton, 1972, 2442. R . D . George, K. M. Mackay, and S. R. Stobart, J.C.S. Dalton, 1972, 974. P. Braunstein and J. Dehand, J.C.S. Chem. Comm., 1972, 164; Compt. rend., 1972, 214, C, 175. R. P. J. Cooney and J. R. Hall, J . Inorg. Nuclear Chem., 1972, 34, 1519. D . N. Hendrickson, Y . S. Sohn, W. H. Morrison, jun., and H. B. Gray, Inorg. Chem., 1972, 11, 808.

47

4u

sf'

H. L. Conder and W. R. Robinson, Inorg. Chem., 1972, 11, 1527. F. J. A. Des Tombe, G. J. M. Van Der Kerk, H . M. J. C. Creemers, N. A. D. Carey, and J. G . Noltes, J. Organometallic Chem., 1972, 44,247. H.-J. Haupt and F. Neumann, 2. anorg. Chem., 1972,394, 67. R. J. Ziegler, J. M. Burlitch, S. E. Hayes, and W. M. Risen,jun., Inorg. Chem., 1972. 11, 702.

L. N. Komissarova, T. M . Sas, and V. G . Gulia, R i m . J . Inorg. Chem., 1971, 16, 1115.

315 The i.r. and Raman spectra of [ S C ( C O ~ ) ~in] ~aqueous solution have been compared with those of aqueous Na,CO,, and the presence of bidentate CO,,- groups has been deduced; v(Sc0) is given as 360cm-l (i.r.).51 The thermal decompositions of the following Sc compounds have been studied using i.r. and other techniques: K,Sc(SeO,), and MSc(SeO,), [M = Rb or C S ] ; ~SC,(S~O,),(H,O),;~~ , and ScI,(H,O), and Sc(0H)I,(H20)6.54 Assignments of i.r. data for ScPO, pre-heated to 1000 "C, ScP04(H20),, and Sc(H,PO,), have been given in terms of Td symmetry of the PO4 groups, whereas for ScPO, pre-heated to 800 "C and [Sc(PO,),],, the symmetry of the PO, groups is said to be C3v.55 1.r. data have been listed for ScX,(phen), and ScX,(bipy), [X = NCS, NOs, or Cl], all of which are believed to contain seven-co-ordinate 5 7 some of the assignments given for v(ML) modes [e.g. v(ScC1) at ca. 470 cm-'1 are in spectacular contrast to normally accepted ranges. 1.r.-active v(ScX) values have been given for anhydrous ScCI, (3 10 cm-l) and ScBr, (280 ~ m - l ) . ~ ~ No vibrational data on yttrium compounds were collected during last year. Compounds of lanthanides and actinides are considered in Sections 13 and 14. Vibrational Spectra of Transition-elentent Compounds

4 Titanium, Zirconium, and Hafnium The polymeric structure of [(n-C,H,),TiH], gives rise to the very low value for v(Ti-H-Ti) of 1140 cm-l ( 8 W 8 5 0 cm-l in the deuteiiated compound), compared with the value of 1450 cm-l for [(T-C~H,),T~H],.~~ In contrast, [(n-C5H5)(C5H,)TiH],[one of several products from the action of Na on (7r-C5H,),TiCl,] shows v(TiH) at 1960 and 1815 cm-l (1355 and 1305 cm-l in the corresponding deuteriate).,O 1.r. bands at 1350 and 1780 cm -l have been assigned to v(ZrH,Zr) and v(ZrHAl), respectively, in the tetranuclear compound (2); these bands shift to 980 and 1290cm-I, respectively, on deuteriation.,' 61

B. Taravel, F. Fromage, P. Delorme, and V. Lorenzelli, Compt. rend., 1972, 275, B, 589.

H. Tetsu, L. G. Korotaeva, and B. N. Ivanov-Emin, Russ. J. Inorg. Chem., 1971, 16,

957. 63

H. Tetsu, L. G. Korotaeva, and B. N . Ivanov-Emin, Russ. J. Itrorg. Chetn., 1971, 16, 1552.

64

L6

L7

c8

eo

N. P. Shepelev, I. V. Arkangel'skii, L. N. Komissarova, and V. M. Shatskii, Russ. J . Inorg. Chem., 1971, 16, 1706. L, N. Kornissarova, P. P. Mel'nikov, E. G . Teterin, and V. F. Chuvaev, Russ. J . Inorg. Chem., 1971, 16, 1414. L. N. Komissarova, Yu. G. Eremin, V. S. Katochkina, and T. M. Sas, Russ. J. Inorg. Chem., 1971, 16, 1570. L. N. Komissarova, Yu. G. Eremin, V. S. Katochkina, and T. M. Sas, R i m . J. Inorg. Chem., 1971, 16, 1708. R. W. Stotz and G. A. Melson, Itiarg. Chem., 1972, 11, 1720. J. E. Bercaw, R. H. Marvich, L. G. Bell, and H. H. Brintzinger, J. Atner. Cheni.

SOC., 1972, 94, 1219. E. E. van Tarnelen, W. Cretney, N. Klaentschi, and J. S. Miller, J.C.S. Chern. Comtil., 1972, 481.

P. C . Waites, H. Weigold, and A. P. Bell, J. Organonretallic Chem., 1972, 43, C29.

3 16


Further i.r. data have been reported for Me,TiCI,, CD,TiCI,, and (CD,),TiCl,, but definitive assignments were not possible.e2 In 1:1 adducts of MeTiCl, with MeCOCH,CH,NMe,, MeOCH2CH,SMe, Me,NCH,CH,SMe, and o-Me,NC,H,CH,NMe,, v(TiC) is in the range 459484 cni-l ; two geometrical isomers were identified for MeTiCI3(Me,NCH,CH,SMe), corresponding to the Me-Ti bond being trans to the SMe or NMe, groups of the ligand.63 Further details and some additional examples have now been given 6 4 of the spectra of methyltitanium halogenoanions included in last year's report, e.g. [Me,Ti,Cl,]-, [Me,Ti2C1Br,] , [Me,Ti2Bre12-, [ Me2Ti,C1,Br,]2-, and [ MeTiC1,Br,l2-. Assignments for the low-frequency vibrations of (n-C5H5)TiX3and (7r-C5Me5)TiX,[X = C1 or Br] are listed in Table 4.65 Similar values for v(Ti-ring) (430-440 cm-l) and v(TiC1) (310-320 cm-l) have been proposed for complexes Spectra of (7r-C5H5)TiC1,(L) [L = bipy, phen, py, or a-pi~olylamine].~~ (7r-C5Me5)Ti(CO), and [(7r-C5H5),TiI2have also been r e p o r t e ~ i . ~In~ (Et,N),Ti-CH=CMe,, v(TiC) and v(TiN) are at 495 and 612cm l , respectively;67corresponding values for (Et,N),Ti--(Me)= CH, are 533 and 620 cm-l. Isothiocyanato-complexes of titanium have been formulated as in Table 5 on the basis of v(CS) and G(NCS) frequencies.6s In K2[M(NCSe),], Table 4 Lowfrequency compounds

uibrationslcm-l of (n-C5H5)TiX, and (7r-C5Me,)TiX,

(7r-C5H,)TiC13 453

(7~- C, M e5)Ti CI

460

404

408

327

338

{ ::: -

160

I I5 210

,

(r-C,H,)Ti Br, 425

(T-C, M e,)Ti Rr,,

438

{ { :; 130

3 30

264 -

110

174

J . F. Hanlan and J. D. McCowan, Cunad. J . Chem., 1972, 50, 747 R. J. H. Clark and A. J. McAlees, Inorg. Chem., 1972, 11, 342. m R. J. H . Clark and M. A. Coles, J.C.S.-Dalfon,1972, 2454. 0. S. Roshchupkina, V. A. Dubovitskii, and Yu. G . Borod'ko, J . Strucf. Chetn., 1972, 12, 928. R. S. P. Coutts. R. L. Martin, and P. C. Wailes, Austral. J . Chem., 1972, 25, 1401. H. Burger and 1 I.-J. Neese, J . Organomefnllic Chpm., 1972. 36, 101. tin A. M . Sych and V. P. Dem'yanenko, R i m . J . Itiorg. Chem., 1971, 16, 1593. Oz

63

Vihrationcif Spcc*tr.aof Transition-element Compoirnds

317

Table 5 Low-frequency modeslcm-I of some isotliiocyanato-complexes of tituniitrn Compound

B un4N la [ W NCS), 1 [Me,N] [Ti0(NCS),lb

v(Ti--NCS) 336

v(Ti-amine)

&Ti-NCS)

Symmetry"

-

146

Oh

-

158

D4 A

232 212

{ ::: 158

D2 h D2 h

a Skeletal symmetry deduced from the vibrational data. * A polymeric structure is proposed on the basis of i.r. bands at 800 and 730 cm-' assigned to v(Ti0Ti); G(Ti0Ti) given as 236 cm- I .

v(MN) is at 249 (M = Zr) or 228 cm-l ( M = Hf).6Q The extraction of Zr and Hf thiocyanato-complexes by solvents such as (BunO),PO has been studied using i.r. In alkylphosphine adducts (1:l) of TiCI,, v(TiC1) is in the expected 298-375 cm-l range but v(TiP) is significantly dependent on the nature of the phosphine; values are 410 (MePH,), 375 (Me,PH), 370 (Me,P), and 320 cm-* (Et3P).71 An accurate and rapid Ranian spectroscopic method has been developed for determining low concentrations of anatase in rutile TiO, pigments (0.03-10%).72 In Li,TiO,, i.r. values for v(Ti0) ( 7 2 G 7 4 0 cm-l) support crystallographic evidence for the presence of Ti04 tetrahedra rather than TiOs octahedra (similar results were obtained for Li4Ge04).73Complexes MeOTiCl,(L) [L = MeOCH,CH,NMe,, MeOCH,CH,SMe, or Me,NCH,CH,SMe] 7 4 show v(Ti0) in the 605-615 cm-l range with v(TiC1) between 270 and 400cm-l. Other systems for which v(M-0) or v(M=O) data have been given are: co-precipitated hydroxides of Bi"' and oxytitanium(rv) complexes with various Schiff bases;', [TiO(S0,),]2-, [TiO[Ti(S0,),]2-, [Tiz0(S04)4]2-,and [Ti,0(S0,)J4- salts and their thermal decomposition the complexes TiOCl,L, (L = benzidine, o-phenetidine, etc.);78 tetrakis-(df-mande1ato)zirconium and volatile double alkoxides of hafnium(1v) such as NaHf,(OEt),, K,Hf,(OPr'),,, KHf(OBut)&,HfA1(OPri),, and HfGa2(0Pri)lo.80Vibrations of the biden69

io i1

iz 73

74 i6

i' 77

713

no

A. Galliart and T. M. Brown, J . Inorg. Nuclear Chem., 1972, 34, 3568. 0. A . Sinegribova and G. A. Yagodin, Russ. J . Inorg. Chem., 1971, 16, 1194. C. D. Schmulbach, C. H. Kolich, and C. C. Hinckley, Inorg. Chem., 1972, 11, 2841. R. J. Capwell, F. Spagnolo, and M. A. DeSesa, Appl. Spectroscopy, 1972, 26, 537. B. L. Dubey and A. R. West, Nature Phys. Sci.,1972, 235, 155. R. J. H. Clark and A. J. McAlees, J.C.S. Dalton, 1972. 640. C. Gh. Macarovici and Gh. Morar, 2. anorg. Chem., 1972,393, 275. N. S. Biradar, V. B. Mahale, and V. H. Kulkarni, Inorg. Nuclear Chem. Letters, 1972, 8, 997. S. A. Filatova, Ya. G . Goroshchenko, E. K. Khandros, and G . S. Semenova, Russ. J. Inorg. Chem., 1971, 16, 832. M. M. Khan, J . Inorg. Nuclear Chem., 1972, 34, 3589. E. M. Larsen and E. H. Homeier, Inorg. Chem., 1972, 11, 2687. R . C. Mehrotra and A. Mehrotra, J.C.S. Dalton, 1972, 1203.

3 18

Spectroscopic Properties of Inorganic and Organometnllic Compoimis

tate AcO- ligands in L,M(OAc), [L4H, = octaethylporphin; M = Zr or Hf] have also been assigned.81 TiCl,(acac) has been shown by X-ray crystallography to be a centrosymmetric dimer (3); comparison with TiCl,(acac), and [Ti,CI,] - enabled

i.r. bands to be assigned to v(TiC1) terminal (399 cm-l) and v(TiC1) bridging (276 and 246 cm-1).82 A partial assignment has been given of i.r. and Raman bands of [PCI4],[Ti,Cll0]in terms of modes predicted for a bridged M,CI,, system with D2h ~ y m m e t r y .Complexes ~~ of MCl, (M = Ti, Zr, or Hf) with chlorinated alkyl cyanides such as CH,Cl,-,CN (n = 1 or 2) have also been studied by i.r. spectros~opy.~~ Spectra of ZrX, (X = Cl or Br) and ZrX,L, (X = CI, Br, or I; L = various) are included in a review of certain d" complexes.86

5 Vanadium, Niobium, and Tantalum When (tr-CSHs)2NbBH4[v(BH) = 2450cm-lI is treated with Ph3P or PhPMe,, the complexes (r-C6HS),NbH(Ph3P) [v(NbH) = 1625 cm-l] or ( T - C ~ H ~ ) ~ N ~ H ( P ~ P[v(NbH) M ~ , ) = 1630 cm-l] are formed.86 In [(tr-C6H6)BNbH2(PhPMea)l[PF6],86 v(NbH) is at 1740 cm-l. Partial assignments [e.g. v(VC) = 368-369 cm-'1 have been presented 87 for K4[V(CN)7],2Ha0and K,[V(CN),(NO)],H,O. In a range of dimethylniobium halides and their adducts, v(NbC) is at ca. 490 cm-l in the i.r.88 Unassigned i.r. and Raman data are available for (Et,N)MF, and (EtBN),MFS(M = Nb or Ta).8BInternal modes (i.r.) of the NCS- groups have been assigned for [TaO(NCS),(MeCN),], NH4[TaO(NCS),],2MeCN, [TaS(NCS),(PhNCCl,)], and NH4[TaS(NCS),(PhNCCl,)],80 while u(MN) i.r. values (overall, 228-328 cm-l; generally, 300-320 cm-l) have been 82

J. W. Buchler and K. Rohbock, Inorg. Nuclear Chem. Letters, 1972, 8, 1073. N. Serpone, P. H. Bird, D. G. Bickley, and D. W. Thompson, J.C.S. Chem. Comm., 1972,217.

83 84

86

n7 xy

D. Nicholls and K. R. Seddon, Spectrochim. Acta, 1972, 28A, 2399. G. W. A. Fowles, K. C. Moss, D. A. Rice, and N. Rolfe, J.C.S. Dalton, 1972, 915. D. A. Miller and R. D. Bereman, Co-ordination Chem. Reo., 1972, 9, 107. C. R. Lucas and M. L. H. Green, J.C.S. Chem. Comm., 1972, 1005. A. Miiller, P. Werle, E. Diemann, and P. J. Aymonino, Chem. Eer., 1972, 105, 2419. G. W. A. Fowles, D. A. Rice, and J. D. Wilkins,J.C.S. Dalton, 1972, 2313. 3. C. Fuggle, D. W. A. Sharp, and 3. M. Winfield, J.C.S. Dalton, 1972, 1766. H. Bohland and F. M . Schneider, Z. anorg. Chem., 1972, 390, 5 3 .

Vibmtional Spec I rn of Ti.nrtsition-eleinertt Compoimds

319

‘

proposed for complexes of the types Nb(NCE)4L,, Ta(NCS),(py), and Ta(NCE),(bipy) [L = py or Jbipy; E = S or Se].gl New i.r. datag2 (300-1100cn~-1) on pure V 4 0 3 , V 2 0 4 , and V z 0 5 are quite different from those of previous workers. The absence of coincidences between Raman and i.r. bands shows that from the possible structures proposed for Nb203 from crystallographic studies, the Dzd(P3rnl) space group is correct; assignments of the spectra are given based on quadratic central force-field calculation^.^^ A re-assignment has been put forward for the spectra of the [V20,]*ion, the principal difference being in v,,,,,(VOV) (680-780 cm- l ) and (5-550 cm-l); the actual values for these modes depend v,,,(VOV) on the cation.@*The i.r. spectra (300-4000 cm-l) of orthovanadates having the apatite structure, M,(VO,),X [M = Ca, Sr, or Ba; X = F, C1, or Br], have been assigned in terms of the known C,, unit cell group as follows (symbols refer to Td modes of V043-):95 v,(E,) = 826-850 cm-*; v3(A. 2Eu) = 846-882 and 786-820cm-l; v4(Au 2E,) = 2-3 bands, 356-417 cm-l. Variations in the v 0 d 3 - internal modes with cation M2f and halide X- are also discussed. Site-group and unit-cellgroup analyses have also been carried out for M3(VOJ2 [M = Sr or Ba].06 Raman powder spectroscopy has been shown to be a sensitive method for determination of stoicheiometric variations in lithium niobates and tantalates.@’ Several other vanadates or heteropolyanions containing vanadium have been ~ t u d i e d . ~ ~ - l ~ ~ Two papers on VO(acac), have appeared,lo3sLo4 and further work is clearly needed to reconcile the differing conclusions drawn. A study of the intensity and frequency variations in the v(V=O) mode has led to the conclusion that in THF or EtOH no great disruption of the double-bond character of the V=O linkage occurs, whereas in py or CHC13 there is a significant lowering in VO bond According to other workers,lo4 two series of adducts VO(acac),(L) [L = alkylpyridine] are formed depending on the nature of L, differentiated by having v(V=O) lowered by 42 _+ 4 or 29 2 4cm-l. X-Ray data show that the former series are

+

@l 82 OY u4

*6

97 OH

8@

loo lol lo)

luy lop

+

J. N. Smith and T. M. Brown, Inorg. Chern., 1972, 11, 2697. G . Fabbri and P. Baraldi, Analyt. Chem., 1972, 44, 1325. J. H. Denning and S. D. Ross, J . Phys. ( C ) , 1972, 5 , 1123. R. G. Brown and S. D. Ross, Spectrochim. Acta, 1972, 28A, 1263. E. J. Baran and P. J. Aymonino, 2. anorg. Chem., 1972, 390, 77. E. J. Baran, P. J. Aymonino, and A. Muller, J . Mol. Structure, 1972, 11, 453. B. A. Scott and G. Burns, J . Amer. Cerani. Sac., 1972, 55, 225. A . S. Povarennykh and S. V. Gevork’yan, Mineral. Sbornik (Looo), 1970, 24, 254. B. Reuter and G. Colsmann, 2. anorg. Chern., 1972, 394, 138. A. 1. Ivakin and A . P. Yatsenko, Russ. J . Inorg. Chem., 1971, 16, 893. D. U. Begalieva, A. B. Bekturov, and A. K. Il’yasova, Rum. J . Inorg. Chem., 1971, 16, 1464. A. A. Fotiev, A. G . Rustamov, and A. A. Mambetov, Rum. J . Inorg. Chem., 1971, 16, 1604. R. Larsson, Acta Clietn. Scand., 1972, 26, 539. M . R. Caira, J. M . Haigh, and L. R . Nassimbeni, J . fnorg. IVrirlear Chem., 1972, 34, 3171.

320

Spec froscopic Properlies qf' Inorganic mid Organonietallic Conipoirnds

cis-isomers (4) whereas the others have the Irans-configuration ; the ciscompounds have more complicated spectra in the 30&--600 cm-' range because of the lower symmetry and the presence of two different V - 0 bond lengths.lo4 0

+*

/ v / 0/

0 -

\

I

Assignments of v(M=O) have also been given for many other complexes containing vanadyl(1v or v) groups,105-115 and for some niobyl(v) 116 Oxohalogenovanadium species have received particular attention. Assignments for the four [Ph,E][VO,X,] salts (E = P or As; X = F or CI) have been given in terms of CZvsymmetry for the anions (Chapter 4), and simple valence force constants calculated.l12~ 113 The ammonium compound NH4[V02F2],on the other hand, is considered to contain polymeric [-VF,(O)-0-VF,(O)-1, chains, and the following assignments have been made on this basis: v(V=0)(968,975, and 982 cm-l), vasynl(-V-O-V-) (738 and 806 cm-l), v,,,(-V-0-V-) (486 and 520 cm-l), vBYI11(VF2) (578 cm-l), and v,,,,(VF2) (448 cm-l).l14 The [V0Cl5l2- ion has also been characterized [v(V=O) at 917 cm-l].l15 Absence of a band attributable to v(V=O) indicates that VOCl and M,[VOC14] (M = K, Rb, or Cs) are [-V-0-V-1, p01yrners.l~~ The product C10H26P4012V, from reaction of VCI, with tetraethyl methylenediphosphonate, has been formulated as a pol ynuclear six-coordinate species, partly on the basis of i.r. dafa.ll8 lo69

A. T. Casey, D. J. Mackey, R. L. Martin, and A. H. White, Austral. J. Chem., 1972, 25, 477. E. Higginbotham and P. Hambright, Inorg. Nuclear Chem. Letters, 1972, 8, 747. lo' A. Hodge, K. Nordquest, and E. L. Blinn, Inorg. Chim. Acta, 1972, 6 , 491. loB G. 0. Carlisle and D. A. Crutchfield, Inorg. Nuclear Chem. Letters, 1972, 8, 443. l o o L. V. Kobets, N. I. Vorob'ev, V. V. Pechkovskii, and A. I. Komyak, Zhur. priklad. Spektroskopii, 1971, 15, 682. 1 1 0 R. G. Cavell, E. D. Day, W. Byers, and P. M. Watkins, Inorg. Chem., 1972, 11, 1591. K.-H. Thiele, W. Schumann, S. Wagner, and W. Bruser, 2. anorg. Chem., 1972, 390, 280. E. Ahlborn, E. Diemann, and A. Muller, J.C.S. Chem. Comm., 1972, 378. l r 3 E. Ahlborn, E. Diemann, and A. Muller, Z . anorg. Chem., 1972, 394, 1. 114 R. Mattes and H. Rieskamp, Z . Nuturjbrsch., 1972, 27b, 1424. 116 J. Selbin, C. J. Ballhausen, and D. G. Durret, Inorg. Chem., 1972, 11, 510. 1 1 6 K. A. Uvarova, Yu. I. Usatenko, N. V. Mel'nikova, and Zh. G. Klopova, Russ. J. Inorg. Chem., 1971, 16, 1141. 1 1 7 V. T. Kalinnikov, A. I. Morozov, V. G. Lebedev, and 0. D. Ubozhenko, R i m . J . Inorg. Chem., 1971, 16, 1088. Iln C. M. Mikulski, N. M. Karayannis, L. L. Pytlewski, R. 0. Hutchins, and B. E. Maryanoff, Inorg. Nuclear Chem. Letters, 1972, 8, 225.

Vibrntionnl Spectra of Transition-element Conipoirnds

32 1 In the i.r. spectrum of Nb[S,P(OEt),l,, bands at 403, 356, 274, and 215 cm-l are all assigned as v(NbS) because they are absent from spectra of the sodium salt of the ligand.ll9 Data on [MS,I3- and [MSe4I3- (M = V, Nb, or Ta) 24 have been included in Chapter 4. A review of the chemistry of certain d" complexes contains references to vibrational spectroscopic studies of e.g. MX,L, ( M = Nb or Ta; X = F, C1, Br, or I ; L = unidentate ligand), Nb(NR2)4,[Nb(NCS),I2--, [Nb(OR)Cl5I2-,and Nb(S,CNR,), [R = various], with particular reference to metalligand In the far4.r. spectra of MVBr, compounds (M = NH,, Rb, or Cs), a doublet in the 210-240cm-1 region has been assigned to vmyIII(VBr); in CsVBr,(H,O),, v(VBr) is at 240 cm-l, while for MVBr,(H,O), [M = NH,, K, Rb, or Cs] broad bands approximately at 470, 620, and 720 cm- are attributed to V ( V - O H , ) . ~ ~New ~ vanadium(i1) halide complexes VX,(4-pi~oline)~ have been characterized, showing v(VX) in the i.r. at 306, 286 [superimposed on v(VN)], or 220 cm-l for X = C1, Br, or I, respectively.*21 Possible structures have been proposed for [M,Xl2]Y,,nH2O (M = Nb or Ta; X = C1 or Br; Y = CI, Br, or I) partly on the basis of i.r. data.*22 In the complexes L4MF3 and L,NbOF (L4H2 = octaethylporphin; M = N b or Ta), v(MF) is in the 540-600 cm-l range.*l 6 Chromium, Molybdenum, and Tungsten

Two groups of workers have reported v(WH) in (R2PhP)3WH, [R = Me or Et 124]. Data are also available for v(MH) in (rr-C,H,),WH, and ( ~ T - C ~ H ~ ) ~ W ( H ) C Hand C I , ,in~ ~(~T-C~H~)~M(H){-CC(CO~M~)=CHCO,~ Me} (M = Mo or W), (rr-C5H5)2Mo(H)(-C(CF,)=CHCF3), and ( 7 ~ C,H,),Mo(H){-CH(CN)CH,X} (X = H or CN).12, Complexes [WH,(PR,),] {PR, = PMe,Ph, PMePh,, or g(diphos)},l2' shown to be stereochemically rigid in CsDe at room temperature (n.m.r.), all show complex i.r. v(WH) patterns in the region 1700-1850 cm-'. Skeletal modes of But4Cr and (neo-C5Hl,),Cr have been located in the range 300-600 cm-l, with v(CrC) probably at 385 and 375 cm-l, respectively.128 1.r. spectra in the v ( C 0 ) and 300-700 cm-l regions have been discussed for solutions of 37 compounds LM(C0)5 [L = various; M = Cr, Mo, or W]; the E (in C,,) v(M-C) mode is taken to be in the range 360-390 (M = Mo or W) or 440--470 cni-l (M = Cr), and shows a 119

I20 121 122

12.1 I?4 1 :5

R. N. McGinnis and J. B. Hamilton, Inorg. Nuclear Chem. Letters, 1972, 8, 245. H. J. Seifert and A. Wiisteneck, Inorg. Nuclear Chem. Letters, 1972, 8, 949. M. M. Kharnar and L. F. Larkworthy, Chem. a n d Ind., 1972, 807. H. Schtifer, B. Plautz, and H. Plautz, Z. anorg. Chem., 1972, 392, 10. J. R. Moss and B. L. Shaw, J.C.S. Dalton, 1972, 1910. B. Bell, J. Chatt, and G. J. Leigh, J.C.S. Dalton, 1972, 2492. Kon Swee Chen, J. Kleinberg, and J. A. Landgrebe, J.C.S. Chem. Comm., 1972, 295. A. Nakarnura and S. Otsuka, J. Amer. Chem. SOC., 1972, 94, 1886. B. Bell, J. Chatt, G. J. Leigh, and T. Ito, J.C.S. Chem. Comm., 1972, 34. W. Kruse, J. Organometallic Chem., 1972, 42, C39.

322 Spec t i m c o p ic Properties oJ Ii r orgcinic aiid 0i-gcurome tullic C 'o 1ipoi uI d s linear correlation with the electronegativity of the donor atom in L.129 The same authors have studied 26 complexes cis-[M(CO),(chel)] (M = Cr, Mo, or W; chel = bidentate chelate having N, P, As, or S donor atoms); bands in the region 365-563 cm-l are (questionably) attributed to v,,,(M-C) of two trans M-C X-Ray studies have shown that in {N,P,(NMe2)8}W(CO), the phosphonitrile acts as a bidentate rr-ligand through one ring-N atom and one exocyclic group; in agreement with this it is found that its four v(C0) values are close to those of (en)W(C0),.131 Factor-group splitting is believed to be the reason why (N3P.&I,)Cr(CO), shows twice as many i.r. v(C0) bands (numerical data not given) as (B,N,Me,)Cr(CO),. A vibrational analysis has been carried out on K,[Cr(CN),(NO)], assuming the free-ion symmetry C,, since crystal-field effects on the spectra were not observed. 1.r. bands (to 100cm-l) were assigned by analogy with existing data on the Fe and Mn analogues, and by using 15N0substitution. Dichroism observed in crystal polarized spectra could not be explained in terms of either of the two (previously proposed) alternative crystal structures, but no firmer conclusions could be drawn.la3 The i.r. spectrum of the hydrated compound K,[Cr(CN),(NO)],H,O has been found to differ from that previously given. Assignments for this and the related compounds K,[M(CN),(NO)] (M = Cr or M o la4)have been proposed. In isothiocyanato-complexes, v(M-NCS) has been assigned as follows : K,[M(NCS),] (315 cm-l, M = Mo; 281 cm-I, M = W),13, K[W(NCS),] (305 crn-l),lS6 [Mo(NCS),(bipy)] (305 ~ m - 9 ,and ~ ~[W(NCS),L,] ~ (275 cm-l, L = py; 282 cm-l, Lz = b i ~ y ) , In l ~ the ~ latter two series, v(W-py) and v(M-bipy) are in the 275-305 cm-l range.137 Assignments suggested lS8 for [Ph,As],[Cr(NCO),] include v(CrN) at 345 cm-l. In [MoNCl,]-, v(MN) is at 1052 cm-l, with v(MC1,) at 352 (sym) and 347 cm-l (a~yrn).'~~ 1.r. absorption spectra of vapours over MOO, have been measured in an argon matrix, and bands attributed to ring vibrations of (Moo,),, (MOO,),, and (MOO,), species at 837, 856, and 865 cm-l, respe~tively.'~~ In complexes of the type MOX,(chel) and MO,X,(chel) [M = Mo or W; chel = phen or bipy], the M-0 force constants decrease as X is successively 13*9

lzrn

la0 lS1

R. A. Brown and G . R. Dobson, Inorg. Chim. Acta, 1972, 6, 65. G. R. Dobson and R. A. Brown, J . Inorg. Nuclear Chem., 1972, 34, 2785.

H. P. Calhoun, N . L. Paddock, J. Trotter, and J. N. Wingfield, J.C.S. Chem. Comm., 1972, 875.

N . K. Hota and R. 0. Harris, J.C.S. Chem. Contm., 1972, 407. G . Paliani and A. Poletti, Spectroscopy Letters, 1972, 5 , 105. 134 L. Tosi, J . Chim.phys., 1972,69, 1052. lYL L. Tosi, Compt. rend., 1972, 274, B, 249. C. J. Horn and T. M. Brown, Inorg. Chem., 1972, 11, 1970. lY7 T. M. Brown and C. J. Horn, Inorg. Nuclear Chem. Letters, 1972, 8 , 377. 138 R. A. Bailey and T. W. Michelsen, J . Inorg. Nuclear Chem., 1972, 34, 2935. R. D. Bereman, Inorg. Chem., 1972, 11, 1148. l P 0 P. A. Perov, V. N. Novikov, and A. A . Mal'tsev. Vestnik Moskoc. Univ., Khim., 1972, Isa

13, 89.

Vibmtiorml Spectra of Tt.urisitiori-element Cornpormd.r.

323

varied in the sequence F, C1, Br; values (CM-') for v(Mo0) in the (phen) series are as follows:1i1 MoOX,(phen) [980, X = F; 975, X = C1; 967, X = Brl; Mo02X2(phen)[945 and 925, X = F; 943 and 905, X = CI; 933 and 900, X = Br; these values refer to v ~ , . ~and , ~ , vasrIl, respectively]. As in previous years, v(M=O) modes have been apparently identified in a wide range of compounds, generally with the usual confidence and despite the fearsome complexity of many of the spectra in the appropriate regions, as follows : [L1H2][MoOX6],MoOX,L1, Mo~O,BT,L~~, and Mo204X2L12 (L' = phen, X = C1 142 or Br;14, L1 = bipy, X = Br;144 L2 = bipy 144 or phen143); (MoO(salen)},O [v(MoOMo) at 750 and 430 cm-l] ;Ira some oxomolybdenum(v) complexes of quinolin-8-01;146 L4MoO(OMe) and L,WO(OPh) [LoH2 = octaethylporphin; v(M0M) of (L,M(0)}20 (M = M o or W) also given];81 MoO,(dtc), and Mo,O,(dtc), [dtc = diethyldithiocarbamato; v(Mo0Mo) at 752 (asym) and 428 cm-l (sym)];lo6 WOF,(OEt),-, [n = 0, 1, or 2; v(W-OEt) at 600cm l];la7 WOX,(PR,), [X = C1 or NCS; PR3 = various; S(W0) at cu. 250 ~ r n - l ] WO(O,SF), ;~~~ [v(W-0) at 280, 273, and 214 cm-'; 6(WO) at 184, [v(MoOMo) at 789 and 867 cm-l; 154, and 141 ~ m - ~ ] Mo02C12(H20) ;~~@ structure determined by X-ray diffraction];160 and (NH,),[MoOBr6].l6l A further opinion has been expressed on the position of bands charac0 bridges (M = Mo or W) (cf. previous years' teristic of 'M M' ' 0 ' reports),lK2and modes of the Cr30 group in Cr,O(O,CMe), have been tentatively assigned 163 to i.r. bands at ca. 650 cm-I. More detailed assignments have been made for oxyhalogeno-anions. For [Ph,E][CxO,X] (E = P or As; X = F or Cl),15, v,,,(Cr03) = 905910cm-l, v(CrX) = ca. 638 (X = F) or ca. 437cm-' (X = Cl), and V , , , ~ ( C ~ O= , ) ca. 950 and ca. 930cm-l. In the case of Rb[Mo20zFQ], i.r. and Raman spectra (Table 6) are said to be consistent with bridging F atoms but terminal 0 atoms.ls6 A similar situation (bridging F, terminal 0) was deduced m for M[Mo02F3](M = NH4, K, Rb, Cs, or T1) and M[W02F3] (M = Rb or Cs), and the structure ( 5 ) proposed on the lP2

144

147

14n 149

lil

lbJ

15J

164 lrr5

lag

R. Kergoat and J. E. Guerchais, Bull. SOC.chim. France, 1972, 1746. H. K. Saha and M. C. Halder, J . Inorg. Nuclear Chem., 1972, 34, 3097. H. K. Saha and A. K. Banerjee, J . Inorg. Nuclear Chem., 1972, 34, 1861. H. K. Saha and A. K. Banerjee, J . Inorg. Nuclear Chem., 1972, 34, 697. A. Van Den Bergen, K. S. Murray, and B. 0. West, Austral. J . Chem., 1972, 25, 705. W. Andruchow and R. D. Archer, J . Inorg. Nuclear Chem., 1972, 34, 3184. Yu. A, Buslaev, Yu. V. Kokunov, and V. A. Bochkaveva, Rum. J . Inorg. Chem., 1971, 16, 1393. A. V. Butcher, J. Chatt, G. J. Leigh, and P. L. Richards, J.C.S. Dalton, 1972, 1064. R. Dev and G. H. Cady, Inorg. Chem., 1972, 11, 1134. F. A. Schroder and A. N. Christensen, 2. anorg. Chem., 1972, 392, 107. G. Y.-S. Lo and C. H. Brubaker, jun., J . Co-ordination Chem., 1972, 2 , 4. P. C. H. Mitchell and R. D. Scarle, J.C.S. Dalton, 1972, 1809. R. Grecu and D. Lupu, Rev. Roumaine Chim., 1971, 16, 1811. E. Diemann, E. Ahlborn, and A. Miiller, 2. anorg. Chem., 1972,390, 217. A. Benter and W. Sawodny, Angew. Chem. Internat. Edn., 1972, 1 1 , 1020. R . Mattes, G. Miiller, and H . J. Becher, Z,anorg. Chem., 1972, 389, 177.

324

Spectroscopic Properties of' Inorgarlic and Oqmonict allic Coniporrnds F

(5)

basis of the vibrational data (e.g. Table 6 ) was confirmed by a singlecrystal X-ray study of C S [ M O O , F ~ ] . ~ ~ ~ In the i.r. spectra of [Cr(Me,SO),]X, (X = C104 or I), splitting of the flu (in 0,) V,,~,(CTO~)and 8asvI,1(CrOs) modes, each into two components, has been 0 b s e r ~ e d . l ~ ~

Table 6 Assignmetitslcm-' of the vibrational spectra of Rb[ M o 2 0 2 F , ] and Cs[MoO,F,] Assignment

Rb[Mo,O,F,] lK5 Rainan 1033 -

68 5 -

576

Cs [MOO,F,] lS6 I.r. Ranian 970 974 919 912 581a 580" -

-

Assigned to an axial MoF, grouping by analogy with K,MoO,F,(H,O).

Optical and i.r. spectroscopy have been used to study the symmetry of Cr04,- ions in alkali halides.158 1.r. spectra (400-1300 cm-l) of tungstates of the scheelite (CaW04) type (Sr, Ba, and Pb cations) and of the wolframite (FeWO,) type (Mg, Cu, Ni, Co, Zn, Mn, and Cd cations) have been Polymo1ybdates,leo polytungstates,ls1P162* 163 and their thermal decomposition products l6l*162 have been studied by i.r. and other techniques. The formation of molybdates 165 and tungstates ls5, bY interaction of component oxides 164* 166 or by hydrolysis of MO,(dien) complexes ( M = Mo or W)le5 has also been followed using vibrational l B 4 9

157 158 150 100

181 182

lo3 164

loe

E. Koglin and W. Krasser, Ber. Bunsengesellschaft phys. Chem., 1972, 76,401. S. C.Jain, A. V. R. Warrier, and S. K. Agrawal, Chem. Phys. Letters, 1972, 14, 21 I . M. L. Zorina and L. F. Syritso, Zhur. priklad. Spektroskopii, 1972, 16, 1043. A. B. Kiss, S. Holly, and E. Hild, Acta Chim. Acad. Sci. Hung., 1972, 72, 147. R. Ripan, D.Stgnescu, and M. PuycaSin, Z . anorg. Chem., 1972, 391, 187. R. Ripan, M. PuScaSin, D. StBnescu, and P. Boian, 2. anorg. Chem., 1972, 391, 183.

M. V. Mokhosoev, N. A. Taranets, and M. N. Zayats, Russ. J . Znorg. Chem., 1971, 16, 1012. T. G . Alkhazov, V. M. Khiteeva, Sh. A. Feizullaeva, and M. S. Belen'kii, Russ. J . Znorg. Chem., 1971, 16, 902. R . S. Taylor, P. Cans, P. F. Knowles, and A. G . Sykes, J.C.S. Dalton, 1972, 24. R . Albrecht and R. Mobius, 2. anorg. CIIPIU., 1972, 392,62.

Vibrational Spectra of Transition-element Compounds 325 spectroscopy. Other miscellaneous applications to compounds in this section include a study of adsorption of py and H 2 0 onto o r - c h r ~ m i a , ~ ~ ~ and an investigation of short-time polymerization of C2H4 with Cr" and CrV1surface species on oxide carriers.ls8 Assignments of the Raman spectra of K,[MOS,]X species (M = M o or W ; X = C1 or Br) are listed in Table 7.IB9 Co-ordination of the oxytri-

Table 7 Assignments of the Raman spectra/cm-l of K3[MOS3]X species Mode

Vl(A1) 1'2

(A,)

Description v(MO) VBYdMS3)

K3[MoOS31CI 858 459

{ t:;

K,[MoOS,] Br 874 458

1::

K,[WOS,] R r 872 452

K,[WOS,]CI 875 469

468

453

thiotungstate(v1) anion to some metal(rr) ions in [M(WOS,)2]2- salts ( M = Co, Ni, or Zn) occurs uia sulphur atoms only [v(WS)t at ca. 490, v(WS),, at ca. 440, v(WO)t at ca. 9 2 0 ~ m - ~ ] .Some ' ~ ~ assignments for other thio-anions of Mo and W are given in Table 8;l7'1 172 the polarizing

Table 8 Raman datalcrn-l on thiomolybdates and thiotungstates Compound Ref. v(M0) v(MS) TIMoO,S, TIWO,S, TIMoOS, TIWOS3 CuWOS3d TIMoS, CUMOS,~ TIWS, Cu2WS4G Cu( N H4)W S4' PbWS4d ZnWS,d Cu WSeod

Symmetric mode.

845", 829b

875", 824b 83 1

860, 851 91OC -

_-

-

___

Asymmetric mode.

461", 46gb' 465", 455b 444", 459b 465", 450b 445c 445a, 465b 49Y, 48Y, 44@ 475", 457b, 446b 474, 452, 413 452c, 466, 433 ca. 45gC ca. 435" ca. 284g

1.r. value (cm-l).

171 171 171 171 172 171 172 171 172 172 172 172 172

Impure compound.

* v(CuS) also assigned at 282 (and 217 ?) cm-' in the Raman spectrum. fv(CuS) also assigned a t 248 cm-' in the i.r. and 257 (and 233 ?) cm-' in the Raman spectrum. value (cm-l) for v(WSe).

''" Ian 1(18

li*

1.r.

A. Zecchina, E. Cuglielminotti, L. Cerruti, and S. Coluccia, J. Phys. C'hem., 1972, 76, 571.

H. L. Krauss and H. Schmidt, 2. anorg. Chetn., 1972, 392, 258. A. Muller, W. Sievert, and H. Schulze, 2. Naturfarsch., 1972, 27b, 720. A. Muller and H. H. Heinsen, Chern. Ber., 1972, 105, 1730. A . Muller, Ch. K. Jsrgensen, and E. Diemann, Z. atiorg. Chem., 1972, 391, 38. A. Muller and R. Menge, Z.anorg. Chenr., 1972, 393, 259.

326


effects of the T1+ cation on the anions is discussed in ref. 171. Other data on [MX41a- (M = M o or W ; X = S or Se)24have already been mentioned. The transverse optical phonon frequencies of MoS, and MoSe, occur The i.r. spectra below in the i.r. at 380 and 245 cm-l, re~pective1y.l~~ 500 cm-l of Cr(ethylxanthato), and Cr(dimethyldithiocarbamato), have been listed and compared with data obtained from the single-crystal absorption and emission electronic spectra of these The formation of Cr,Te,O from the action of heat on CrTe in air has been followed by i.r. and X-ray ~ e t h 0 d s . l ~ ~ The Raman spectrum of [CrC1,I3- has now been obtained and the i.r. spectrum re-investigated for [M(NH3)6]3+salts (M = Co, Rh, Cr, or Ir); the nearly regular octahedral symmetry of the anion has been thereby ~ 0 n f i r m e d . l The ~ ~ compounds were shown to crystallize in space group 7';( Z = 4), and a unit cell group analysis was used in making the following assignments (cm-l; M = Rh):176 vl = 286 (Raman)

is4

=

199 (i.r.)

v2 = 237 (Raman)

v:, = 162 (Raman)

v3 = 315 (i.r.)

v6

= 182 (i.r., Rb+ S a l t )

Complete assignments of the allowed vibrations of [ M,Cl9l3- ions (M = Cr or W) have been proposed on the basis of D3,,symmetry as shown in Table 9;177a full normal-co-ordinate analysis was carried out, and the force constant for direct W-W interaction in [W2C1J3- estimated as 1.15 f 0.1 mdyn A-l. Some comments have been made on the i.r. spectra [internal H,O and v(M-OH2) modes] of [M&]X4(H20)2 compounds ( M = Mo or W ; X = C1, Br, or I).178For [MO6CI~]C12(MeC0,)2, a polymeric structure with bridging acetato-groups has been proposed on the basis of i.r. data; v(MoC1) is said to be at 333 cm ('inner' Mo-CI bonds) and 255 crn--l ('outer' Mo. .C1 interaction^).^^^ The observation of v(Mo-C1) bands in the i.r. region (243-341 cm-l) expected for octahedral co-ordination of Mo'"has led to the proposal that the ligand L is unidentate in MoCl,L, (L = pyrazine, quinoxaline, or 4,4'-bipyridyl) but bidentate in MoC14L ( L = bipy).lsO In the seven-coordinate complexes [M(CO),(T)I]+ [M = Mo or W ; T = bis-(2-pyridylmethy1)ami ne, bis-(2-pyridylmethyl)methylamine, or bis-(2-pyridy le thy1)amine],lR1v(M1) is in the range 139-142 cm-l. Other halogeno-compounds

-

Ii4 li5

li7

'~IO

lyl

0. P. Agnihotri, J . Phys. and Chem. Solids, 1972, 33, 1173. W. J. Mitchell and M. K. DeArmond, J . Mol. Spectroscopy, 1972, 41, 33. S. S. Batsanov, L. M. Doronina, T. A. Volkova, and V. E. Borodaevskii, Rum. J . Inorg. Chem., 1971, 16, 1545. H . H . Eysel, Z . anorg. Chern., 1972, 390, 210. R. J. Ziegler and W. M. Risen, jun., Inorg. Chem., 1972, 11, 2796. H . Schiifer and H. Plautz, Z . anorg. Chenr., 1972, 389, 57. G. Holste and H. Schtifer, Z. anorg. Chem., 1972, 391, 263. W. M. Carmichael and D. A. Edwards, J . Inorg. Nuclear Chem., 1972, 34, 1181. J . G . Dunn and D. A. Edwards, J . Orgnmonieta~licChenz., 1972, 36, 153.

Vibrational Spectra of Trunsition-element Compounds 327 Table 9 Assignments for the fundamental modes of vibrutionlcm-' in [M2ClQI3-ions Assignment a

Cs3Cr,Clgb

I.r. -

360 261 184 342 234

'14

v16 '16 v17

v18

-

-

Raman 375 280 161 121 -

-

-

335 233

ca. 78 320 222 131 I13

K3W,ClQc 1.r. Raman 332 257 139 115 313 232d 158 285 281 215 209 181 178 96 91 76

-

-

-

ca. 76 294 226 123 107

a Based on Dlh symmetry; A ; ( v 6 ) and AI, (v,)species are forbidden. Assignments also given for Et,N+ and BundN+salts. Assignments also given for Cs+ and Bun,N+ salts. Value for Cs+ salt.

of M o or W studied by vibrational spectroscopy include Mo(chel)CI, [chel = NN-ethylenebis(salicyla1dimine)or N-substitutedsalicylaldimine]ld5 and various W'" halide complexes of N-and S-donor ligands.le2 7 Manganese, Technetium, and Rhenium Crystallographic data on the new carbonyl hydride H2Re2(CO), are consistent with structure (6); Raman bands at 1382 and 1272 cm-l (shifting to 974 and 924 cm-' in the deuteriate) are consistent with the presence of bridging H atoms.lE3 In K8[Re(CN),],3H20, v(ReC) is given as 907 crn-l in the For the carbonyl derivatives (7), v(Mn--0) modes are at 475 and 450cm-l

M. A. Schaefer, Diss. Abs. Internat. ( B ) , 1972, 32. 5678. M. J. Bennett, W. A. G. Graham, J. K. Hoyano, and W. L. Hutcheon, J . Amer. Chem. SOC.,1972,94, 6232. In40. E. Skolozdra, A. N. Sergeeva, and K. N. Mikhalevich, R i m . J. Inorg. Cheni.. 1971,

IRa Ia3

16, 861.

328

Spectroscopic Properties of'Inorganic and Organometallic Compounds

(M = Ge) or 450 and 445 cm-l (M = Si).185 On the basis of an i.r. study it has been concluded that [Mn(CO),(NO)] has a C,, trigonal-bipyramidal structure (axial NO group) in the vapour phase and in solution (C,H, and CCI,), rather than the C2,form suggested by X-ray work on the crystalline form at - 110 T; assignments made {largely by comparison with [Fe(CO),]} are given in Table 10.1n6 Table 10 Mode

Vibrational assignments for [ Mn(CO),(NO)] Description

v/cm--l

A1 v1

A2

Mode

Description

E

v(Co)eq

v10

1'2

v11

v3

1/12

v4

v13

v5

'14

v6

v15

v7

'16

V8

v17

VQ

V18

6( MnNO)

8(MnCO) 4MnC)eQ 8(MnCO) 8(CMnC) 8(CMnN)

6(C M nC)

8(CMnN)

vlcm-l 2020 657 64 I 456

417 I02 102 52 52

1.r. bands (to 650 an-') have been listed for species [ReCl,+,(py),(NO)]~t(n = 0, m = 2 ; n = 1, m = 1; or n = 2, rn = 0 ) , and v(N0) has been assigned in the 1725-1770 cm-l range.lH7N-Co-ordination has been sug-

gested for ( B U ~ ~ , N ) ~ [ R ~ , ( N Con S ~ )the , ] basis of i.r. bands at 273 and 300cm-l arising from u(ReN),188while in complexes Mn(NCS),(L) [L = @)I, v(MnN) is in the 250-260 cm-' region.leQ

( 8 ) K'

=

11 or Me.

RZ == M e or €it

A general review of the chemistry of Mn in higher oxidation states includes references to a range of spectroscopic results, e.g. on [Mn04]"ions (n = 1, 2 , or 3).lQoAssignments of the i.r. spectra have been given for K[TcO,] and Ag[TcO,], and force constants calculated.1g1 The i.r. spectrum (CC14 solution) of ButORe03 (obtained from reaction of Re,O, with But,O or ButOH) has been compared with data for Me3SiOReO,, and values for u,,,,,(Re03) (967 cm-') and vsym(ReO,)(1006 cm-l) H. C. Clark and T. L. Hauw, J . Organoriietallic Chem., 1972, 42, 429. G. Barna and 1. S. Butler, Canad. J . Spectroscopy, 1972, 17, 2. Iy7 D. K. Hait, B. K. Sen, and P. Bandyopadhyay, 2. anorg. Chem., 1972, 388, 184. lHU R . R. Hendriksma, Inorg. Nuclear Chpm. Letters, 1972, 8, 1035. lne B. Chiswell and K. W. Lee, Inorg. Chini. A d a , 1972, 6 , 567. lUo W. Levason and C. A . McAuliffe, Co-ordination Chem. Rev., 1972, 7, 353. lol J. Hanuza and B. Jezowska-Trzebiatowska, Bull. Acad. polon. Sci., S&r. Sci. chiin.. 1972, 20, 271.

lwa

lH6

Vibrational Spectra of Transition-ekement Compounds

329

have been discussed in terms of the high formal charge on 1.r. and Raman data on ReO,Cl(py),(H,O),, which was recently assigned the structure [Re(OH),(py),]Cl, have been shown to be consistent only with the octahedral trans-dioxo-structure [ReO,(py),]+ ; K,[ReO,(CN),] and [ReO,(en),]C1,2H20 are also believed to have this Suggestions have been made for v(Re0) in Re(acac), and Re(hfac),. 1.r. and Raman data have been reported for trans-[ReCl,(acac),], shown to be a monomer and not a dimer as previously believed; the new cis[ReX,(acac),] compounds (X = CI, Br, or 1) were also studied.lg5 Values for v(Re0Re) lS7 or v(Re=O) l V 7have been given [(dtc),for L,ReO(OPh) and (L,ReO),O [L4H, = octaethylp~rphin],~~ ReO],O (dtc = diethyldithiocarbannato),los[ReO(NH,),],,lBfi and some dithiocarbamato-complexes of Re"' and ReV.lg7 More detailed studies have been carried out on oxohalogeno-compounds of Re, and three reports19H-200 have been concerned with ReOCI, (see Chapter 4). Data are also available for Re0,CI lg9 and for Re,O,CI,,lgg~,O0 for which the structure 03Re-O-Re(C1),=0 is proposed.200The conipound previously described as 'JS-ReOCI,' has now been shown by X-ray diffraction to be (Re0,Cl),Re,0,C1,,199 having v(Re=O) at 1039, 1003,970, and 930 cni-l, v(Re0Re) at 830 cm-l, and v(ReC1) at 350 cm--'. The compounds ReOCI,( MeCN),lBs [Ph,P][ReOBr,],lgs and trans-[ReOCI,(OH,)] (v(ReC1) at en. 350 cm-l} ,01 also show v(Re=O) in the expected region. Oxohalogeno- and halogeno-anions of technetium have been characK,Tcterized by i.r. spectroscopy, viz. TcO,CI, TcOCI,, and TCOCI,;?~~ o q ; w 203 (NH,),[TcOCI,], Cs,[TcOCI,], [TcO,(en),]CI, K,[TcCI,], and Cs,[TcCI,] ;lgl and K,[TCO(OH)C~,].~~~ Force constants have been computed for several of these species.1g1 The far-i.r. reflection spectrum of MnTe over the temperature range 30--350 K has been Electronic reflectance and i.r. spectroscopy [v(MnBr) at 230 cm-l] show that Cs,MnBr, and Rb,MnBr, contain tetrahedrally co-ordinated anions.2o5 The presence of two v(MnC1) bands (360, 335sh cm-l) in the i.r. R1p

1051

lgfiv

C. Ringel and G . Boden, Z.anorg. Chent., 1972, 393, 65. N. P. Johnson, J. Inorg. Nuclear Chem., 1972, 34, 2875. 194 W. D. Courrier, W. Forster, C. J . L. Lock, and G . Turner, Cunud. J . Chern., 1972, 50, 8. lR5 W. D. Courrier, C. J. L. Lock, and G. Turner, Cunad. J . Chern., 1972, 50, 1797. lUtl D. A . Edwards and R. T. Ward, J.C.S. Dalton, 1972, 89. J . F. Rowbottom and G . Wilkinson, J.C.S. Dalton, 1972, 826. I p s C . G . Barraclough and D. J. Kew, Ausrml. J . Chem., 1972, 25, 27. ~~9 C . Calvo, P. W. Frais, and C. J . L. Lock, Cunad. J . Chern., 1972, SO, 3607. Loo K. I . Petrov, V. V. Kravchenko, D. V. Drobot, and V. A. Aleksandrova, Russ. J . Inorg. Chern., 1971, 16, 928. P. W. Frais and C. J. L. Lock, Canad. J . Chem., 1972, 50, 181 1 . 2 o z A. Guest and C. J . L. Lock, Cunad. J . Chern., 1972, SO, 1807. "'3 V. I . Spitsyn, M . I . Glinkina. and A. F. Kuzinn, Doklady Chern., 1971, 200, 875. '(I( 1,. V. Povstyanyi, V. I. Kut'ko, and A . 1. Zvyagin, Fiz. trerd. Tclr, 1972, 14, 1.561. .llli H.-J. Scifcrt and E. Dau, %. a ~ ~ o r C g ./ W I I I1979, ., 391, 302. lg3

330


spectrum of [Co(en),][MnC1,],2H20 has been attributed to a Jahn-Teller effect, but possible crystal symmetry effects were ignored.20s 1.r. data have been given for [Re,C1,,]3- salts 207- 208 and a normal-co-ordinate calculation has been performed.208The computed normal modes show that none of the vibrations is localized in any bond or angle; the Re-Re stretching force constant calculated ( I .35 mdyn A-l) indicates multiple bonding.208 1.r. data are also available for Re,CI,, Re,Br,, and the new compound Re,Br,Cl, (9).207 Br Br

(9)

The observation of two i.r.-active v(ReF) bands for ReF,(CO), (650 and 580cm-l) is consistent with fac-geometry ( A and E modes under CSv symmetry).20e Other complexes for which v(MX) values (cm-l) have been given include the following: MnCI,L, [L = p y 0 (270, 310), Ph3P0 (340), or Ph,AsO (280, 330); v(Mn0) at 41&-455 Mn(CO),{PhP(CH2CH2PPh2)2}X[X = Br (209) or I (1 90)],211 [Re(CO),X(Ph,PCH,CH2CN)la {X = C1 (288) or Br (198)},21’2and M(CO),LX [L = a 7rbonded dinitrile, NCCH,CN or NCCH,CH,CN; M = Mn, X = C1 (287) or Br (220-228); M = Re, X = Cl (288) or Br (195-205)].213 General ranges for v(MnX) in [Mn1I1(porphyrin)X(OH2)](X = halide or pseudohalide) have been given in a review of manganese porphyrin complexes.214 8 Iron, Ruthenium, and Osmium Assignments (often supported by deuteriation studies) have been given for v(MH) or v(MD) in several compounds of these elements as follows: H,FeC04,41 H,FeL, [L = P(OEt),, PhP(OEt),, &(diphos), Ph,PMe, PhPMe,, PhP(OPr’),, e t ~ . ] , ~D2Fe(PF3)4,21e l~ H,Fe(PPh2H)4,217H,Ge2 08

2 07 20R 209

“1 0

“1

W. Levason, C. A. McAuliffe, and S. G . Murray, Inorg. Niiclear Chem. Letters, 1972, 8, 97. M. A. Bush, P. M. Druce, and M. F. Lappert, J.C.S. Dalton, 1972, 500. K. I. Petrov and V. V. Kravchenko, Rriss. J . Inorg. Chem., 1971, 16, 930. T. A. O’Donnell and K. A. Phillips, Znorg. Chem., 1972, 11, 2562. E. Contreras, V. Riera, and R. U s h , Inorg. Nuclear Chem. Letters, 1972, 8, 287. I. S. Butler, N . J. Coville, and H. K. Spendjian, J. Organometallic Chem., 1972, 43, 185.

zia B. 21s

114 216

216 “17

N. Storhoff, J. Organometallic Chem., 1972, 43, 197.

M. F. Farona and K. F. Kraus, J.C.S. Chem. Comm., 1972, 513. L.J. Boucher, Co-ordination Chem. Reo., 1972, 7 , 289.

D. H. Gcrlach, W. G. Peet, and E. L. Muetterties, J. Amer. Chem. SOC.,1972, 94, 4545. T. Kruck and R. Kobelt, Chem. Ber., 1972, 105, 3765. J. R. Sanders, J.C.S. Dnlron, 1972, 1333.

Vibrational Spectra of Transition-element C 'orzipounds

33 1

FeH(CO),,,l K[FeH(PF3)4],216trans-[FeHX(PPh,H),] (X = C1, Br, I, NCS, or SnC13),217EtFeH(Ph2PEt),,218 [FeH(L)(diphos),]X (L = N,, Me,CO, MeCN, PhCN, or NH,; X = BPh, or CIO,) and [FeH(diphos),]BPh4,,lQ H,RuL, [L = P(OMe),, P(OEt),, P(OPri),, YhP(OEt),, or PhPMe,],21s H,Ru(PPh,H), and trans-[RuHX(PPh,H),] (X = C1, Br, I, NCS, or SnC1,),z17 RuHCI(CO)(PR,), and RuHCl(CO)(PR,),(py) (R = C6H11),220 (HCO,)RUH(PP~,),(P~M~),~~~ [Ru(H){P(OMe),Ph},]BPh,, [(C8H12)RuHL3]BPh4 (L = N2H4, py, or 4-picoline), and two isomers of [(CsH12)RuH(Me2NNH2)3]BPh4,222 and OsHCl(CO)(PR,) and OsHCl(CO)(PR3)(py) (R = C 6 H l l ) ~ ~ ~ ' Assignment of the Fe-H bending modes in H,Fe(CO), (gas-phase) has been attempted in terms of CZv~ynimetry.*~ In (C2H4)Fe(CO)4,a23 v(Fe-C2H4) is at 356 cm-l. In related compounds corresponding modes are as follows : (C4H4)Fe(C0)3 (398 cm-l),,,4 (C(CH,),}Fe(CO), (372 ~ m - l ) , , and ~ ~ (C,H,),Fe(CO) [394 (vaBYlll) and 297 cm-I (vsym)].228 Partial i.r. assignments [e-g. v(CO), 8(MCO), and/or v(M-CO)] have been given for {C(CH,),)Fe(C0)3,225(C,H6),Fe(C0),226 (OC),Fe{Pt(py),Cl}2,227(C3F7)Fe(CO),(NH,),I and [(C3F,)Fe(CO),(NH3)3]+,22s(n-C5H5)I

1

(OC),Fe-C=CMeC(O)N(SO,Cl)CH,

I

and (T-C~H,)(OC),F~-CHCM~,C-

(0)N(S0,Cl)CH,,22Qand [Os(NH3),CO]X, and c~s-[OS(NH~)~CO(N,)]X, (X = C1, Br, or An examination of the v(C0) region in the spectra of O S ~ O ~ ( C O ) , ~ suggests that the molecule has Td symmetry in solution; although a partial normal-co-ordinate analysis was carried out, v(OsO,) could not be clearly distinguished from v ( 0 s C ) and ~ ( O S C O ) . ~ ~ ~ An i.r. and Mossbauer spectroscopic study has led to the suggestion that there is little interaction between ions in [Co(NH,),],[Fe(CN),],,1OH209 Li4 [cO(NH3)618[Fe(CN)6]7,HzO, and Na[Co(NHd6] [Fe(CNhI,4H20, e.g. because no v(CN)I,frequencies were

220

221

2J3

L1b JJ6

las 227

1L8 230 Li2

V. D. Bianco, S. Doronzo, and M. Arcsta, J . Organometallic Chem., 1972, 42, C63. P. Giannoccaro, M . Rossi, and A. Sacco, Co-ordination Chent. Rec., 1972, 8, 77. F. G . Moers and J. P. Langhout, Rec. Trau. chim., 1972, 91, 591. S. Komiya and A. Yamamoto, J. Organometallic Chem., 1972, 46, C58. J. J. Hough and E. Singleton, J.C.S. Chem. Comm., 1972, 371. D . C. Andrews and G . Davidson, J . Organometallic Chem., 1972, 35, 161. D. C. Andrews and G. Davidson, J . Organometallic Chem., 1972, 36, 349. D. C. Andrews and G. Davidson, J . Organometallic Chem., 1972, 43, 393. G . Davidson and D . A. Duce, J . Organometallic Chem., 1972, 44, 365. B. Munchenbach and J. Dehand, Naturwiss., 1972, 59, 647. H . Krohberger, J. Ellermann, and H. Behrens, Z . Naturforsch., 1972, 27b, 890. Y. Yamamoto and A. Wojcicki, Znorg. Nuclear Chem. Letters, 1972, 8 , 8 3 3 . A. D. Allen and J. R. Stevens, Canad. J . Chem., 1972,50, 3093. W. Van Bronswyk and R. J . H. Clark, Spectrochitn. Acta, 1972, 28A, 1429. N. A. Verendyakina, G. B. Siefer, Yu. Ya. Karitonov, and B. V. Borshagovskii, Russ. J. Inorg. Chetir., 1971, 16, 1447.

332

Spectroscopic Propertics of'Inorgcrnic arid Organometallic Compounds

A M U B F F calculation, using a full 13-atom model, has been carried out on the [Fe(CN),N0I2The frequencies, forms of the modes, and force constants of [Ru(N0)XJ2- salts (X = C1, Br, or I) have been calculated and significant mixing of v(N0) and v(RuN) stretching vibrations has been found; the effect of varying X or the cation (K+, Rb', or Cs+) on various frequencies and force constants was Partial assignments [e.g. v(N0) or v(FeN)] have been given for several monoand bis-nitrosyliron(1) complexes with such ligands as diethyldithiocarbamato, butylxanthato, or d i t h i o p h ~ s p h a t o . ~ ~ ~ has been so forniulated The compound ( T - C ~ H ~ ) ( C O ) ~P(O)(CF,), F~on the basis of i.r. and n.m.r. data.236 The new nitrido-complexes Cs,[RuNX,] (X = C1 or Br) show v(Ru=N) at ca. 1047 cm- l.?07 Deuteriation of [Ru(NH,),(N,)]X, (X = Br or I) has shown233H that of the four i.r. bands in the 390--5OOcn-' region the highest three are v(Ru-NH,) and the other band [424 (X = Br) or 415cm-' (X = I) in the NH, series] is v(Ru-N,), thus invalidating previous assignments. However, the existing assignment of ~(0s-",) at 518 cm-l i n [Os(NH,),(N2)]C12is The metal isotope effect ("Fe and 57Fe)has been very effectively used to identify metal-ligand vibrations in the two forms of [Fe(NCS),(phen),].23Q At 298 K the compound is in the high-spin state whereas at 105 K it adopts the low-spin configuration. In addition to the effect of isotopic substitution, the assignments in Table 11 were made by analogy with the spectra

Table 11 Assignments of metal -1igand stretching modes/cm--l in [Fe(NCS),(phen),] isomersa High-spin form (298 K) Low-spin form (105 K) - vP7Fe)

v(Fe-NCS)

252.0

4.0

v(Fe-phen)

220.0

4.5

V ( ~ ~ Fv ~( )~ ~-Fv("'Fe) ~ )

6.0

All other isotopic shifts observed were d & 0.5 cm--'.

of trans-[Fe(NCS),(py),] (high-spin) and [Fe(phen)J2+ (low-spin). The results show that the Fe-(NCS) and Fe-(phen) bonds are stronger in the B. B. Kedzia, B. Jezowska-Trzebiatowska, and 3. Ziolkowski, Buff. Acrrd. pdoir.

Sci., Sdr. Sci. chim., 1972, 20, 237. ?:I4

235

L'37

2s8 ?:jU

B. P. Khalepp, Shornik Aspir. Rab. Kazan. Gos. Utiio. Tochnye. Nauki: Mekh., Fiz.,

1970, 2, 150. B. P. Khalepp and S. A. Luchkina, Sbornik Aspir. Rab. Kazan. Gos. Unio., Mat., Mekh., Fiz., 1970, 91. R . C. Dobbie, P. R. Mason, and R. J. Porter, J . C . S . Chem. Comm., 1972, 612. D. Pawson and W. P. Griffith, Cheni. and tnd., 1972, 609. M. W. Bee, S. F. A . Kettle, and D. B. Powell, J.C.S. Chem. Cotnm., 1972, 767. J. H. Takemoto arid B. Hutchinson, Inorg. Nuclear Chent. Lelters, 1972, 8, 769.

Vibrational Spectra of Trnnsition-elemrrit Coniporinds

333

low-spin c o r n p l e x e ~ ,in ~ ~agreement ~ with bond-length data previously obtained crystallographically for the two spin types of [Fe(NCS),(bipy),]. 1.r. assignments are available for the amrnines [Os(NH,),(N,)]X,, [Os(NH,),CO]X,, ~is-[0s(NH,),(N~)~lBr,, and cis-[Os(NH,),(CO)(N,)]X2 (X = C1, Br, or and [Ru~(CI),(NH,),C~~],~H~O [n = 2 or O].240 Assignments have been given for v(M=O) in the new complexes transCs2[Ru02X4](X = C1, Br, CN, or &0,), trans-[RuO,(NH,),]CI,, and ~ ' in OsO,(py), os@,(py)4, tvans-[RuO2(py),C1,] ( 7 9 G 8 7 2 ~ m - ' ) , ~ and RuO,(OH),(py), O S O ~ ( ~ ~ ) ~ ( C ~ and H ~some O ~ ) related , anionic species [v(Ru02) at ca. 800 cm-l; v(Os0,) at 85&900 (asym) and 790-850 cni-l (~ym)].~,l OsOCI, is probably square pyramidal.1Q8 1.r. spectroscopy (6G5000cm-1) has been used to show that the thermal conversion of lepidocrocite into hematite takes place via maggernite ( ~ - F e , 0 , ) . ~In~ ~some oxo-bridged dimeric iron complexes,243 v,,,,,,(FeOFe) is near 840 cm-l, whereas in basic trinuclear acetates of Fell', bands at ca. 530 cm-1 are assigned to vibrations of the (Fe,O) gr0up.153 v(FeS) is found at 325-330 and 370-376 cm-l in [Fe(NN-di-isopropyldithiocarbamato),]"+ (n = 0 or l).,,, A review 245 of some aspects of the co-ordination chemistry of iron"' includes references to previously reported i.r. and Raman data [with emphasis on v(Fe-ligand)] on such complexes as FeCI,(H20)6, FeC1,(dioxan), FeCI,(DMSO),, FeCl,(py),, FeCl,(pyrazole),, FeX,( Ph,M) [X = C1 or Br; M = As or PI, [FeL,](Cl04)3 (L = p y 0 or phenazine), [FeX,]- (X = CI or Br), [FeX,I3- (X = F, CI, or CN), and FeX(dtc),. A Raman spectral study has been made of the species present in aqueous FeCI, solution^.^^^ In near-saturated solutions, bands due to [FeCI,]- are found. At lower concentrations there is evidence for formation of FeCI3(H20), [Raman bands at 31 8(pol), 165, ca. 390, and ca. 120 cm-'1 having two axial H 2 0 molecules and three equatorial C1 groups. Under conditions of high Fe3+ concentration but low C1- concentration, [FeCI,(H20),J+ is thought to be The species believed to be [R,NCI,R,N][FeCl,] (R = n-octyl) shows a far4.r. band at 189 cm-l (in addition to [FeCI,]- modes) in benzene solution, attributed to an anioncation Proposals have been made for the position of v(FeX) modes in iron(rn) fluoro-complexes (e.g. [FeF,]-, [FeFJ2-, and [FeF,I3-) 248 and some FeX, (X = CI or Br) complexes of amidesZ4* E. E. Mercer and L. W. Gray, J . Amer. Chem. SOC.,1972, 94, 6426. W. P. Griffith and R. Rossetti, J.C.S. Dalton, 1972, 1449. 2 4 1 G . S. Sakash and L. S. Solntseva, Zhur. priklad. Spektroskopii, 1972, 16, 741. us H. J. Schugar, G. R. Rossman, C. G. Barraclough, and H. B. Gray, J . Atner. Chem. SOC.,1972, 94, 2683. w E. A. Pasek and D . K. Straub, Inorg. Chem., 11, 259. 246 S. A. Cotton, Co-ordination Chem. Reo., 1972, 8, 185. 2 4 6 A. L. Marston and S. F. Bush, Appl. Spectroscopy, 1972, 26, 579. 2 4 7 R. A. Work and R. L. McDonald, J . Inorg. Nuclear Chem., 1972, 34, 3123. 2 4 8 E. N. Deichman, Yu. Ya. Kharitonov, and A. A. Shakhnazaryan, Russ. J . Inorg. Chem., 1971, 16, 1731. 2 4 g T. Birchall and M . F. Morris. Connd. J. Cheni., 1972, 50, 201.

210 241

334

Spectroscopic. Properties of Iiiorgnrtic arid Orgniionietallic Conlporrrids

The far4.r. spectra of R U X ~ ( P Y complexes )~ (X = C1, Br, or I) have been assigned in terms of cis configurations with v(MX) at 313 and 325 cm-I (X = Cl) or 168 and 175 cm (X = Br); v(MNj appeared as two bands in the 281-308cm-' range."O Assignments for v(RuX) in the expected regions have also been given for c~is-[RuCl,(CO),(py),_,] (n = 2 or cis-[RuX,(CO),L] (X = C1 or Br; L = EtCN, PhCN, or H2C=CHCN),251 cis- and trans-[RuX,(.2r-C,He)RuCI,(L) [L = PPh3, PMePh,, (EtCN),(MPh,),] (X = C1 or Br; M = P, As, or Sb),263RuCI,(HDMA) and Ru,Cl,(HDMA) [DMA = NN-dimethyIa~etamide],~~~ (n-CsH,)RuCI(PPh,)(R) [R = Me or Ph] and (.~~-C,H,)RUC~(~-C,H,),~~~ and twentyseven compounds of types such as trans-[RuC1,L2], cis-[Ru(CO),C1,L2], rner-[Ru(CO)C12Ls], cis-[Ru(CO),CI,L], and Ru(NO)CI,L, [L = Ph2MCHBMPh2,cis-Ph,MCH=CHMPh,, or cis- or rrans-Ph,MCH=CHPh ; M = P or (n-CBH,)RuC1, is believed to be dimeric, partly on the basis of v(RuC1) data.262* 267 Bridging [260 and 290 (X = C1) or 195 and 21 1 cm-l (X = Br)] and terminal [331 (X = C1) or 234 cm-l (X = Br)] v(RuX) modes have been identified in the i.r. spectra of the dimers [Ru(CO),X,], (X = C1 or Br).251 1.r. spectral studies of v(RuX) have been used in the determination of configuration of two isomers (cis and trans) of RuC1,(CO),(PPh,),,26s and of RuX,(MPh,)L2 complexes (10) [X = CI or Br; M = P or As; L = Me2S,py, &(phen),or +(bipy)].25Q The new arylamido-complexes [OSC~,(NC,H~X)(PP~~)~] (X = H, C1, or OMe) eeo show v(OsC1) at 310-320 cm-l.

p61

263 284

2Gb 25R

1b7 2KH

D. W. Raichart and H. Taube, Inorg. Chem., 1972, 11, 999. E. Benedetti, G . Braca, G. Sbrana, F. Salvetti, and B. Grassi, J . Organometallic Chem., 1972,37, 361. R . A. Zelonka and M. C. Baird, J . Organornetallic~Chem., 1972, 35, C43. B. E. Prater, J . Organometallic Chem., 1972, 34, 379. B. R. James, R. S. McMillan, and E. Ochiai, Inorg. Nuclear Chem. Letters, 1972, 8, 239. R. A. Zelonka and M. C. Baird, J. Organometalfic Chem., 1972, 44, 383. J. T. Mague and J. P. Mitchener, Inorg. Chem., 1972, 11, 2714. R. A. Zelonka and M. C. Baird, Canad. J. Chem., 1972,50,3063. S. Cenini, A. Fusi, and G. Capparella, Inorg. Nuclear Chem. Letters, 1972, 8, 127.

2b8

2eo

E. S. Switkes, L. Ruiz-Ramirez, T. A. Stephenson, and J. Sinclair, Inorg. Nuclear Chem. Letters, 1972, 8, 593. B. Bell, J. Chatt, J. R. Dilworth, and G . J . Leigh. Inorg. Chim. Acta, 1972. 6 , 635.

Vibra t iona I Spec t ra of Transif io11 -e le i nen t Conip0N I I ds

335

9 Cobalt, Rhodium, and Iridium Compounds of these elements for which v(MH) assignments have been given are listed in Table 12.261-277 1.r. spectroscopy has been used to show that in the solid state [(n-dienyl)FeCo(CO),(rr-diene)]complexes (diene = norbornadiene, cyclohexa-1,3-diene, or 2,3-dimethylbuta-l,3-diene)exists as either cis or trans carbonyl-bridged tautomers, an equilibrium being established in solut i ~ n . ~ Reaction ~* between AICl, and NaCo(CO), (in excess) gives a compound AICo,(CO), whose v(C0) bands closely resemble those of C O ~ ( C Oand ) ~ ~which is tentatively formulated as (1 l).278Values of v(C0)

have been listed for uncharacterized addition products from reaction of SPF,Br, SPF,CI, or OPF,Br with such complexes as Ir(CO)X(PPh,), or Ir(CO)Cl(PMePh,), [X = C1 or Br].2*o In complexes IrIMeX(CO)(PButR2) [X = C1 or Br; R = Et, Pr”, or Bun], v(1rMe) is said to be in the 122G1232 cm-l region.278 The following variation of v(Co-allyl) in (XC3H4)Co(C0), has been discussed :2a1 G. M. Intille, Inorg. Chem., 1972, 1 1 , 695. I. Ojima, M. Nihonyanagi. and Y . Nagai, J.C.S. Chem. Comm., 1972, 938. 263 P.-C. Kong and D. M. Roundhill, Inorg. Chem., 1972, 11, 1437. J. V. Kingston, F. T. Mahmond, and G. R. Scollary, J. Inorg. Nuclear Chem., 1972, 34, 3197. 586 J. T. Mague, Inorg. Chem., 1972, 11, 2558. E. K. Barefield and G. W. Parshall, Inorg. Chem., 1972, 11, 964. 2a7 C. Cocevar. G. Mestroni, and A. Camus, J. Organometallic Chem., 1972, 35, 389. 2 e 8 E. R. Birnbaum, J. Inorg. Nuclear Chem., 1972, 34, 3499. yB8 G. P. Khare and R. Eisenberg, Inorg. Chem., 1972, 11, 1385. 2 7 0 M. S. Fraser and W. H. Baddley, J. Organometallic Chem., 1972, 36, 377. *’l C . Masters, B. L. Shaw, and R. E. Stainbank, J.C.S. Dalton, 1972, 664. 5 7 a B. L. Shaw and R. E. Stainbank, J.C.S. Dalton, 1972, 2109. 2 7 3 S. A. Smith, D. M. Blake, and M. Kubota, Inorg. Chern., 1972, 11, 660. 274 S. Doronzo and V. D. Bianco, Inorg. Chem., 1972,11, 466. 2i6 A. ArAneo and T. Napoletano, Inorg. Chim. Acta, 1972, 6 , 363. 2 7 8 B. L. Shaw and R. E. Stainbank, J.C.S. Dalton, 1972, 223. I i 7 A. ArAneo, T. Napoletano, and P. Fantucci, J. Organomrtallic Chem., 1972, 42, 471. 278 A. R. Manning, J.C.S. Dalton, 1972, 821. l i S K. E. Schwarzhans and H.Steiger, Angew. Chem. Infernat. Edn., 1972, 11, 5 3 5 . C. B. Colburn, W. E. Hill, and D. W. A. Sharp, Inorg. Nuclear Chem. Letters, 1972, 8, 625. 281 A. L. Clarke a n d N . I. Fitzpatrick, J . Orgunornetollic Chem., 1972, 43, 405.

2R1

2b2

336

Spec*trosc*opirProperties X = ?-Me = 360

vjcni-'

lilor-gorlic.mid Orgcrnometnllir Conlporlt1rl.v

of

1-Me 364

2-Ci 369

14 365

1-C1

370

In [MCI(C,H,),],, i.r. bands at 398 and 502 cm- (M = Rh) o r 448 and 537 cm-l (M = Ir) have been assigned to V(M--C,H~).~~,1.r. spectra of [(TPC,H,),CO][COI,L] ( L = PPh, or OPPh,) have been given.2Lx3

Table 12 Compounds f o r which v(MH) assignments have been gifielr ( M = Rh or Ir) Coniportnd RhHCI,( PR,), RhH( PPh,),(SiEt,)CI [RhHCI(MeOPPh,),]+ Rh H( CO)X,(chel) [ R hH Cl(chel),] X [ RhH,(diars),]BPh, [RhH,{P(OPh)3)4I RhH,[P(OPh),],(chel) [RhH,(PPh,),(biPY)l [I r H( pi peridine),X ]X I rHCI(CO)( PPh,),L I r H( CO)( PPh,), L +

+

IrH(CO)(AsPh,),(fumaronitrile)

IrHCI,(PBut,R), [PBut, MeH] [Ir,CI,H(PBut, Me),] IrHCI,(PBut,R),L IrHCI( PPh,),(O,CRl) IrHCI( PPh,),( L)(0,CR2) [IrHX(chel),]Y [I r H,(c hel),] Y I rH2(M Ph3)2(chel) [~rH,(C~)(PPh,),lC(CF,CO,),HI IrH,X(CO)(PButMe,) I rH ,Y (CO)( PBut R,), I rH,X( AsPh,),( CN C6H4-p)

1 1 1 }

Ref: 261 a 262b 263 264' 265d 266' 267 268f 269y 270h 271' 2723

273k 274l 275m 263

276" 277"

PR, PMe,, PEt,, PMe,Ph, PEt2H, PEtPh2, o r PPh,; isomeric forms with H trans to CI o r to PR, distinguished by their v(RhH) values. "his substance may be a mixture of stereoisomers having a different configuration t o the compound of the same formula X = C1 or Br; chel = phen o r bipy. previously obtained. chel = PhMePCH,CH2chel -- the nrrho-carbonPMePh, X = [Rh(CO),Cl,] or CI; chel = diars, X = PFI. L = 2-mercapto-5NCO, NCS, o r NCSe. bonded ligand o-(PhO)2POC,H,. f X methylbenzenethio; configuration given. L = fumaronitrile, cinnamonitrile, benzylR -idenemalonitrile, fumaric acid, o r dimethyl fumarate. R = Me, Et, or Pr". Me; L = CO, MeNC, py, 4-methylpyridine, or P(OMe),. R = Et; L = CO, MeNC, or MeCN. R = Pr"; L = C O o r MeNC. Abnormally high values were noted for the compounds with L = py o r 4-methylpyridine. R' = R P or p-O,NC,H,. L = CO; R2 = Me, Et, Pr", Ph, H, CF3, o r MeCHCl. L = py; R 2 = Me, Et, or Ph. L = PhCN; PMe,Ph; R2 = Ph. L = p-MeC,H,NC; R2 = Me. * X = C1, R2 =- Me o r Pr". L Br, or 1; Y X, Clot, or BPh,; chel = vinylenebis(dipheny1phosphine). M = P or As; chel = S,CNEt, o r S,COEt; structure having trans MPh, groups, with cis H atoms given. " X = C1 o r Br. Y = C1; R -= Et, Pr", or Bu". Y - Br; R = Pr". OX = H , F, C1, Br, I, o r N3. a

7

3

2H2 ~3

A. L. Onderdelinden and A. van dcr Ent, Inorg. Chim. A d a , 1972, 6, 420. M. Van den Akker, R. Olthof, F. Van Bothuis, and F. Jellinek, Rec. Trai..t h i m . , 1972, 91, 75.

Vibrational Spectra of Transition-element Compounds

337 In [C0(CN)&l3- complexes there is a linear relationship between v(CN) and polar substituent constant of L:284 L = none or H 2 0 alkyl

alkenyl benzyl H

t hioalkyl

I Br

CN

v(CN)/cm-l

=

2082 2087-2090 2090-2094 2094 2097 21 10 21 16 2122 2127

Assignments of the i.r. spectra of cis-[Co(NH3),X3] (X = C1 or Br) and rrans-[Co(NH,),CI,] include assignments for v(CoN) (472-500 cm-l) and a mode described as v(CoX) and G(NCoN) (273-358 cm-1).28t 1.r. data (375-5000 cm-l) are also available 286 for [Co(NH,),J3+, [Co(NH,),(N0,)I2+, cis- and truns-[Co(NH,),(NO,),If, 1,2,3- and 1,2,4-[Co(NH3),(NO2),], trans-[Co(NH,),(NO,),]-, and [Co(N02)J3-. In [Co(CO),(NH3)(PPh3)(CONH2)],287 v(Co-NH,) has been assigned to a medium intense i.r. band at 329 cm-l. Very approximate normal-co-ordinate calculations, using five-atom M-NHS models, have been used to aid assignments of rhodium 288 and iridium 2 *9 ammines and their deuteriates; proposed values (i.r., cm-l) for v(MN) are: [Rh(N H3)6CIlC12 [Rh(ND,)5ClICI2 [Rh(NH,)$r]Br, [Rh(ND,),BrlBr,

[Ir(N H3)6C11c12 [1r(ND3)6C11C12

471, 478, ca. 489, 506 434, 442, 453, 470 470, 5 0 0 433,466 477, 486, 500, 516, 527 442,450, ca. 460,477,491

Tentative assignments for v(CoN) (ca. 230-240 cm-I) have been offered for complexes CoX2(2,2'-dithiodipyridine)and CoX2(4,4'-dithiodipyridine) [X = C1 or Br].290 The internal vibrations of the cations in [Co(en),I3+ salts (and the N-deuteriated species) are essentially the same in the solid state and in solution in H 2 0 or D20, indicating little cation-anion interaction.2e1 X-Ray data show that the trinuclear basic acetates [Rh,0(CX3C02),(Hz0)3]C104,H,0(X = H or D) are isostructural with the known Cr"' 284

2H5

T. Funabiki and K. Tarama, Bull. Chem. SOC. Japan, 1972, 45, 2945. M. Linhard, H. Siebert, B. Breitenstein, and G. Tremmel, 2. anorg. Chem., 1972, 389, 11.

2nE 28i

J. Csaszar, Magyar KPm. Folydirat, 1972, 7 8 , 154. H. Krohberger, H. Behrens, and J. Ellermann, J . Organometallic Chem., 1972, 46, 139.

28n

"@O

Yu. Ya. Kharitonov, N. A. Knyazeva, G. Ya. Mazo, I. B. Baranovskii, and N. B. Generalova, Russ. J . Inorg. Chem., 1971, 16, 1050. Yu. Ya. Kharitonov, N. A. Knyazeva, G. Ya. Mazo, I. B. Baranovskii, and N. B. Generalova, Russ. J . Inorg. Chem., 1971, 16, 1172. J. R. Ferraro, B. B. Murray, and N. J. Wieckowicz, J . Inorg. Nuclear Chem., 1972, 34, 23 1.

suL

R. W. Berg and K . Rasmussen, Spectroscopy Letters, 1972, 5 , 349.

12

Spectroscopic Properties of'Inorganic and Organometallic Compounds analogue; group-frequency assignments given include v,,,,(Rh,O) at 302 (X = H) or 298 cm-1 ( X = D) and vBRJTm(Rh30) at 382 and 397 (X = H) or 380 cni-I (X = D).2B21.r. data are also available for (MeCO)Rh(tetrap h e n y l p ~ r p h y r i n ) , NH4CoP0,,H20 ~~~ and its thermal decomposition and two geometrical isomers of each of the complexes [CoX(PPh,)(dimethylglyoxiniato),] (X = C1, Br, or I).2B6 I n dialkyl sulphide complexes MX3L, [M = Rh, X = C1, Br, or I ; M = Ir, X = C1 or Br; L = Me$, Et,S, (CH2)aS, or (CH,),S], v(MS) is in the 270-325 em-' i.r. range; i.r. [v(MS) and v(MX)], u.v., lH n.m.r., and dipole moment measurements all indicate mer geometry.2Bs Splitting into three components of v3 (in Td) of the anion in [R3NH][CoCl,] in benzene solution has been attributed to lowering of symmetry to CZvas a result of R,NH.-.ClCoCl, interactions since the [R4N]+ salt shows a single v(CoC1) i.r. band at 297 cm-l; [R,N][CoCl,] is said to be a pseudo-tetrahedral polymer even in solution (R = n-octy1).2B7Raman and i.r. spectra of alkali-metal and silver salts of some hexahalogenoiridates have been assigned. The v,(a,,) fundamental shows some variation with the nature of the cation (Mi):2Ba

3 38

[IrC1,]2[II-CI~]~[IrBr,12[IrBr,13[IrI,]Z-

Av/cm-l (M+) 352 (K'), 341 (Cs + ) 323 (K+), 331 ( A g i ) 216 (K+), 207 ( C s + ) 200 ( K i ) , 198 (Ag+) 156 ( K i )

Dramatic differences between relative Raman intensities of v 1 and v 2 for [IrX,I2- species (X = Cl, Br, or I) suggest that the supposed occurrence of dynamic Jahn-Teller effects may in some cases be quenched by spinorbit interaction and/or by charge transfer.208 A variation of v3(IrCl) (308-323 cm-l) in the isomorphous series M,[IrCI,] (M = K, Rb, Cs, or NH,) is recorded.2B0See also ref. 30. Two geometrical isomers of [CoCl(NH,)(tren)]CI, have been isolated, showing v(CoC1) at 342 (purpureo) or 366 cni--l (red Observations on the i.r. of cis-[Co(NH,),X,] (X = Cl or Br) and trans[Co(NH,),CI,] have been mentioned above ; another compound of formula 'Co(NH,),Cl,', described by Werner, has been found to have v(CoCI) '1e3

2Q4

2s6

2D7

"OQ

I. B. Baranovskii, G. Ya. Mazo, a n d L. M. Dikareva, Russ. J . Inorg. Chem., 1971, 16, 1388. B. R. James and D. V. Stynes, J.C.S. Chent. Conrm., 1972, 1261. L. N. Shchegrov, V. V. Pechkovskii, A . G . Ryadchenko, and R. Ya. Mel'nikova, Russ. J. Inorg. Chem., 1971, 16, 1622. A. V. Ablov, A. M. Gol'dman, 0. A. Bologna. Yu. A . Simonov, and M. M . Botoshanskii, Russ. J . Inorg. Chem., 1971, 16, 1167. E. A. Allen and W. Wilkinson, J.C.S. Dalton, 1972, 613. M. G. Kuzina, A. A. Lipovskii, and S. A. Nikitina, Russ. J . Inorg. Chenr., 1971, 16, 1313. G. L. Bottger a n d A. E. Salwin, Spectrochim. Acra, 1972, 28A,925. G . Pannetier and D. Macarovici, J . Thermal Anal., 1972, 4, 187. C.-H. L. Yang and M. W. Grieb, J.C.S. Chern. Comm., 1972, 656.

339

Vibrational Spectra of Transition-elenretit Cotiipoirnds

values of 270 and 282 cm-l and is therefore formulated 301 as the chlorobridged Cis-[{CO.LC1,(NH,),}cl~]~.Fairly complete i.r. and Raman spectral assignments have been given for [Co(NH3),X2]+ and [Co(en),X2] + salts; vaSum(CoX)is at wavenumbers (cm-l) of 280 (X = C1) or 170 (X = Br) with vsym(CoX)at 530 (X = F), 360 (X = Cl), or 230cm-l (X = Br).302 Values of v(CoX) in the expected regions have been noted for the tetrahedral complexes CoX2L, (X = C1 or Br; L = 2 - b r o m o t h i a ~ o l e ) . ~ ~ ~ Other references listing v(CoX) inodes have already been mentioned.12-16, 31, 33-36, 290 Assignments of v(RhX) and v(1rX) modes, generally made in structural characterization, have been given in a range of complexes as listed in Table 1 3 . 2 6 3 - 2 6 6 , 273, 276, 282, 288, 898, 304-316 Table 13 Compounds for which v(RhX) or v(1rX) assignments have heen

[(OC)CI,Rh-C(Ph)N( R1)C(Ph)=N Me], > (Me,PhP),CI,Rh-C( Ph)N(Me)C(Ph)=N Me [(OC)C13Rh-C(Ph)NHR2], > [(OC)C13Rh- C(Me)NHC6H4Me-o] (Me,PhP),Cl,Rh-C( Me)NHC,H,Me-o (Ph3P)(OC)C13Rh-C(Ph)NH R' 1 (chel), Rh C1 (chel)RhC1,Rh(cod) RhCIL, RhCI(CO),L Rh2CI,L, RhCI(TPP0)L RhCI(TPPO)(CO)(Ph3P) [RhCI(TPPO)], 301

302

303 304

306 308 3 07 3U8 4 OY

31 0

311

313 318

314

916

310

>

305b

307d

C1 > Br

N

NO, > I ( + Me)

Data on [MesPt(NH3)3]+have been mentioned in an earlier section., 317 3111

:Izo

322

y23

324 325

x!"

A. E. Keskinen and C. V. Senoff, J. Organometallic Chem., 1972, 37, 201. H. C. Clark and A. Kurosawa, J. Organometallic Chern., 1972, 36, 399. M. W. Adlard and G. Socrates, J. Inorg. Nuclear Chem., 1972, 34, 2339. M. W. Adlard and G. Socrates, J.C.S. Dalton, 1972, 797. U. Agarwala and Lakshmi Agarwala, J. Inorg. Nuclear Chem., 1972, 34, 251. K. Thomas, J. T. Dumler, B. W. Renoe, C. J. Nyman, and D. M. Roundhill, Inorg. Chem., 1972,11, 1795. C. Eaborn, A. Pidcock, and B. Ratcliff, J. Organometallic Chem., 1972, 43, C5. H. F. Klein and H. H. Karsch, Chem. Ber., 1972, 105, 2628. H. C. Clark and L. E. Manzer, Inorg. Chent., 1972, 11, 2749. D. F. Clegg, J. R. Hall, and G. A. Swile, J . Organometallic Chem., 1972, 38, 403.

342


A novel mode of bonding of acetoacetate esters, through the terminal aceto-carbon atom, has been reported; the complexes CIPd(CH,COCH,C02CH2R)L2[R = Me, L = py or *(bipy); R = Ph, L = py, 4-methylpyridine, 2,6-lutidine, or $(bipy)] have been characterized, showing v(PdC) in the 498-543 cm-l region.327 Vibrational data on Zeise’s salt (ix. and Raman) and some related complexes (i.r.) support previous assignments (Specfrochirn. Acta, 1969, 25A, 749), for example:328

v(PtC)/cm-l K[P~CI~(CZH~)I,H,O K[PtCl,(C2H4)1 K[PtCI,(C,D,)I K [Pt Br3(C,H4) 1

480, 490, 450, 484,

Y( PtX)/cm-l

390 400 384 393

336, 336, 336, 241,

330 328 326 225

Unassigned i.r. data are available329for bdC(CF,),bL, [L PMePh,,

or

i(diphos)],

I

I

PdC(CF,),OC(CF,),OL, I

[L

= =

P(OPh),, P(OMe),,

I

P(OMe),Ph, or Me,AsCH,Ph], and PdC(CFs)20C(CF3)20(PMePh2)2. Species M(CO), [M = Ni, Pd, or Pt; x = 1-41 have been identified by i.r. spectroscopy in the v(C0) region o n matrices produced from cocondensation of (M + CO) or (M + CO + Ar); although wavenumbers are given there are no detailed assignments to specific species given in this preliminary see also Chapter 4. In NiI,(CO)(PMe,),, v(NiC) is at 483 cm-1.931 Reactions of M(PPh3), [M = Pd, x = 4; M = Pt, x = 3 or 41 with CO at high pressures have been monitored by i.r. spectroscopy, and v(C0) data used to identify Pt(C0)2(PPh3)2,Pt(CO),(PPh,), and Pd(CO),(PPh3),, but in no cases were M(CO)4 species formed.332 Reaction of Ni(CNBut), with ClC02Et gives 333 ‘NiCI(CNBut),’ having v(NC) = 2180cm-l. Vibrational data are available for some cyanocomplexes of nickel(ir) 334 and p l a f i n u m ( ~ v ) . ~ ~ ~ The metal isotope effect has been used in making i.r. assignments for chelate complexes M{S(CH2),,NH2}, and M(S(CH,),NMe,}, (M = Ni or Pd; n = 2 or 3),336 and rrans-[Ni(chel),X2] {chel = 2,5-dithiahexane7

s28

s28

330 331 83a 333

s34

336 3~’R

S. Baba, T. Sobata, T. Ogura, and S. Kawaguchi, Inorg. N ~ c l e a rChein. Letters, 1972, 8, 605. J. Hubert, P. C. Kong, F. D. Rochon, and T. Theophanides, Cannd. J . Chern., 1972, 50, 1596. H. D. Empsall, M. Green, and F. G . A. Stone, J.C.S. Dalton, 1972, 96. H. Huber, P. Kundig, M. Moskovits, and G . A . Ozin, Nature Phys. Sci., 1972, 235, 98. M. Pankowski and M. Bigorgne, J . Organotnetallic Cheni., 1972, 35, 397. T.Inglis and M. Kilner, Nature Phys. Sci.,1972, 239, 13. S. Otsuka, M. Naruto, T. Yoshida, and A. Nakamura, J.C.S. Chern. Comm., 1972, 396. C . A. McAuliffe, M. 0. Workman, and D. W. Meek, J . Co-ordination Chein., 1972, 2, 137. M. N . Memering, Diss. Abs. Iiitenrat. ( B ) , 1972, 32, 5674. C.W. Schlgpfcr and K . Nakamoto, Itiorg. Chirrt. Acta, 1972, 6 . 177.

Vibrational Spectra of Transition-element Compo~nds 343 2-(ethylthio)ethylamine, 2-(methylthio)ethylamine, or NN-dimethylethyle~~ediamine}.~~' Typical results for metal-ligand stretching modes are shown in Table 14. Other assignments of v(hlN) relevant to this section

Table 14 Metal isotope efects on the far-i.r. spectra of some complexes of Ni and Pd Complex

58Ni(SCH,CH2NMe,), e2Ni(SCH,CH,NMe,), Pd(SCH,CH,N Me,)," trans-[58Ni(2, 5-dit hia hexane),CI,] tran~-[~~Ni(2,5-di t hiahexane),Cl,]

v( M N)/cm-l 371.2 367.5

394 266.7b 261 .7b

v( MS)/cm-

397.3 394. I 367 232: 209.6 232,c 205.6

OAssignments for Pd in natural abundance made on intensity grounds; note the reverse order of 4 M S ) and v(MN) compared with the Ni analogue. * v(NiC1) modes. Symmetric mode involving no motion of metal atom.

are for the five-co-ordinate complexes [Ni(tscR,)X]X (tscR, = cyclopentanone-, cyclohexanone-, or cycloheptanone-thiosemicarbazone;X = C1 or Br; ca. 290 and ca. 240 ~ m - 9 adducts , ~ ~ ~of trans-[NiC/3-ketoenolato),] with piperidine, piperazine, methylpiperazine, or morpholine [300385 cm-l; v(Ni0) in acetylacetonato-adducts at 57&568 and 4124 1 6 ~ m - ~ ] trans-[PdCl,(morpholine),] ,~~@ (supposedly at 500 ~ m - l ) , ~ and ~O trans-[PtLJ,] (L = py, 3- or 4-methylpyridine, 4-ethylpyridine, or 3 3 dimethylpyridine; tentatively at 245-294 ~ m - l ) . ~ * The l variation in v(PtN) noted in ref. 341 has been examined in more detail (with some disagreement in assignments) in a study of the i.r. spectra of trans-[MX2Lz] ( M = Pd or Pt; X = C1 or I ; L = py, 4-methylpyridine, or 4-ethylpyridine) [bromides were excluded because of the proximity of v(PtBr) to V ( P ~ N ) ] . ~The ~ , variations of v(MX) with L, and of v(MN) with X (Table 15) are considered to be too large to be due to differing basicity in L but may possibly arise from different molecular packing in the crystalline state.342 The mode of co-ordination of pseudohalide ligands to elements of this section has continued to be an active field.318-320s 343-346 Thus on the basis of i.r. (or with other) data [generally just v(CN) values] structural 3341

JJ7 3~'8

'Ip0

J41 343

s4a 344

J46 y4t(

C. W. Schliipfer, Y . Saito, and K. Nakamoto, Inorg. Chim. Actu, 1972, 6 , 284. B. Beecroft, M. J. M. Campbell, and R . Grzeskowiak, Inorg. Nuclear Chem. Letters, 1972, 8, 1097. G . Marcotrigiano, R. Battistuzzi, and G . C. Pellacani, Cunad. J . Chem., 1972,50,2557. R. A. Singh and E. B. Singh, J . Inorg. Nuclear Chem., 1972, 34, 769. G. W. Watt, L. K. Thompson, and A. J . Pappas, Inorg. Chem., 1972, 11, 747. M. Pfeffer, P. Braunstein, and J. Dehand, Inorg. Nuclear Chem. Letters, 1972, 8, 497. L. Sacconi and D. Gatteschi, J . Co-ordination Chern., 1972, 2 , 107. M. V. Artemenko, E. A, Chistyakova, P. A. Suprunenko, and G. I. Kal'naya, Russ. J . Inorg. Chem., 1971, 16, 1026. K. K. Chow and C. A. McAuliffe, Inorg. Nuclear Chem. Letters, 1972, 8, 1031. J . L. Lauer, M. E. Peterkin, J. L. Bumeister, K . A . Johnson, and J. C. Lim, hiorg. Chefti., 1972, 11, 907.

344

Specrroscopic Properties of Inorganic and Organometallic Compounds

Table 15 v ( M X ) and v(MN) assignments in Pd and Pt halide complexes of pyridine and substitutedpyridines“ Complex trans-[PdCl,(py),] trans-[PdI,(PY),l trans-[PdC12(4-Mepy),] trans-[Pd12(4-Mepy),] trans-[PdC1,(4-Etpy)2] trans-[Pd12(4-Etpy),] trans- [Pt C1,( py),] trans- [PtI,(PY),l trans- [PtC12(4-Mepy),] trans-[Pt12(4-Mepy),] trans-[PtCl,(4-E t py),] trans-[Pt12(4-Etpy),]

Y( MX)/cm-l

358 177 356 208 373 195 342 183 3 50 199 354 193

v(MN)/cm-l 278 278 302 320 306 278 282 293 317 32P 328 264

Taken from ref. 342. 4-Mepy = 4-methylpyridine; 4-Etpy = 4-ethylpyridine. A substantially different value (256 cm-’) was tentatively proposed in ref. 341.

conclusions have been drawn regarding [HP~(NCS)(BU~,P)~] (N- and Sbonded isomers),31e [Ni(NCS),(PhzAsCH2CHzNMeCH2-),] (N-bonded and bridged [N- plus S-bonded] isomers),343the 1:2 complex of Ni(NCS), with 2-benzylbenzimidazole (as [L,Ni(SCN)2NiL2][SCN],),344 and [Pd(SCN),(cis-Ph,PCH= CHPPh,)] (S-bonded on the basis of G(SCN) at 410 ~ r n - 9 . Values ~ ~ ~ for v(PdX) in N-bonded [Pd(Et,dien)X]f complexes [Et,dien = NNN’N’-tetraethyldiethylenetriamine;X = NCS (365), NCSe (360), NCO (365), N3 (380), NO2 (320cm-l)I have been compared with those in the S-(or Se-)bonded [Pd(dien)X]+ salts [X = SCN (320) or SeCN (318 ~ m - ~ ) ] . ~ ~ ~ Some i.r. data are also available for Cs2[PtI,(N0,)(NH,),] and its reaction products with Br, or 12,347 and for clathrates involving [Ni(CN)4]2-.348s 34a The following assignments of metal-phosphorus modes have been made :

347 348

349

360 361

v( M P)/cmRef. Ni12(CO)(PMe,)2 228 33 1 Ni( PHd4 296 350 “i(PM%)412+ 215 35 1 Ni(PMe3),X, 21 5-21 6 351 (X = CI, Br, C N , or NO,) Ni(PM%),(NCS), 218, 190 35 1 trans- [CI Pd(CH C&)(PPh,),] ca. 445 352 G. S. Muraveiskaya and I. I. Antokol’skaya, R u n . J. Znorg. Chem., 1971, 16, 868. S. Akyiiz, A. B. Dempster, R. L. Morehouse, and N. Zengin, J.C.S. Chem. Comm., 1972, 307. A. Sopkova, E. Matejcikova, J. Chomic, and J. Skorsepa, ‘Proceedings of the 3rd Conference o n Co-ordination Chemistry’, 1971, p. 33 1. M. Trabelsi, A. Loutelier, and M. Bigorgne, J. Organometallic Chem., 1972, 40, C45. A, Merle, M. Dartiguenave, and Y.Dartiguenave, J. Mol. Structure, 1972, 13, 413. Ya, M. Kimel’fel’d, E. M. Smirnova, N. 1. Pershikova, 0. L. Kaliya, 0. M. Temkin, and R. M. Flid, J. Strucf. Chem., 1971, 12, 1013.


345 A preliminary report of the formation of binary CO, complexes of Ni in Ar matrices363 was quickly shown by the same authors to be erroneous.364 The bands originally attributed to Ni(COa), species were shown in fact to be due to Ni(N2), complexes, the N, being an impurity in the gas mixture; this clearly illustrates the caution needed in interpreting results from matrix-isolation studies. Partial i.r. data have been given for Pd(hmcc), [(hmcc)H = ligand (14);

-

How

~~~ v(Pd0) = 570 ~ m - l ] , [(Ph,P)Pd-OC(O)CH,]n

H02C

[v(C=O)

at

1545

' '

~ m - l ] , the ~ ~ ~bis(hydroxy-bridged) complexes [L,M(OH),ML,](BF,), [M = Pd; L = Ph3P. M = Pt; L = py, Ph3P, or Et3P. v(Pt0) at ca. 480 cm-1],367and nickel-silica 337 Metal-sulphur vibrational assignments made are listed in Tables 14 and 16.346, 360-363 3369

Two new v(Ni-halogen) assignments reported are worthy of note. In [Ni(NN-di-n-butyldithiocarbamato),I], v(Ni1) is at the acceptably high value of 275 cm-l for this Ni"' complex.361 In the five-co-ordinate Nil' species [Ni(tscR,)X]X (X = C1 or Br; tscR, = cyclopentanone-, cyclohexanone-, or cycloheptanone-thiosemicarbazone) the v(NiC1) (256270 cm-l) and v(NiBr) (219-224 cm-l) values are intermediate between the ranges normally found for four- and six-co-ordination ;338 similarly, v(Ni1) is at 153 and 194 cm-l in Ni12(CO)(PMe3)2.331 A single-crystal X-ray study has shown PtCl, to be isostructural with PtBr, and a-PtI,. Fifteen of the 21 i.r. bands predicted for the octahedral chain were found (377s, 364sh, 345wm, 337s, 324sh, 310w, 290m, 274s, 235wbr, 2Ww, 182s, 167sh, 140w, 130w, and IlOwm), and the data were said to be consistent with the existence of terminal and bridging C1 363 354 366 358

36i

388

359 360

361 9 6a

3 IIs

H. Huber, M. Moskovits, and G. A. Ozin, Nature Phys. Sci.,1972, 236, 127. H. Huber, M. Moskovits, and G . A. Ozin, Nature Phys. Sci., 1972, 239, 48. D. K. Rastogi, Austral. J . Chem., 1972, 25, 729. S. Baba, T. Ogura, S. Kawaguchi, H. Tokunan, Y. Kai, and N. Kasai, J.C.S. Chem. Comm., 1972,910. G . W. Bushnell, K. R. Dixon, R. G. Hunter, and J. J . McFarland, Canad. J . Chem., 1972,50, 3694. V. V. Sviridov, G. A. Popkovich, and S. A. Serova, Russ. J . Inorg. Chem., 1971, 16, 925. R. A. Bailey and T. W. Michelsen, J . Inorg. Nuclear Chem., 1972, 34, 2671. J. Willemse and J. A. Cras, Rec. Trav. chim., 1972, 91, 1309. J. Willemse, P. H. F. M. Feuwette, and J. A, Cras, Inorg. Nuclear Chem. Letters, 1972, 8, 389. B. J. McCormick and B. P. Stormer, Inorg. Chrm., 1972, 11, 729. E. A. Allen and W. Wilkinson, Spectrochinr. Actn, 1972, 28A,725.

346

Spectroscopic Properties of Inorganic arid Organometallic Compounds

Table 16 Assignments of v(MS) modesn Conipound v( MS)/cm-’ Ref. 267-293 359b M[P~(SCN),I [Pd(dien)(SCN)] 320 346 [Ni(Bu,dtc),]+ 370, 387, 410 [Ni(Bu,dsc),] + 327, 317, 284c 360d [Pd(Bu,dtc),] + 333. 360. 383 [Pt(Bu,dtc),]+ 341, 365 J [Ni(Bu,dtc),] I 36ld> 377 “i(Rl,tc)zl 377-- 394 3621 “i(R22tC)2(PY)21 trans-[MX,(sulphide),] 286-346 cis-[PtY,(sul phide),] 268--360 363g a See also Table 14. M ” = Co, Ni, Fe, Cu, Pb, Mn, Zn, or Cd. v(NiSe).

}

}

(Uu,cltc) = NN-dibutyldithiocarbamato; Bu2dsc = Bun2NCSe,. Square-pyramidal geometry suggested by a n e.s.r. study. f R*,tc and R2,tc = NN-dialkylthiocarbamato; R1 = Me, Et, or Pr”, or R1, = (CH,),; Ra = Pr”, or R2, = (CH,),; v ( N i 0 ) at 520--539 cm I . M Pd or Pt; X = CI, Br, or I ; Y = Cl or Br; (sulphide) = Me$, Et,S, (CH2)PS,or (CH,)5S; the slightly wider range of v(MS) in the cis-compounds was noted. 7

Mixed Pt” halides have been shown (using X-ray measurements) to be individual compounds and have the following i.r. bands:365 PtICl PtCI, PtBrCl PtIBr PtBr,

v( Pt Cl)/cm-l 275, 340 319 307, 360 -

-

v(PtBr)/cm--’ -

240 238 240

Assignments of bridging v(PdX) or v(PtX) modes have been proposed in = Br, 209 and 200 ~rn-l),~,,[(PhMe2P),PtX2HgYz](X = Y = C1, 295 and 270 cm-l; related compounds also [(Ph2PCH2PPh2)PtC12Pt(Ph2PCH,PPh2)] (249 ~ m - ’ ) , ~ ~[(PhMe,P)RPdCI,PdR(PMe,Ph)] * {R = H,C= C(Me)CH,C(CF,)=C(CF,), 261 ~ m - l } and , ~ ~the ~ o-carbon-bonded chelates [o-R1,N=C(R2)C,H,PdC1], (R’ or R2 = H, Me, Ph, etc.; 254-320 ~ r n - 9 . The ~ ~ ~bis-arene complexes cis-[Pd{C(NHR)Y),Cl,] (Y = MeO, PhNH, Me,N, p-MeC,H,NH, etc.; R = various) appear to have loosely bound C1 atoms,371v(PdC1) having the low values of 263-305 cm-I. v(PtC1) values have been used to suggest the magnitude of the trans influence of the appropriate groups in trans-[PtL,(ArSO,)Cl] (296304 cm-l; L = Et,P, Et,As, Et,Se, or Et,Te; Ar = Ph, Me, or p-CIC,H,;

[(BU~~P)~P~X~P~(PBU~,),][BX,], (X = C1, 303 and 279 cm-l; X

364

366 s88 s67

388

389 lli0

M. F. Pilbrow, J.C.S. Chem. Comm., 1972, 270. S. S. Batsanov and L. A. Vostrikova, Russ. J. Inorg. Chem., 1971, 16, 1792. P. M . Druce, M. F. Lappert, and P. N. K. Riley, J.C.S. Dalron, 1972, 438. R. W. Baker, M. J. Braithwaite, and R. S. Nyholm, J.C.S. Dalton, 1972, 1924. F. Glockling and R. J. I. Pollock, J.C.S. Chem. Comm., 1972, 467. T. G. Appleton, H. C. Clark, R. C . Poller, and R. J. Puddephatt, J . Organometallic Chenz., 1972, 39, C13. 11. Onoue and 1. Moritani, J. Orgnnometollic Cliem., 1972, 43, 431. B. Crociani, T. Boschi, C. G. Troilo, and U. Croatto, Inorg. Chhl. A d a , 1972, 6 , 6 5 5 .


347 the ArSO, groups are S-bonded to Pt),3721373 trans-[Pt(PPh,),(COR)CI J (254-272 c m - l ; R in the acyl ligand = Ph, p-MeOC,H,, CH,=CH, or CH,=CMe),374 and trans-[Pt(PMe,Ph),(R)CI] (272 cm- l, R = Me3SiCH, ; 340 cm-l, R = C1).375In trans-[Pd(PEt,),ClL]+, the variation of v(PdC1) (330-275 cm-l) with the nature of the trans ligand L [= CO, p-MeC,H,NC, P(OPh),, P(OEt),, PPh,, PEt,, py, or 2,4,6-trimethylpyridine] parallels the known o-donor strengths of these l i g a n d ~ . ~ ~ ~ Other v(PdX) and v(PtX) assignments have already been mentioned 342 or are listed in Table 17.527, 341, 346, 35% 363, 377-383 3289

Table 17 Further references to compoiinds Jbr which v(PdX) or v(PtX) assignments have been proposed Ref.

Compound"

[Pd(Et,dien)X] + [H,C=CHCH,S(CH,),SPd Br], [MeS(CH,),SPdI],

}

[ClPd(CH2COCH,CO2CH,R)L',I trans- [PdCI(CHCI,)( PPh,),]

352

trans-[PdC12L2,] trans- [PdCl,L3,] [Pd2C14L221 [Pd,CI,(P"C),] [Pd2C12(P1--C)21 frans-[PdCl(P'- C)(PPh,)] trans-[PdCl(P2- C)(PPh,)] [PdCl(P1- C)pyp trans-[Pd X2(su1phi de),] trans- [Pt X,(sul p hide),] cis-[PtY,(sulphide),] trans- [Pt I,( ami ne),]

378

363

[(cis-Ph,PCH=CHPPh,)PtCI,] c~~-[{H,C=CH(CH,),C(O)M~}P~Y~) [(O-NCC6 H, PPh2)2 Pt CI,]

[(u-NCC,H~PP~,)P~CI,I, (Ph,P),PtCl(CCl= CCI,)

346 377" 327

)

34 1

379 380

381d

382"

F. Faraone, L. Silvestro, S. Sergi, and R. Pietropaolo, J. Organometullic Chetn., 1972, 34, C55. 3 7 3 F. Faraone, L. Silvestro, S. Sergi, and R. Pietropaolo, J . Orgumornetallic Chetii., 1972, 46, 379. 3 7 4 S. P. Dent, C. Eaborn, A. Pidcock, and B. Ratcliff, J . Organometallic Chern., 1972, 46, C68. 37G M. R. Collier, C. Eaborn, B. Jovanovid, M. F. Lappert, L. ManojloviC-Muir, K. W Muir, and M. M. Truelock, J.C.S. Chem. Comm., 1972, 613. 376 W. J. Cherwinski, H. C. Clark, and L. E. Manzer, Inorg. Chem., 1972, 11, 1511. 3i7 L. Cattalini, J. S. Coe, S. Degetto, A. Dendoni, and A. Vigato, Inorg. CBem., 1972, 11, 1519. 3i8 A, J. Cheney and B. L. Shaw, J.C.S. Dalron. 1972, 860. 3 7 @ R. B. King and P. N. Kapoor, Inorg. Chem., 1972, 11, 1524. 3n0 B. T. Heaton and D. J. A. McCaffrey, J. Organometullic Chem., 1972, 43, 437. YH1 D. H . Paync and H. Frye, Inorg. Nuclear. Chem. Letters, 1972, 8, 73. :IBJ D. T. Clark and D. Briggs, Nature Phys. Sci., 1972. 237, 16. *IH:' A. J. Cheney and B. L. Shaw, J.C.S. Dnltort, 1972, 754.

348

Spectroscopic Properties of'Inorgarlic and Organometallic Compounds

Table 17 (cunt.) Compounda trans-[PtCl,L2,]

[Pt2C12(P1--C),I [Pt2C12(P2--C)21 trans-[Pt C1(Pl- C)L2] trans-[Pt C1(P2- C)L3] [Pt Cl(P1- C)py1" trans-[Pt Cl(P1-C)(PPh3)] ci~-[PtCl(P~-C)(PPh3)l trans-[PtCI(P2-C)( PPh,)]

Ref.

383

X = C1, Br, or I ; Y = CI or Br; Et,dien =- NNN'N'-tetraethyldiethylenetriamine; R = Me or P h ; L' = py, +(bipy), etc.; L2 = PBut(o-tolyl),; Ls = PBut,(o-tolyl); (P'-C) = o-CH,C,,H4PBut(o-toly1); (P2-C) = o-CH2C,H,PBut2; (sulphide) = : Me$, Et& (CH2)& or (CH2),S; (amine) = py or 3-methyl-, 4-methyl-, 4-ethyl-, or 3,5-diSome closely related complexes also studied. methyl-pyridine. Mixture of cis- and trans-isomers. Structures proposed on the basis of v(PtC1) and v(CN) data. Compound formed by surface isomerism of (Ph,P),Pt(C,Cl,) during X-ray photoelectron spectroscopic study.

11 Copper, Silver, and Gold Assignments have been given for v(AuC,) (53@-570 cm-l) and some other modes in a range of dimethylgold complexes Me,AuC1(EMe2) [E = S or Se], Me,AuX(RS(CH,),RS)AuMe,X [X = C1, n = 2 or 3, R = Me or E t ; X = Br, I, or SCN, n = 2, R = Me or E t ; X = SCN, n = 3, R = Me], and [ M~,AU(M~SCH,CH,SM~)](N~,).~~~ Reaction of MeAu(PMe,Ph) with F,C-C=C-CF, gives a stable 2:l adduct formulated as in (15) on the basis of i.r. and n.m.r. data;386v(AuMe) is at 502 cm-' with v(CC) of the bridging acetylene at 1565 and 1586 cm-l.

Unassigned i.r. data have been listed for fluorocarbon complexes derived from tertiary-phosphine-gold methyls.38e Data on [ Me,Au(NH3)2]+have been mentioned in a n earlier section.2 Metal isotopic substitution has been used in making assignments of the i.r. spectra of en and alkyl-substituted en complexes of copper, for example :387 384 385 3n8

3u7

H. Schmidbaur and K. C. Dash, Chem. Ber.. 1972, 105, 3662. A. Johnson, R. J. Puddephatt, and J. L. Quirk, J.C.S. Chem. Comm., 1972, 938. C. M. Mitchell and F. G. A. Stone, J.C.S. Dalfon, 1972, 102. G.W. Rnyner-Canhan1 and A. B. P. Lever, Cunutl. J. C'hem., 1972, 50, 3866.

Vibrational Spectra of Transition-element Compouiids 03Cu(en)C12 ‘Vu(en)CI,

v( CuN)/cm -l 375, 317.5 373, 315

349

v( CuCl)/cm-I 265 264

In N-alkyl derivatives, ~ ( C U Nvaries ) in the range 269-400cm-l. For bis[pyridine-2-(N-cyanocarboxamidato)]aquocopper(11), the crystal structure of which was determined,388v(CuN) has been given as 302cm-l. I n the Cur complexes L,Cu(ClO,), wavenumbers/cm-l of v(CuN) are appreciably higher than in related Cu” systems: 425 and 375 (L = 2-methylpyridine), 400 and 306 (L = 2,5-dimethylpyridine), 277 and 259 (L = 2-ethylpyridine), and 260 and 248 (L = 2-i~opropylpyridine).~~~ 1.r. (NO,- modes), electronic, and (especially) e.s.r. spectral studies indicate distorted cis-octahedral structures for [Cu(chel),(NO,)]NO, [chel = 2,6-dimethyl-o-phenanthrolineor 3,3’-dimethylene-4,4’-dimethyl2,2’-biq~inoline].~~~ Partial i.r. data are also available for some new dinuclear Cull chelates such as of the [NN’-bis-(3-aminopropyl)oxamidato]copper(r1) li gand.3Q1 1.r. bands in the region ca. 33&390cm-’ are assigned as v(AuP) in (Me,P)AuX, [(Me,P),Au]Y, and [(Me,P),Au]Y (X = NO, or BF,; Y = C1, Br, I, or X).,02 1.r. bands at 798 and 810cm-1 have been assigned to vasym(CuOCu)in [ C U ( N H , ) ( C ~ O ~ ) ]For ~ . ~ ~(DPPH)Cu(chel) ~ [DPPH = 2,2-diphenyl-1picrylhydrazyl; chel = acac, trifluoroacetylacetonato, or N-methylsalicyla l d i - i m i n a t ~ ] values , ~ ~ ~ for v(Cu0) are said to be 449-458 cm-l. Reaction of an Ag20 surface with O,, C02, and H,O vapour has been studied using i.r. techniques.3Q6When [C~(arginine)~(ClO,)~] (shown by i.r. to contain bidentate C104- groups) is slowly recrystallized from water, the product contains unco-ordinated Clod-, viz. [Cu(arginine),(H20)](C10,),, and is converted back into the anhydrous material when pressure is applied during KBr disc preparation.3Qs 3B7-402 Assignments for v(MS) and v(MSe) modes are listed in Table 18.3841 s8a

88D 390

8Ds

393

3D4

A. C. Bonamartini, A. Montenero, M. Nardelli, C. Palmieri, and C. Pelizzi, J. Cryst. Mol. Structure, 1971, 1, 389. A. H. Lewin, R. J. Michl, P. Ganis, and U. Lepore, J.C.S. Chem. Comm., 1972, 661. Ph. Thomas, D. Rehorek, H. Spindler, R. Kirmse, and H. Hennig, Z. anorg. Chem., 1972, 392, 241. H. Ojima and K. Nonoyama, Z. anorg. Chem., 1972, 389, 75. H. Schmidbaur and R. Franke, Chem. Ber., 1972, 105,2985. L. Cavalca, A. C. Villa, A. G. Manfredotti, A. Mangia, and A. A. G. Tomlinson, J.C.S. Dalton, 1972, 391. F. Leh and J. K. S. Wan, Canad. J. Chem., 1972, 50, 999. T. L. Slager, B. J. Lindgren, A. J. Mallmann, and R. G. Greenler, J . Phys. Chem.,

1972, 76, 940. S. T. Chow and C. A. McAuliffe, Inorg. Nuclear Chem. Letters, 1972, 8, 913. 307 K.H. Schmidt, A. Muller, J. Bouwma, and F. Jellinek, J. Mol. Structure, 1972, 11,275. J. G. M. van der Linden and P. J. M. Geurts, Inorg. Nuclear Chem. Letters, 1972,8,903. 399 J. G. M. van der Linden and W. P. M. Nijssen, 2. anorg. Chem., 1972, 392, 93. ‘0° G. Marcotrigiano, R. Battistuzzi, and G. Peyronel, Inorg. Nuclear Chem. Letters, 1972, 8, 399. 4 0 1 R. A. Potts, J. Inorg. Nuclear Chem., 1972, 34, 1749. I o 2 E. A. Allen and W. Wilkinson, Spectrochim. Acta, 1972, 20A,2257.

350

1

Spectroscopic Properties of Inorganic and Organonietailic Cornpoiitids

Table 18 Assignments for v(MS) und v(MSe) uibrationslcm-' (M = Cu or Au)

cu,vs,

cot~tpolltlli"

Cu,NbS, Cu,TaS, Cu,NbSe, Cu,TaSe, Cu(S,CN Et,), [Cu(S,CNEt,),lrI,I Cu(Se,CNEt,), ICu(S%CNEt,),l[I,l [Au(S,CNEt,),]Br [Au(S,CNBun,),][AuBr, ] Br,Au(S,CNEt,) [A u(Se,CN Et,),] Br [Au(Se,CNBu",),][AuBr,] Br,Au(Se,CNEt,) Au[SC(NH,),I,X Au [SC(N H2)212Y,H,O AuCI,(Me,SO) AuCI.9[(CD3)2SO] AuCl(su1phide) AuBr(su1phide) Me,AuCI(Me,S) Me,AuCl( Me,Se) Me,AuZ[RS(CH,),SR]AuZMe, [ Me,Au{ MeS(CH,),SMe} ]NO,

v(MS) or v(MSe) 285 267, 244 267, 244 169, ca. 144 170,358 141

398 240 3 10 378 380

Ref.

397b

398C

1 ;;; J

399"

378 253

262-284 430 399

400

}

270-286 263, 2950

4016

402'

7

258-3 150 270, 306

X = C1, Br, or 1; Y = BF4, CFSC02, o r C l o d ; (sulphide) = Me,S, (CH,),S, or (CH2)sS; Z = CI (n = 2 or 3, R = Me or Et), Br (n = 2, R = Me or Et), I (n = 2, R = Me o r Et), o r SCN (n = 2, R = Me o r Et; n = 3, R = Me). *Considerable covalent character in the Cu-S or Cu-Se bonds is indicated. v(CN) Values given for these and some related compounds. Conductance data show compounds to contain ionic X o r Y groups; internal models of SC(NH,), ligands assigned, showing S-coordination to Au. v ( S 0 ) a t 1198 cm-l shows S-co-ordination to Au. f v(AuS) could not be observed for analogous AuX,(sulphide) complexes (X = C1 or Br; expected region ca. 3 0 0 cm-*). Modes described as v(AuSQ) or v(AuSeQ), where Q = C1 or 2.

Complexes [CuL,]X (L = Ph3PS, Ph,AsS, etc.; X = C10, or BF4) have been so formulated on the basis of i.r. spectral (internal modes of X) and conductivity data.4o3 1.r. bands of matrix-isolated CuCl have been attributed to trimeric (393.5, 383, 285, and 101 cm-l) and tetrameric species (324, 248, 234, and 218 cm-l), since mass spectral data indicated these to be the main components of CuCl vapour ; simple normal-co-ordinate calculations were performed.404 The observation of three v(CuC1) i.r. bands in benzene solutions of [R,N]CuCl, (387, 316, 215 cm-l; R = n-octyl) is said to indicate that the 'O* 404

J. A. Tiethof, A. H. Hetey, P. E. Nicpon, and D. W. Meek, Znorg. Nuclear Chem.

Lerrers, 1972, 8, 841.

S. N. Cesaro, E. Coffari, and M. Spoliti, Inorg. Chim. Acfu, 1972, 6, 513.

Vibrational Spectra of Transition-element Conipounds

35 1 anion is polymeric; under similar conditions the [R,NH]+ salt shows two v(CuC1) modes (313, 263 cm-l), apparently as a result of R3N-H- .C1 in t ~ r a c t i o n s . ~ ~ ~ Fluorination of AuF, in the presence of XeF, in excess affords [XezFll] [AuF,]-, which has been characterized partly by Raman data.405 I n addition to modes due to the (known) cation, Raman bands at 586 and 223 cm-l are found, which are attributed to the [AuF,]- ion; the corresponding caesium salt gives values of 595 (v,, a,,), 520 (v,, e,), and 224 cm-l (vg, t,,). Also reported are Raman data for Cs[AuF,]: 588 (vl, a,,), 561 (v4, b,,), and 237 and 230 cm-1 (v3, b1,).400" AuI has been studied by Raman spectroscopy ;406 see Chapter 4. Copper(1) halide complexes have received some attention. v(CuX) values [232 and 162 (X = Cl), 202 and 145 (X = Br), or 175 and 128 (X = I)] and other data show that CuX(o-Me,NC,H,AsMe,) complexes are dimers, (chel)CuX,Cu(chel), with X-bridges (for X = C1 this has been shown previously by X-ray diffra~tion).~~' On the other hand, the high value (375 crn-l) of v(CuC1) in Cu,Cl2(cis,trans-cyclo-octa-l,3-diene), together with the observation of a single v(C=C) band at 1505 cm-l, indicates the presence of terminal Cu- C1 bonds, viz. ClC~(diene)CuCl.~~* In CuCl complexes (2:1, 3:2, 4:3, I:], or 2:3) with Ph,P(CH,),PPh, (n = 1 or 2), v(CuC1) is in the 236-287 cm-l range.4og 3*7 Other references giving v(CuX) data have already been Far4.r. bands have been listed for Cu,Cl,O(Ph,PO), but not assigned.410 A new Cu" iodide complex [Cu(py)I,,H,O] shows v(OH,) at ca. 3400 cm * in the i.r., showing the HzO molecule to be ~o-ordinated.~~, Notable developments in v(Au- halogen) correlations have taken place. In a large series of complexes LAuX (L = neutral unidentate ligand), ranges of v(AuX) are 310-342 (X = Cl), 205-235 (X = Br), or 155-190 cm-l (X = 412 The order of decreasing trans influence of L in these compounds, as indicated by the v(AuC1) values, is (in part):412

-

+

Ph,AsS > Ph,PS > Ph,As > Ph3Sb

-

Ph,P > Et3P.

For related compounds LAuX,, ~ ( A u X )falls in the range 300-370 412 The most definitive assign(X = Cl) or 202-270cm-I (X = Br).4021 ments of v(AuX) in Au"' complexes have been made using both i.r. and Raman spectral measurements for the complexes (sulphide)AuX, [X = C1 or Br; (sulphide) = Me$, Et,S, (CH2),S, or (CH,)6S]:402 406

Ia8 .Iui

40n

410

411

K. Leary and N. Bartlett, J.C.S. Chem. Comm., 1972, 903. D. Breitinger and K. Kohler, Inorg. Nuclear Chem. Letters, 1972, 8, 957. L. Volponi, B. Zarli, G . G. De Paoli, and E. Celon, Inorg. Nuclear Cheni. Let/ers, 1972, 8, 309. H. A. Tayim and A. Vassilian, Inorg. Nuclear Chem. Letters, 1972, 8, 2 15. N. Marsich, A. Camus, and E. Cebulec, J. Inorg. Nuclear Chem., 1972, 34, 933. B. Carr and J. F. Harrod, Canad. J . Chern., 1972, 50, 2792. B. K . Mohapatra, Chem. and Ind., 1972, 383. D. R. Williamson and M. C. Baird, J . Itiorg. Nuclear Chern., 1972, 34. 3393.

3 52

Spectroscopic Properties of Inorganic a i d Organometallic Coinpolmds v,,,,(tr~ns-AuX.J : ( a l ) v,,,(trans-AuX,) : (al) v(AuX) trans to L: (b1)

x

=

c1

36&-366 335-340 3 12--324

X = Br 258-270 2 32-260 202-235

Some mixed halogeno-complexes have also been e.g. (Ph,P)AuCIBr,. The new air-stable adducts (p-XC6H,)AuCl,L (X = H, Me, or C1; L = Prn2S,Ph3P, or Me,P) are apparently cis,413v(AuC1) for the Au-CI bonds trans to the aryl group falling in the range 276-294cm-l whereas the other v(AuC1) modes are at 310-365 cm-l. However, when L = py there are no bands in the 276-294cm-l region, suggesting a trans formulation. As measured by v(AuCI), the trans influence of the groups in these Au"' complexes is (cf. ref. 412 cited above):413 Ar > PR, > SPP, > C1 > py

Other assignments of v(AuX) are for certain [AuBr2]- salts (250-255 cm-I), Br,Au(S,CNEt,) (216 and 243 cm-l), and Br,Au(Se,CNEt,) (222 and 247 ~ m - ~ ) . ~(See @ *also footnote g to Table 18.) 12 Zinc, Cadmium, and Mercury Chemisorption of hydrogen on to ZnO gives rise to an i.r. band at 1705 cm-l, attributed to v(ZnH) [v(ZnD) at 1225 cm-1].p14 The new complex mercury(I1) cations [MeHgLIf (L = PMe,, AsMe,, SMe,, or py) show v(HgC) in the 536-563 cm-1 range.415 In MeHgSMe (537 cm-l) 416 and (XCH,),Hg [510 and 530 (X = Cl), 488 and 510 (X = Br), or 475 and 488 cm-l (X = I)],'"' somewhat lower values are found for v(HgC). In the latter series,417trans-conformations dominate in the solid state but the melts contain appreciable amounts of gauche-conformers. The difference between v(HgC) in [MeHg(NH,)]+ (547 cm-l) and [MeHg(OH,)]+ (566 cm-l) has already been mentioned,2 and reference to the spectrum of (PhCH2),Hg 418 is made in the preceding chapter in relation to the spectra of related germanium and tin compounds. A careful comparison of the i.r. spectra of Hg(C,H,), and Hg(C6D6),in the v(CH) region has confirmed the presence of five fundamentals, and that the o-bonded structure Hg(h1-C5H5),is correct.41g The vibrational spectra of Ph2Hg, (CID6),Hg, and PhHgX (X = C1, Br, or I) have been

u4 416

416

417

419

K. S. Liddle and C. Parkin, J.C.S. Chem. Comm., 1972, 26. R. J. Kokes, A. L. Dent, C. C. Chang, and L. T. Dixon, J. Amer. Chem. Soc., 1972, 94, 4429. P. L. Goggin, R. J. Goodfellow, S. R. Haddock, and J. G. Eary, J.C.S. Dalron, 1972, 647. R. A. Nyquist and J. R. Mann, Spectrochim. Acfa, 1972, 28A, 511. Y. Imai and K. Aida, Spectrochim. Acta, 1972, 28A, 517. M. Drgger and G. Gattow, Spectrochim. Acta, 1972, 28A, 425. J. Mink, L. Bursics, and G. VCgh, J. Organometallic Chem., 1972, 34, C4.

Vibrational Spectra of Transition-element Conipounds 353 studied and a normal-co-ordinate calculation has been performed for the in-plane vibrations of the PhHgX system.420 1.r. data are available for MeOCH2CH2HgCl421 and PhCH2HgCHzT.422 The pyrolysis of XHg(CC13) [X = CCl,, Cl, or Ph] has been studied by i.r. spectroscopy using matrix-isolation methods.423 Complexes Zn(CN)2,2RNH, (R = Prn or Bun) are deduced as being octahedral chain polymers on the basis of Y(CN) and other i.r. data.424 In Hg(CN)aL1 and Hg(CN)2L22[L2 = py or methyl-substituted pyridine; L1 = La or methyl-substituted pyridine N-oxide], v(HgC) is in the 424486 cm-' range.4226* 426 Metal-isotopic substitution (a486eZn)has been used in making assignments for ZnX2(py)2,4a7ZnX,(2,2'-dithi0dipyridine),*~~ and ZnX2(4,4'dithiodipyridine) 428 [X = Cl or Br]. Substitution of [2H6]pyfor py enabled and ~ ' the application of high v(2nN) to be distinguished from ~ ( Z n x ) , ~ pressures was used to discriminate between veym(ZnX)and Some assignments are given in Table 19.

Table 19 Some vibrational assignmentslcm-' for 64Zn and 6eZn halide complexes Complex a 8 4 Z nC12(~~)2 6eZnClp(py)a s4znCla([2Htil~~)a 6 4 Z n B r a (12~ ~ 68ZnBr2(PY)2 64ZnBr,([2HslPY), " 4 Z nIa(~~)2 " Z ~ I ~ ( P)2 Y 64ZnId[2Hsl~~)a 84ZnC12(2,2'-dtdp) 88ZnC1,(2,2'-d tdp) 64ZnBr,(2,2'-dt dp) 88ZnBr2(2,2'-d tdp) 64ZnC12(4,4'-dtdp) s8ZnC12(4,4'-dtdp) 64ZnBr2(4,4'-d td p) 68ZnBr2(4,4'-dtdp)

vaeym(ZnX) 329.2 324.4 328.4 257.0 251.7 255.3 227.4 223.0 225.5 322" 321 \

v,yrn(znX) 296.5 294.1 296.3 223.0" 219.3c 221.7" obsc." obsc.C ubsc.c

295 29 1

Y

340 335 248 244

267 26 1

299 296 20 1 197

J

v(ZnN)b 222.4, 203.9 218.8, 201.5 218.6, 199.8 obsc.,d 184.5" obsc., 183.8c obsc., 181.3c 217.0, 168.8c 214.5, 168.lC 213.9, 161.6c 224 220 21 2 210 21 3 21 1 226 22 1

Where two values are given, these are vaeyrn(ZnN)and a dtdp = dithiodipyridine. uey,(ZnN), respectively. Coupled modes. obsc. = obscured. Includes contribution from ligand mode. J. Mink, G. Vtgh, and Yu. A. Pentin, J. Organometallic Chem., 1972, 35, 225. J. C. Soyfer, P. Audibert, and N. Giacchero, Bull. Soc. pharm. Marseille, 1971, 20, 77. R. Scheffold and U. Michel, Angew. Chem. Internal. a n . , 1972,11, 231. I Z 3 A. K. Mal'tsev, R. G. MikaClyan, and 0. M. Nefedov, Dokludy Phys. Chem., 1971,

IZo

421

42'L

201, 1027.

K. Mockel and W. Miiller-Litz, 2. anorg. Chem., 1972, 393, 81. I. S. Ahuja and A. Garg, J. Inorg. Nuclear Chem., 1972, 34, 2074. 426 I. S. Ahuja and A. Garg. J. Znorg. Nuclear Chem., 1972, 34, 2681. IL" Y. Saito, M. Cordes, and K. Nakamoto, Spectrochim. Acta, 1972, 28A, 1459. 428 J. R. Ferraro, B. Murray, A. Quattrochi, and C. A. Luchetti, Spectrochim. Acfa, 1972, 28A,817.

416

354

Spectroscopic Properties of Iirorgartic mid Organometallic Compounds

v(MN) modes have been located in generally accepted regions for the following complexes: M(SCN)L2 (M = Zn or Cd; L = py, PhNH,, or derivatives of these) ;4e8 CdX,(pyrazine), CdX,(py),, and CdI,(PhNH,), [X = CI, Br, or M(chel),,nH,O [M = Zn, n = 4; M = Cd, n = 8 ; M = Hg, n = 1 ; chel = 3-(4-pyridyl)tria~oline-5-thione];~~~ MX,(triam), Zn,X,(triam), and Hg,I,(triam) [X = C1, Br, or I ; triam = N N N ' N"N"N"-hexamethyl-3,6-diazaoctane-l,8-diamine] ;432 and [MeHg(py)](N03).416 In the novel compound Hg(PBut,),, a product from reaction of secondary phosphines with HgBut2, a Raman band (absent from the i.r. spectrum) at 370 cm-' is attributed to vsYm(HgP2);the derived force constant of 2.16 mdyn A-l is said to be consistent with considerable Hg-P doublebond character.433 In NO3- or BF4- salts of the cations [XHg(PMe,)]+ and [Hg(PMe,),12 (X = C1, Br, I, CN, or Me), v(HgP) is in the 347-375 cm-l range, while some related AsMe, complexes give v(HgAs) at ca. 250 ~ m - l . * ~ ~ Raman spectra of the crystalline polymeric compounds [HgOHINO,, [Hg,O,](NO,),, and [Hg30B](N03)2,H20[from hydrolysis of aqueous Hg(NO,),] show that the frequency of the most intense v(Hg0) mode depends on the number of Hg atoms bonded to a common oxygen atom.43* From a Raman spectral study of concentrated aqueous zinc nitrate solutions at 50, 70,and 88 "C, contact-ion-paired nitrate, solvent-separated nitrate, and 'free' NO3- have been shown to be present. Apart from various NO3- internal modes, bands were identified as due to v(Zn-OH,) (390-399 cm-l) and v(Zn-ONO,) (260 ~ m - 9 .A~comparison ~ ~ of the i.r. spectra of (MeC02),Zn(NH3), and (HC02),Zn(NH3), has led to the suggestion that the former compound has octahedral co-ordination at Zn (bidentate acetato-ligands giving a trans-[ZnO,N,] skeleton), whereas the formate is tetrahedrally co-ordinated (unidentate formato-ligands giving a CZv[ZnO,N,] Fairly complete i.r. and Raman data have been presented for (MeCO,),Hg,, (MeCO,),Hg, and their fully deuteriated derivatives. Bands assigned as v(Hg0) are as follows:44

I.r./cm-l (CH3C02)2Hg2 (CD,C0,)2Hg, (CH3C02)2Hg (CD3 g 428

4:i0 p91 432

433 434 436 436

268 250 313 -~

Rarnanlcm-' 29 5 283 279 255

I. S. Ahuja and A. Garg, J . Inorg. Nuclear Chem., 1972, 34, 1929. M. Goldstein and W. D. Unsworth, J . Mol. Structure, 1972, 14, 451. B. Singh and R. Singh, Indian J . Chem., 1971, 9, 1013. A. Cristini and G. Ponticelli, J.C.S. Dalton, 1972, 2602. M.Bandler and A. Zarkadas, Chem. Ber., 1972, 105, 3844. R . P. J. Cooney and J. R. Hall, Ausrrul. J . Chem., 1972, 25, 1159. A. T. G. Lemley and R. A. Plane, J . Chem. Phys., 1972, 57, 1648. A. I. Grigor'ev and E. G. Pogodilova, J . Sfruct. Chem., 1971, 12, 240.

Vibrational Spectra of Tratisition-element Compounds 355 The series [XHg(O,CMe)l, (X = C1, Br, I, or CN) appear to be true 'mixed compounds', whereas for X = SCN the probable formulation is Hg(SCN),,Hg(O,CMe), [v(HgO) at 313 cni l, v(HgS) at 276 and 300 ~m-l].~~ In complexes of various sulphoxides (R1R2SO)with mercuric chloride, v(Hg0) is said to be in the 3 9 2 4 2 3 cm-' range.437 For the bis(monothiocarbamato) chelates M(OSCNR), [M = Zn or Cd; R = piperidyl or pyrrolidinyl], v(M0) and v(MS) are given as 471--491 and 375--388 cm-*, respectively; the mercury complex Hg(OSCNC,H,), shows an i.r, band at 1571 cm-l assigned as v(C=O), indicating that the oxygen atom is not ~o-ordinated.~~~ v(MS) assignments (cm-l) have been given for: MeHgSMe (329),41s [MeHg(SMe,)](NO,) (304),415 M[Cd(SCN),] (M = Co or Ni) (227),359 M(SCN),L, [L = py, PhNH2, or derivatives of these; M = Cd (229 --270) or Hg (248-290)],429 Hg(SCN),(LO) [29O--305 ; (LO) = methyl-substituted pyridine N - o ~ i d e ]HgX,{S=C(SR2)(NR1,)} ,~~~ (21 5 -225; X = C1, Br, or I; R1 = Me, R2 = Me, Et, PhCH,, or PhCOCH,; R1 = Et, R2 = PhCOCHz),439HgX2{SC(NH2)2)(232-254; X = C1, Br, or I),440 and M{MeC(S)CHC(E)COEt), 1332-390; E = S ( M = Zn, Cd, or Hg) or 0 (M = Zn or Cd)].,,I 1.r. data for the gas-phase and matrix-isolated MX, species (M = Zn, Cd, or Hg; X = F, C1, Br, or I) have been reviewed with emphasis on the reliability of deduced geometry.29 The i.r. and Raman spectra of HgX, (X = C1, Br, or I) have been measured in dioxan or benzene solution.442 The Raman spectra of molten or glassy ZnC1,-AlCl, mixtures indicate that [ZnC1J2- ions are not present, although gradual changes in band positions and intensities occur when AlCl, is progressively added to molten ZnCl,, suggesting some breakdown of the polymeric [ZnCl,], The Raman spectrum of molten Cs,ZnCl, at 620 "C has been illustrated in a paper describing a simple furnace for obtaining high-temperature Raman this spectrum has also been discussed.443 Ranian spectra of Cd(NO,), with either KCl or KBr in equimolar NaN0,-KNO, melts indicate that the predominant complex ions present are [CdLcI,] or [CdBr,12-, respectively.445 Assignments in terms of the appropriate line group or sheet group symmetry have been given for the i.r. and Raman spectra [v(CdN) and v(CdX,), modes] of CdX,(py),, CdX,(dioxan), and CdY ,(pyrazine) 437 438 499

410

14* p42 44s

444

F. Biscarini, L. Fusina, and G. D. Nivellini, J.C.S. Dalton, 1972, 1003. B. J. McCormick and D. L. Greene, Inorg. Nuclear Chem. Letters, 1972, 8, 599. H. C. Brinkhoff and J. M. A. Dautzenberg, Rec. Trao. chim., 1972, 91, 117. G . Marcotrigiano and R. Battistuzzi, Inorg. Nuclear Chem. Letters, 1972, 8, 969. A. R. Hendrickson and R. L. Martin, Austral. J . Chem., 1972, 25, 2 5 7 . 1'.B. Brill, J . Chem. Phys., 1972, 57, 1534. C. M. Begun, J. Brynestad, K. W. Fung, and G. Mamantov, Inorg. Nidear Chem. Letters, 1972, 8, 79. G . M. Begun, Appl. Spectroscopy, 1972, 26, 400. J. H. R . Clarke, P. J. Hartley, and Y . Kuroda, Znorg. Chem., 1972, 11, 29.

356

Spectroscopic Properties of Itiorganic atid Orgariometallic Compounds

[X = C1 or Br; Y = CI, Br, or I], which are deduced to have octahedrally co-ordinated halogen-bridged structures. Tetrahedral co-ordination was determined for Cd12L2[L = py, PhNH2, or i ( d i ~ x a n ) ] . ~ ~ ~ Addition of iodide ions to solutions in 40% aqueous HF containing HgO and K M F s salts ( M = Ti or Sn) affords the species (HgI)2MF6, which have been shown408 to belong to space group D i i . The Raman spectra of these species contain the [MF,l2- fundamentals and bands attributed to planar zig-zag [HgI+], chains (the HgI+ ion is isoelectronic with Aul) :408 (HgI),TiF,

C h a h libration

E} 74

38, 26

(HgI),SnF, 136 64

39, 23

In addition to u(HgX)t modes, i.r. bands for the complexes (PhMe,P),PtY2HgX2(Y = Cl or Br, X = Y or I) have been assigned to v(PtC1Hg)b [294-298 and 268-278 ~ m - l ] .Values ~ ~ ~ for u(HgXHg)b in the presumed dimers HgX,{SC(NH,),} have been given as 192 (X = Cl), 144 (X = Br), or 106 cm-l (X = I), but no account was taken of the possible existence of geometrical isomers.440 Other compounds for which v(MX) data are available are as follows (see also Table 19 4 2 7 * 428): [XHg02CMe], (X = CI, Br, or I);44 [XHg(Co(CO),},]- (X = C1, Br, or I);4s fXHg(PMe,)]+ (X = Cl, Br, or I) and [CIHg(AsMe,)li ;415(R1R2SO),nHgC12(n = 1, 1.5, or 2; R1 and R2 = various);437HgX2[S=C(SR2)(NR1,)] (X = C1, Br, or I ; R2 = Et, R1 = PhCOCH2; R2 = Me, R1 = Me, Et, PhCH2, or PhCOCH2);43eHgX2(dioxan) [X = CI, Br, or I];442MX2L2( M = Zn, Cd, or Hg; X = Cl, Br, or I ; L = quinoline or isoquinoline) ;446 HgCl2[S-p-(2-pyridy1ethyl)-~c y ~ t e i n e ] and ; ~ ~ CdX,(dien) ~ [X = CI, Br, or I].448Data are also available for HgBr2-AgNO, melts449and ZnC1,,2RNH, (R = Prn or 13 Lanthanides Anhydrous cyanides M1(CN)2and M2(CN), [M1 = Eu or Yb; M2 = Ce, Pry Sm, Eu, Ho, or Yb] have been prepared and v(CN) values given.45o* 451 In some cases a weak i.r. band at 450-510cm-1 has been identified, probably v(MC) or V(MN).~~O The absence of coincidences between Raman and i.r. bands of La203 shows that of the possible structures previously proposed, that having the I. S. Ahuja and A. Garg, Inorg. Chim. Acta, 1972, 6, 453. R. H. Fish and M. Friedman, J.C.S. Chem. Comm., 1972, 812. Cow, D. Galizzioli, D. Giusto, and F. Morazzoni, Inorg. Chim. Acta, 1972, 6 , 343. V. D. Prisyazhnyi and S. P. Baranov, Ukrain. khim. Zhur., 1972, 38, 385. I. J. McColm and S. Thompson, J. Inorg. Nuclear Chem., 1972, 34, 3801. I. Cotquhoun, N. N. Greenwood, I. J. McColm, and G. E. Turner, J.C.S. Dalton, 1972, 1337.

un G. 44B 450 4G1

Vibrational Spectra of Transition-element Compounds 357 D& space group is probably correct. Assignments given on this basis were made using quadratic central force-field c a l c ~ l a t i o n s .The ~ ~ far-ir. spectra of CeO, and the non-stoicheiometric Pr and Tb oxides have been studied over the range 10-250 cm-l at liquid-helium t e m p e r a t ~ ~ e s . ~ ~ ~ 1.r. data have been given for several series of oxyacid salts of lanthanides: simple and double sulphates of Eu, Gd, and Tb;453Tm,(S04)3,8HzO;454 twenty-three phosphato-complexes (including hydrates, basic salts, and double phosphates) of Pr, Sm, and Yb;455Ln,(CO,),,nH,O [Ln = La, Ce, Pr, or Nd (n = 8); Ln = Sm, Eu, Gd, Tb, Dy, Ho, Er, or Tm (n = 2-3)] and some basic and CsSm(C,O,),,H,O and its thermal decomposition A study of the bending modes of the C104- groups in complexes Nd(C104),,4[Ph,(PhCH,),_,PO] (n = 0, 1 , 2, or 3), together with conductance data, has led to the formulation [NdL,(C104)2]C104.458 When Nd(O,PCI,), [,(PO2) at 1090 and 1230 cm-l, v(PCI) at 550 and 585 cm-l, v(Nd0) at 390 and 410 CM-l] is treated with ZrCI, in POCI,, a liquid laser solution is formed, but the nature of the interaction is not certain.45gIn a study of the i.r. and Raman spectra of Ln(NO,),(hexamethylphosphoramido), [Ln = Dy, Er, or Yb] and some related compounds, suggestions were made for v(Ln0) value^.^^^^ 461 Assignments for v(Ln0) and v(LnN) have been proposed for some lanthanide complexes of (16; R1or R2 = H or Me).462

(16)

The i.r. spectra of the tropolonates [LnT3]n46a and [LnT4]- salts 4 6 a # 4 6 4 have been studied. Bands attributed to v(Ln0) vary with the 4f orbital 452 463

464

466

456 4G7 15w

458

460 461 482

403 464

D. Bloor and J . R. Dean, J . Phys. (C), 1972,5, 1237. L. V. Lipis, V. S. Ii’yashenko, V. N. Egorov, G. V. Yukhnevich, and V. I. Volk, Zhur. priklad. Spektroskopii, 1971, 14, 1044. B. W. Berringer, J. B. Gruber, and E. A, Karlow, J . Inorg. Nuclear Chem., 1972, 34, 2084. K. I. Petrov, Yu. B. Kirillov, and S. M. Petushkova, Russ. J . Inorg. Chem., 1971, 16, 970. P. E. Caro, J. 0. Sawyer, and L. Eyring, Spectrochim. Acta, 1972, 28A, 1167. Zh. Sh. Kublashvili and E. G. Davitashvii, Russ. J . Inorg. Chern., 1971, 16, 807. 0. A. Serra, M. L. Ribeiro Gibran, and A . M. B. Galindo, Inorg. Nucfear Chem. Letters, 1972, 8, 673. C. Y. Liang, E. J. Schimitschek, and J. A. Trias, J . Inorg. Nuclear Cheni., 1972, 34, 1099. J. A. Sylvanovich, jun. and S. K. Madan, J. Inorg. Nuclear Chern., 1972, 34, 1675. J. A. Sylvanovich, jun. and S. K. Madan, J . Inorg. Nuclear Chem., 1972, 34, 2569. A. N. Speca, N. M . Karayannis, and L. L. Pytlewski, Inorg. Chinr. Acta, 1972, 6, 639. L. G. Hulett and D . A. Thornton, J . Mol. Structure, 1972, 13. 115. L. G. Hulett and D. A. Thornton, Chiniiu (Sbl*ifz.),1972, 26, 72.

3 58


population in the lanthanide ion Ln3+,apparently as a result of small but finite crystal-field stabilization (except 4f0, 4f7, and 4f14 ions). The vibrational spectra of europium dihalides (gas-phase) are mentioned in a review.2e The i.r. spectra of the solid compounds EuX, and LnX, (Ln = La, Nd, Sm, Eu, Gd, Er, or Yb; X = halide) have been measured to 200 cm-1.465 The complex i.r. absorption patterns (20-400 cm-l) observed for TnC1,,6H20 and HoC1,,6H20 agree well with frequency values previously deduced from vibronic 14 Actinides The i.r. spectrum of U(BH,), in the vapour phase is consistent with the presence of triply bridging [UH,BH] units with an overall symmetry of T d ;assignments made are analogous to those for Z T ( B H ~(cf. ) ~ last year’s

1.r. assignments have been given for v(U0,) modes in a wide range of compounds : [Et4Nl2[UO2(NC0),(H2O)] ;Ise UO,(SO,),nH,O and their deuteriates (n = 1 or 4);468 U02(S04),(PhNHNH2) and U02(S04),(benzidine),(THF);46B UO,(NN’-ethylenebis(salicylideneiminato)}(MeOH) (crystal structure determined) ;470 U02(S,CNEt2),(Me,NO) (crystal structure determined) ;471 UO,(HL),X, UO,(L),, and U02(H20)2(L)2,PdC12 [X = Cl or NO3; HL = (17); RL or R2 = H, Me, Et, or Ph];472[UO,(CO(NH2)2)JX(NW [X = C1 or 11 and [uo,{Co(NH,),14(H20)lXn(N03)2-n[X = C1, n = 0 . 5 ; X = Br, n = 1 ; X = I, n = 1.1 or 1.7];473

uCH=N(CH,)2NR1R2 (17)

UO,{NN’-diaminebis(salicylideneimine)}(L) [L = EtOH, py, Me,SO, or HCONMe,];474 and (U02),M04 [v(02U-OM03) = 420 ( M = Si) or 440 cm-l ( M = Ge)].475 466

406

407

40M 409

470

471

47 2

473

4i4 47h

M . D. Taylor, T. T. Cheung, and M. A. Hussein, J . Znorg. Nuclear Chem., 1972, 34, 3073. B. W. Berringer, J. B. Gruber, D. N. Olsen, and J . Stohr, J . Znorg. Nrtclear Cheni., 1972, 34, 373. B. D . James, B. E. Smith, and M . G . H . Wallbridge, J . Mol. Structure, 1972, 14, 327. R . Delobel and J.-M. Leroy, Cornpt. rend., 1972. 274, C , 1286. S. M . F. Rahman, J. Ahmad, and M. M. Haq, Z . anorg. Chem., 1972, 392, 316. G. Bandoli, D. A. Clemente, U. Croatto, M. Vidali, and P. A. Vigato, Inorg. Nuclerrr Chern. Letters, 1972, 8, 961. E. Forsellini, G . Bombieri, R . Graziani, and B. Zarli, Inorg. Nuclear Chem. Letters, 1972, 8, 461. M. Vidali, P. A. Vigato, G . Bandoli, D. A. Clemente, and U. Casellato, Znorg. Chini. Acla, 1972, 6 , 671. G. V. Ellert, I . V. Tsapkina, 0. M . Evstaf’eva, V. F. Zolin, and P. S. Fisher, Russ. J . Znorg. Chetn., 1971, 16, 1640. A. Pasini, M. Gullotti, and E. Cesarotti, J . Inorg. Nuclear Chent., 1972, 34, 3821. J.-P. Legros, R . Lcgros, and 8. Masdupuy, Bull. SOC.chim. France, 1972. 3051.


359 A Raman and i.r. study of aqueous solutions of Th(NO,)( has revealed a complex equilibrium between several species, including NO3-, [Th(NO,)],+, and [Th(NO3),l2+;a polarized Raman band at 230cm-l is assigned as Y ( T ~ - O N O ~ ) .The ~ ~ ~i.r. spectrum (NO3- modes) of K,[Th(N03),] suggests that all the NO,- groups are co-ordinated and have C,, The extraction of U02(N03)2with (BunO),PO and (C8H17),P0 has been studied using i.r. Partial i.r. data are available for (C12CHC0J4U [v(U-0) at 460 cm-l] 479 and about 20 neptunium compounds such as Np02(OH),,xH20,Cs,Np(NO,),, Cs,NpO,(NO,), [n = 1 or 21, (NHo)Np02S03,H20,Np02(C0,),xH,0, Na4Np(C03)4,xH20, K6NP(COd69xH20, NP(Cz04)2,6H20, K ~ N P ( G O ~ ) ~ , ~ H ~ O , and C S N ~ O ~ ( C ~ O ~ ) , ~ H ~ O . ~ ~ ~ Far4.r. bands of U02F2have been assigned on the basis of a previously published normal-co-ordinate analysis ( J . Inorg. Nuclear Chem., 197I , 33, 1615) as follows: 260 ( v i , E,J, 234 (v8, &), and 146 cm-1 (v,, A2,,).4H1 Unassigned i.r. bands (460, 550, and 655 cm-') have been given for UOF, (prepared by reaction of UF6 with H 2 0 in an H F slurry).482The splitting of vasYnl(UO2) into two components (930 and 960 cm-l) in the i.r. spectra of NH,[(UO,),F,],nH,O (n = 3 or 4) has been commented Force-constant calculations have been carried out on the [UO2F,I3ion based on data from the luminescent spectrum4*, or vibrational spectrurn485of the potassium salt. Assignments given are: v(UO), 860; v(UF), 376; 6(UO), 289; 6(UF), 220 (in-plane) and 195 cm-l ( o ~ t - o f - p l a n e ) . ~ ~ ~ Suggestions for v(UF) values have also been presented for [enH2][UFe]and [pnH,][UF,] (420-425 ~ m - l ) [RNH,][UF,] ,~~~ (460-470 cm-'; R = Me, Et, Bun, or PhCH2),486KflUF4+, (290-380 ~ m - ' ) , * *and ~ Na,UF,, (360-404 cm-l) ( n = 3, 2, 5, or &).488 A normal-co-ordinate analysis has been carried out on the [NpC1,I2- ion using a modified seven-parameter UBFF; comparison with other data shows that the M-Cl stretching force constants are in the [UCle]2- .c [NpCIe]'- < [PuCI,I*d76 4~

478

B. G . Oliver and A. R . Davis, J . Inorg. Nuclear Cheni., 1972, 34, 2851. A. K, Molodkin, Z. V. Belyakova, and 0. M. Ivanova, Rum. J. Inorg. Chem., 1971, 16, 835. A. M. Rozen, D. A. Denisov, and Z. I. Nikolotova, Zhur.fiz. Khitn., 1972, 46, 566. T. S. Lobanova, A. V. Ivanova, and K. M. Dunaeva, Russ. J . Inorg. Chetn., 1971, 16,

1087. Yu. Ya. Kharitonov and A. I . Moskvin, Doklady Chem., 1971, 200, 613. K, Ohwada, J . Inorg. Nuclear Chem., 1972, 34, 2357. P H a P. W. Wilson, J.C.S. Chem. Comm., 1972, 1241. 4 8 3 V. P. Seleznev, A. A. Tsvetkov, B. N. Sudarikov, and B. V. Gromov, Russ. J . Itwrg. Chem., 1971, 16, 1174. d H 4 Phan Dinh Kien and A. I . Komyak, Zhur. priklad. Spetroskopii, 1972. 16, 1052. m K. Ohwada, T. Soga, and M . Iwasaki, Spectrochim. Acfa, 1972, 28A, 933. K. C . Satapathy and B. Sahoo, 'Proceedings of the 2nd Chemistry Symposium, Bombay, India', 1970, vol. 1, p. 289. u7 T. Soga. K. Ohwada, and M. Iwasaki, Appl. Spectroscopy, 1972, 26, 482. 4n8 K. Ohwada, T. Soga, and M. Iwasaki, J . Inorg. Nriclenr Chem., 1972, 34, 363. 4Hu N. K . Sanyal and L. Dixit, Current Sci., 1972, 41, 562.

4*0 4x1

360


The far4.r. and Raman spectra of UC1,,2(CNCl) [v(UCl) at 170220 cm-l] and ThCI4,2(CNCl) [v(ThCl) at 270-315 cm-’1 are said to be consistent with structures containing only bridging C1 atoms, although it was necessary to postulate the existence of ‘long’ (ca. 290pm) and ‘short’ (ca. 270 pm) M-Cl The i.r. spectra of Cs,PuCl,,SNH,, PuCl,,SNH,, and Pu13,8NH, have been shown; weak features at ca. 500 cm-l may be PUN).^^^ 490 491

J. MacCordick and G . Kaufmann, Bull. SOC.chim. France, 1972, 23. J. M. Cleveland, G. H. Bryan, and R. J. Sironen, Znorg. Chirn. A d a , 1972, 6, 54.

7

Vibrational Spectra of some Co-ordinated Ligands BY G.DAVIDSON

The ligands have been subdivided according to the position of the donor atom in the Periodic Table, except for some which contain more than one possible donor atom (e.g. -NCS, -SCN); these have been treated separately. Each paper is referred to only once in this chapter, and it will be necessary for a reader interested in a complex containing several different ligands to check through all of the possible sections in which it might be mentioned.

1 Carbon Donors Bands due to v(C=C) are found at 1594 and 1574 cm-1 in the i.r. spectrum of 3-neopentylallyl-lithium. It is suggested that these are due to the presence of trans- and cis-isomers (la) and (lb).

An i.r. band at 1500 cm-', characteristic of the n-ally1 group, is observed in (n-1-methylallyl)(cyclo-octatetraene)titanium, (h3-C,H,Me)Ti(h8-C,H8), together with absorptions due to the Iz8-C,H8 ring., v(C=O) modes have been assigned to i.r. absorptions for Cp,Ti(COR)CI (1620 cm-l, R = Me; 1595 cm-l, R = Ph), and for Cp,Ti(COR)I (1610 cm-l, R = Me; 1605 cm-l, R = Et).3 Unassigned i.r. data have been listed for (C,H,),TiCI,, (C,D,),TiCl,, 41

H

(C,H,Me)TiCl, (Me

0 -0:

)?TiCI,, and (C5H5),TiR (R = Ph;

0-,rn-,

H

or p-MeC,H,; 2,6-Me2C6HS;2,4,6- Me,C,H,; C6F5;or CH,Ph). W. H. Glaze, J. E. Hanicak, M. L. Moore, and J. Chaudhuri, J . Organomerallic Chern., 1972,44, 39. H. K. Hofstee, H. 0. van Oven, and H. J. de Liefde Meijer, J . Organometallic Chem., 1972, 42, 205. C. Floriani and G. Fachinetti, J.C.S. Chem. Comnr., 1972, 790. H . A. Martin, M. van Gorkom, and R. 0. de Jongh, J . Organometallic Chem., 1972, 36, 93. J . H . Teuben and H . J . de Liefde Meijer, J. Orgotrorrietallic Cheur., 1972, 46, 313.

36 1

362

Spectroscopic Properties of' Inorgattic m d Orgnnometnllic Corripoirncls

(h6-C5H5)TiX2(X = CI, Br, or I) all give the characteristic h5-C5H, bands. The THF adducts give a similar spectrum, with the addition of bands due to 0-co-ordinated THF, e . g . v,,(COC) has shifted from 1070 to 1035 ( 5 5) cm-l.g 1.r. spectra have been drawn (with no numbers or assignments) for M c' I ,ONNO

(h5-C,H,),ZrMe,, ( h"-C,,Hj)Zr\

Mc

M C

I

, a n d (h"-C,H,),Zr,

,,ON N O MC

The Raman and i.r. spectra of (C5H,),Zr and (C,H,),Hf are rather complex, and cannot be assigned in detail, but it is clear that both hl- and h6-cyclopentadienyl rings are present in each one.8 Partially assigned i.r. and Raman spectra for the trimethylsilyImethy1 complexes Cr(CH,Si Me,),, Mo2(CH2SiMe3),, W,(CH,SiMe,),, V(CH2SiMeJ4, and VO(CH,SiMe,), support certain structural conclusions made regarding these compounds that were arrived at by use of other spectroscopic techniques.@ 1.r. absorptions have been listed, but not assigned, for bis(cyc1oheptatriene)vanadium, V(C,H8)2, while bands characteristic of the tropyliumring ligand were found at 3030, 2940, 1438, 1302, 860, and 810 cm in V(C,H,)2+.lo In the acetylenic carbene complexes M(CO),[C(OEt)C=CPh], where M = Cr or W, v(C=C) is found at 2153, 2154 cm-l, respectively.ll The ethylenic complex W(CO),(C(NMe,)CH=C(Ph)NMe,) has v(C=C) at 1548 cm-'. All of the v(C0) modes for these systems may be assigned in terms of C,, symmetry. The following v(CN) values have been quoted: Cr(CHNMe,)(CO), 1545; Fe(CHNMe,)(CO), 1555 ; RhC13(CHNMe,)(PEt3), 1587; RhCI,(CO)[C(NHPh),](PPh,) 1531 [with v(C=O) at 2090, 2100 cm '1; PtCI,(CHNMe,)(PEt,) 1630 cm-l.12 The carbonyl stretching modes of (butadiene)tetracarbonylchromium (2) are found at 2040, 1977, 1946, and 1932 cm-l.13 This is the first example of a 1,3-diene-tetracarbonylchromiumcomplex.

lo l2

R . S. P. Coutts, R. L. Martin, and P. C. Wailes, Austral. J . Chem., 1971, 24, 2533. P. C . Wailes, H . Weigold, and A. P. Bell, J . Organometallic Chem., 1972, 34, 155. R. V. Lokshin and E. M . Brainina, J . Strirrt. Chem., 1971, 12, 923. W. Mowat, A. Shortland, G . Yagupsky, N. J . Hill, M . Yagupsky, and G . Wilkinson, J.C.S. Dalton, 1972, 533. J . Miiller and B. Mertschenk, J . Orgnnotmtallic Chem., 1972, 34, C41. E. 0. Fischer and F. R. Kreissl, J . Organometallic Chem., 1972, 35, C47. B. Cetinkaya, M. F. Lappert, and K. Turncr, J.C.S. Chem. Comm., 1972, 851. E. Koerner von Gustorf, 0.Jaenickc, a n d 0 . E. Polansky, Angeit-. Chetti. /titrrtrrrr. Edti., 1972, 1 1 , 532.

Vibrationai Spectra of some Co-ordinated Ligands

363 The i.r. spectrum has been listed and some assignments have been proposed, especially the cyclopentadienyl characteristic vibrations, for [Li(C,H,)CrCl,,2THF],(dio~an).~~

Three carbonyl stretching bands are observed for (tellurophen)Cr(CO),, at 1967 (Al); 1895, 1872 (E) cm-l. Splitting of the E mode shows that the local symmetry approximation is inadequate. The dinuclear complex (3) was also prepared [v(CO)at 2064, 2033, and 1995 cm-'].15

(3)

Kjellstrup et al. have published16a a complete set of symmetry coordinates for (h6-CeHe)Cr(CO),. A normal co-ordinate analysis for this complex suggestslsb that many of the observed frequency shifts for C8H6 modes from the free-ligand values may be explained by kinematic coupling effects. The Raman spectrum of (benzene)chromium dicarbonyl has been reported,16Cas have the Raman and low-temperature i.r, spectra of ([2He]benzene)Cr(CO)3.17 Some changes in earlier assignments were suggested. Unassigned i.r. bands have been reported for (phenylacety1ene)- and (styrene)-tricarbonyIchromium.l* v(CH-phenyl), v(CH-aliphatic), v(C=O), and some other characteristic absorptions have been assigned in ArCr(CO),, where Ar = 2-phenylethanol [also v(OH)], 2-phenylethyl toluene-p-sulphonate [also v(OSO,)], or 2-phenylethyl bromide. 1.r. spectra in the v(C0) region have been used to study the protonation of arenechromiurn tricarbonyl and arenechromium dicarbonyl triphenylphosphine I t was shown that the former are not protonated in CF3C02H[no shift to higher frequency in v(CO)], but only in BF,,H,O. The PPh3 complexes, however, showed evidence for protonation in CF3CO2H, and in CF3CO,H-CH,Cl2 mixtures. From the proportions of non-protonated and protonated species in these mixtures, it was shown that protonation ability in ArCr(CO),(PPh,) follows the sequence: Ar = Me3CeH3> MeOC,H, > MeC6H, > C,H, > MeO,CC,H,.

l7 lH

"'I

B. Muller and J. Krausse, J. Organornetallic Chem., 1972, 44, 141. K. t)fele and E. Dotzauer, J. Organornefdlic Chem., 1972, 42, C87. (a) S . Kjellstrup, S. J. Cyvin, J. Brunvoll, and L. Schafer, J. Orgnnomefallic Chctn., 1972,36, 137; ( b ) J. Brunvoll, S. J. Cyvin, and L. Schafer, ibid., p. 143; ( c ) L. Schgfer, G . M. Begun, and S. J. Cyvin, Spectrochint. A d a , 1972, 28A, 803. I. J. Hyams and E. R. Lippincott, Spectrochim. Acta, 1972, 28A, 1741. G. R. Knox, D. G. Leppard, P. L. Pauson, and W. E. Watts, J. Organometallic Chem., 1972, 34, 347. A. Ceccon and G. S. Biserni, J. Orgo~iomefnllicChem., 1972, 39, 313. B. V. Lokshin, V. 1. Zdanovich, N. K. Baranetskaya, V. N. Setkina,and D. N. Kursanov, J. Organomefnllic Chetn., 1972, 37, 33 1.

364


Two novel cyclopentadienyl-moly bdenum complexes have been prepared by Treichel and Dean.2L Compound (4) gives v(C0) at 1934, 1841 cm-l, with v(CN) at 1573 and v(CS) at 1167 cm-'; (5) possesses analogous bands at 2006, 1935; 1616, 1155 cm-l.

---Mo( I

A number of new species containing the di-r-cyclopentadienyl-molybdenum or -tungsten grouping have been prepared.22 Thus, (n-Cp),Mo(CO) gives v(C0) at 1905 cm-I, while v(C=C) modes are found at 1465, 1430, 1450cm--' respectively, for (r-Cp),M(C2H,R), where M = Mo, R = H ; M = W, R = H; and M = W, R = Me. (r-Cp)Mo(CO),(COPh) possesses two v(C=O) bands in its i.r. spectrum (2022, 1934 cm-I), while v(C=O) is found at 1640 cm-l. The tungsten analogue gives absorptions due to these modes at 2126, 1935; 1606 C M - ' . ~ ~ Solid-state i.r. spectra indicate the presence of two forms of aza-allylallene complexes of M o and W (e.g. (~T-C,H,)MO(C~)~[(P-~O~)~CN (p-tol),]); the precise nature of and relationship between these two forms is being elucidated by crystallographic methods.24 Unassigned i.r. data have been listed for LiW(CBF,)6,2Et20.25 An assignment of the vibrational spectrum of the hl-allyl complex (a-C,H,)Mn(CO), has been made.26 The Mn(CO), fragment possesses effective C,, symmetry, and frequencies very close to those observed for (CH,)MWO),. The local-symmetry concept could not, however, be applied to the Mn(C0)4 vibrations in the closely related /z3-allylcomplex (r-C3H6)Mn(CO), (6).27 The v(CO), v(MnC), and G(MnC0) modes all gave more bands than predicted for C,, symmetry, and the effective, overall symmetry of C , must

22

23 24 26

26

2i

P. M . Treichel and W. K . Dean, J.C.S. Chetn. Comtn., 1972, 804. F. W. S. Benfield, B. R. Francis, and M . L. H . Green, J . Organometallic Chem., 1972, 44, C13. A. N. Nesmeyanov, L. G . Makarova, N . A. Ustynyuk, and L. U. Bogatyreva, J . Organometallic Chem., 1972, 46, 105. H. R. Keable and M. Kilner, J.C.S. Dalton, 1972, 153. E. Kinsella, V. B. Smith, and A. G. Massey, J . Organometallic Chem., 1972, 34, 181. H . L. Clarke and N. J. Fitzpatrick, J . Orgatiotti~tnllicChem., 1971, 40, 379. G. Davidson and D . C. Andrews, J . C . S . Drrltotr, 1972, 126.

Vibrational Spectra of some Co-ordinated Ligands

365 be used in their assignment. In addition, a complete and almost unambiguous assignment was made of the internal vibrations of the n-C3H6 unit [see Table 1 , which includes also data from (n-C,H,)Co(CO),; see below].

Table 1 Assignment of vibrations of the n-ally1 group in (n-C3Hs)Mn(CO), and (n-C,H,)Co(CO), (all figures are wauenumber/cm-’) Vibration v(CH,) v(CH) v(CH2) v(CH,) v(CH,) WH,),, ~(CH,), V(CCC),, rr(CH) &CH) v(CCC), pt(CH,), pw(CH2)e pw(CH2)as pt(CH2)akl pr(CHz)as pr(CH2)tl G(CCC)

A” A’

A’ A“ A’ A” A’ A” A’

A” A’ A’ A’ A”

A‘’

A” A‘ A‘

(r-C,H,)Mn(CO), 3078 3025 2973 2964 2948 1503 1462 1397 1214 1155 101 7 1007 9 20 883 980 788 774 52 1

(n-C,Hs)CdCO)3 3087 3023 297 1 2940 1487 1473 1389 1228 1189 1020 1020 951 934 927 805 775 525

v(C=C) has been listed for a number of transition-metal perfluoro-lmethylpropenyl complexes, i.e. containing the M-C(CF,)=CF(CF,) grouping. Examples were C4F7Mn(CO),, C4F7Re(CO),, ClF7Fe(CO),Cp, C4F7Cr(N0),Cp, etc., and v(C=C) in all cases was found to be in the range 1614-1636 cm-1.28 1.r. spectra in the v(C0) region have been used to study protonation [giving higher-frequency v(C0) bands] of phosphine derivatives of CpMn(CO), in solution in CF3C02Hand CF,C02H-CH2C12.2s Protonation of the metal atom is believed to occur, and the ease of protonation increases with increasing electron-releasing properties of both w-ring substituents and the phosphine ligands. 1.r. investigations of ~ ( C = O ) ~ eand ~ ~ v(C=O)carbnyl ~e in a number of complexes of the types (7) and (8) have been made.3o Empirical rules for distinguishing between possible isomers were drawn up. In (n-CsHs)Mn(CO)(CS),, v(C=O) is found at 1991 cm-’, with v(C=S) at 1305, 1235 cm-l, and in ( T - C ~ H ~ ) M ~ ( Cv(C=S) S ) ~ , is at 1338, 1240 cm-1 31 28 *#

30 31

R. B. King and W. R. Zipperer, Inorg. Chem., 1972, 11, 2119. B. V. Lokshin, A. G. Ginzberg ,V. N. Setkina, D. C. Kursanov, and I. B. Nemirovskaya, J . Organometallic Chern., 1972, 37, 347. M. Le Plouzennec and R. Dabard, Bull. SOC.chim. France, 1972, 3600. A. E. Fenster and I. S. Butler, Cunad. J . Chem., 1972, 50, 598.

366

Spectroscopic Properties of Inorganic and Orgarrornetallic Compounds Me

Some approximate assignments have been listed for (9; M = Si, Ge, or Sn), while more detailed assignments were given for Me,M(CHCCF,),Mn(CO), (M = G e or Si): e.g. v(Mn--0) at 475, 450 om-' (Ge), 450 445 cm-l (Si).32 0

The i.r. band of medium intensity at ca. 1700cm-', due to the amido v(C=O) in compounds of the type (10) (e.g. R1 = R2 = Ph), is approximately 100 cm-l higher than in cis-[M(CO),(NH,R)(CONHR)] (M = M n or Re) owing to conjugation and ring-size effects.33a 1.r. and Raman spectra of solids and solution samples of (h6-C6H5)Re(CO), have been assigned 33b in terms of 'local' symmetry, and compared with data for the related Mn complex. Wavenumbers and force constants for the M-CO bands demonstrate the enhanced strength of Re-CO compared with Mn-CO bands. The complex FeEt(acac)(PPh,) gives characteristic i.r. bands of acac and PPh,, together with v(CH) of the ethyl ligand at 2830 cm-l, and C H deformations at 1450, 1350cm-l. FeMe,(PPh,), gives, in addition to PPh, bands, v(CH) of the methyl group at 2850, 2770cm-', and C H deformations at 1510, 1270, 1180 crn-l.,, 1.r. spectra have been listed and approximately assigned for C,F,Fe(CO),(NH3)21 and [C,F,Fe(CO),(NH,)]X, X = I, and Cr(NCS)4(NH3)2.35 v(Fe-C) is found in the range 500-425 cm-l. Ph,MC=CCF, (where M = P or As) react with Fe,(CO),, to give the complex (1 I), showing no v(C=C) band, and v(C0) at 1969w, 1993w, 2006s, 2036m, 2062s, and 2081m (all ~ r n - ' ) . ~ ~ 32 sy

34 9G 38

H. C. Clark and T. L. Hauw, J. Organornetallic Chem., 1972, 42, 429. ( a ) T. Inglis, M. Kilner, and T. Reynoldson, J.C.S. Chem. Cornm., 1972, 774; (b) B. V. Lokshin, Z. S. Klemenkova, and Ya. V. Makarov, Spectrochim. Acta, 1972,28A, 2209. Y. Kubo, A. Yamamoto, and S. Ikeda, J . Organometallic Chem., 1972, 46, C50. H. Krohberger, J. Ellermann, and H. Behrens, 2. Nafurfursch., 1972, 27b, 890. T. O'Connor, A. J . Carty, M. Mathew, and G. J. Palenik, J. Organometallic Chem., 1972, 38, C15.

Vibrntionnl Spectra of sowe Co-ordinnted Lignnd.7

(1 1)

367

(12)

The i.r. spectra of a series of iron carbonyl carbamoyl complexes are consistent with dimerization via hydrogen-bridges in the solid state, i.e. (12), where R = C6H5,C5H4CHPh,,or C,H8CPh3 and L = CO, PPh3, or PEt3.37 The ease of formation of carboxamido-complexes from corresponding Re, Pd, Pt, Mo, and W): carbonyls (of Fe, Ru, MI], L,M(CO).

+ 'RNH,

L,,M(CO),-,(CONHR)-

+

RNH;

has been related to the electron density at the carbonyl carbon, and hence to the C=O stretching force constant. Thus, if f > 17 mdyn A-l, carboxamido formation occurs readily, and i f f < 16 mdyn A-l it does not occur at all.38 Bands in the i.r. spectrum of bis(methy1amino)carbene-tetracarbonyliron, (OC)4FeC(NHMe),, have been assigned s9 by comparison with O=C(NH Me), . R

I

In L(OC),Fe(C=O),Fe(CO),, where R = Me or Ph and L = CO, HzNNHPh, py, NC6Hll, or NH3, v(C=O)keb is found at 1534-1540 (R = Me) and 1492-1506 (R = Ph) c ~ - ' . ~ O A study has been made of the i.r. and Raman spectra (the latter for the solid phase only) of (C2H4)Fe(C0)4.41The following assignments of ethylene modes were proposed: (A,) v(CH,) 2920; 6(CH2) 1508, v(C=C) 1193 (these two strongly coupled): pw(CHz)939; v(Fe-C2H4) 356; (A,) v(CH2) ?; pr(CH2) 1082; pt(CH2) 781; T(C2H4) ?; ( B , ) v(CH,) 2980; 8(CHa) 1447; p4CH-J 1023; CaH4 tilt 305; (B2) v(CH,) 3078; pr(CH2) 710; C,H4 tilt 400 (all in cm-l). In (13), the v(C=C) band in the free ligand (1638 cm-l) disappears on complex formation.42 The complex shows two v(C=O) absorptions at 1744, 1715 crn-l, and four v(C=O) bands (2109, 2049, 2047, 2004 cm-l, together with a number of weaker features in the same region, whose origins are unclear). 97

J. Ellermann, H. Behrens, and H. Krohberger, J . Organornetallic Chem., 1972, 46, 119.

JH

40

Q1 pd

R. J. Angelici and L. J. Blacik, Inorg. Chern., 1972, 11, 1754. K. ofele and C. G . Kreiter, Chem. Ber., 1972, 105, 529. V. Kiener and E. 0. Fischer, J . Organometallic Chem., 1972, 42, 447. D. C. Andrews and G. Davidson, J . Organometallic Chem., 1972, 35, 161. E. Koerner von Gustorf, 0. Jaenicke, and 0. E. Polansky, 2. Naturforsch., 1972, 27b, 575.

368

Spectroscopic Properties of Inorgaiiic and Organometallic Compom a s 0

In Fe(bipy),(tcne),, v(C=N) drops from 2220 cm-' (free tcne) to 21 10 cmon c o - ~ r d i n a t i o n . ~ ~ The complex (14) gives an i.r. band at 1598 cm-l, which is assigned to v(C=C) [v(CO)2021, 1952; v(N0) 1750 cm-' also observed]. Compound

c1 I

(15), however, which is known to be an unsymmetrical wallyl complex from n.m.r. data, gives no v(C=C) absorption at ca. 1600cm-', in agree-

ment with this formulation [v(CO) 1950; Y(NO) 1708 ~ m - l ] . ~ ~ The i.r. and Raman spectra of (cyc1obutadiene)iron tricarbonyl, (C,H,)Fe(CO),, have been reported and almost completely assigned. The vibrations of both the C,H,-Fe and the Fe(CO), moieties appeared to obey the selection rules appropriate for 'local symmetry' of C,,, C,,, respectively. Most of the internal modes of cyclobutadiene were at similar frequencies to those of other n-bonded CnHnsystems, except that the ringbreathing mode was somewhat higher (1234 cm-'); v(Fe-CC,H,) was at 398 cm-l, and the Fe-C,H, tilt at 471 ~ m - l . ~ ~ A vibrational assignment has been proposed for the trimethylenemethane molecule, in [C(CH,),]Fe(CO),, for the first time.** CC, stretches were found at 1348 (E) and 918 ( A , ) cm-l, with skeletal deformations at 802 (Al, out-of-plane) and 471 (E, in-plane) cm-l. The Fe(CO), vibrations were closely similar to those in analogous complexes. (trans,trans-2,4-Hexadiene)irontricarbonyl shows v(C=O) bands at 1687 and 1699cm-l in CS, solution, due to the presence of the isomers (16a) and (16b).47 v(C=O) has been plotted against u, of the para-substituent for a series of (para-substituted 1-phenyl-l,3-butadiene)iron tricarbonyl complexes (17; R = NH,, OMe, H, NHCOMe, Br, COMe, or CN). A straight-line 43

47

T. Yamamoto, A. Yamamoto, and S . Ikeda, Bull. Chem. SOC. Japan, 1972, 45, 1104. G . Cardacci, S. M. Murgia, and A. Foffani, J . Organometallic Chem.. 1972, 37, C1 I . D. C. Andrews and G. Davidson, J. Organometallic Chem., 1972, 36, 349. D. C. Andrews and G . Davidson, J . Organometallic Chem., 1972, 43, 393. M. Brookhart and D. L. Harris, J . Organonietaiiic Chem., 1972, 42, 441.

369

plot was observed, clearly showing the transmission of electronic effects, but the exact mechanism of this transmission could not be a s ~ e r t a i n e d . ~ ~ The reaction between the azabullvalene (18) and Fe,(CO), affords the complexes (19), v ( C 0 ) at 2016, 2000, 1942cm-', v[C(OMe)=N] at OMe

I

1625 cm-', and (20), v ( C 0 ) at 2056, 2000, 1974 cm-l, v(C=O) at 1720 cm-l 4 8

Me0

\Fe/ A vibrational assignment has been proposed for (C,H,),Fe(CO). The internal modes of the two C4H, ligands show that there is very little interaction between them, and that electronically they are very similar to C4H6 in (C,H,)%(CO),. v(C0) occurs at 1982 cm-I (in C,H,, solution), with the two 8(Fe-C-0) modes at 532 and 576 cm-1.60 1.r. bands have been listed for di-isoprene-, di-l,3-pentadiene-, isoprenecyclo-octatetraene-, and 1,3-pentadienecyclo-octatetraene-carbonyliron.61 1.r. intensity studies on (h6-C6H,)Fe(CO),X, where X = C1, I, CN, SnCl,, C(O)Me, or (C6H6CH2C6H6)Fe(C0)J?Ph3, led Darensbourg to the conclusion that the cyclopentadienyl ligand is acting primarily as a donor.62 49

Go

b2

J. M. Landesberg and L. Katz, J . Organometallic Chem., 1972, 35, 327. Y. Becker, A. Eisenstadt, and Y. Shvo, J.C.S. Chem. Comm., 1972, 1156. G . Davidson and D. A. Duce. J . Organometallic Chem., 1972, 44, 365. A. Carbonaro and F. Cambisi, J . Organometallic Chem., 1972, 44, 171. D. J. Darensbourg, Inorg. Chem., 1972, 1 1 , 1606.

13

370


The i.r. spectra of [(n-Cp)M(CO),], ( M = Fe or Ru), have been investigated as functions of solvent and t e r n p e r a t ~ r e . The ~ ~ data for the iron compound are consistent with those obtained previously, while for the Ru complex they are assigned on the basis of four isomers being present, cisbridged, trans-bridged, trans-nonbridged, and a polar non-bridged structure, probably (21). A number of a-carbaborane complexes of iron have been prepared,64 e.g. CpFe(CO)z-o-(BloC2Hll) and its 1,2-dimethyl derivative, together

with some derivatives containing the n-CpFe unit, and the carbaborane a-bonded to the cyclopentadienyl ring. Numbers of characteristic i.r. absorptions were listed in each case. Two optical isomers of (22) have been isolated. They show v(C=O) at 1920 cm-l, and v(C=O) (of the acetyl group) at 1595 ~ m - l . ~ ~ Using previously published data, Schiifer et ai. have published a normal co-ordinate analysis on Fe(C6H6)2and Fe(C6D6)2.68 Stereoisomers of the ferrocenic alcohols (h6-C5H5)Fe(h6-l ,2-MeC,H3CH(0H)Me) have been i~olated.~'They give rise to distinctive spectra in the v(0H) region. The ferrocenic alcohols (23; R1, R2 = Me or Ph) all give a band in the v(0H) region that is characteristic of an Fe. - H - 0 interaction (ca. 3570 cm-l), i.e. in all cases the OH is cis with respect to the Fe atom.66

Q

53

54

b6

66 57 K8

J. G. Bullitt, F. A. Cotton, and T. J. Marks, Inorg. Chem., 1972, 11, 672. L. I. Zakharkin, L. V. Orlova, B. V. Lokshin, and L. A. Fedorov, J . Organometallic Chem., 1972, 40,15. H. Brunner and E. Schmidt, J . Organomerallic Chem., 1972, 36, C18. L. Schlifer, J. Brunvoll, and S. J. Cyvin, J . Mol. Structure, 1972, 11, 459. C. Moise, D. Sautrey, and J. Tirouflet, Bull. SOC.chim. France, 1971, 4562. C. Moise, J.-P. Monin, and J. Tirouflet, Biill. SOC.chim. France, 1972, 2048.

Vibrational Spectra of some C’o-ordinuted Ligunds

37 I

v(C=O) has been reported for a number of a-carbonyl ferrocenes, e.g.

formylferrocene (1 663), acetylferrocene (1 663), ferrocenoyl chloride ( 1 766), ferrocenoic acid ( 1 692), and methyl ferrocenoate ( 1 712 cm-1).5* Their products from photodecomposition in H,O-Me2S0 or H20-py were all believed to contain carboxylate groups. Some characteristic i.r. bands have been listed for 1,3-terferrocenyl (i.e. 1,3-diferrocenyIferrocene)(24).60 ( T - C ~ H ~ ) R U C ~ ( T - Cgives ~ H ~i.r. ) bands at 2910, 2870, 1201, 992, 969, 944, 910, 784, and 582 cm-l, characteristic of the r-ally1 group.G1a A full assignment for ruthenocene has been arrived at through i.r. and Raman studies (including single-crystal data) at ambient and liquidnitrogen temperatures.61b Inactive modes were located as weak i.r. bands at - 196 “C. It was shown that, contrary to previous assignments, the i.r.active ring ‘tilt’ mode of (h5-C,H,),Ru is of lower energy than the Ru-Ring bond stretch. Electrochemical oxidation of Cp2Ru at a mercury anode forms [Cp,Ru-Hg-RuCp,]* t(C104)i-.62 1.r. and Raman spectra of this and the PFB- amd BF,- salts have been reported, with a Raman band at 1 10 cm-l assigned to v(Ru-Hg). Other assignments included : 338 cni-l, symmetric Ring-Ru-Ring stretch; 190 cm-l, Ring-Ru-Ring bend. The Cp-Ru-Cp deformation was assigned similarly (194 cm-l) in the ~ assignments should be adducts Cp,Ru,HgX, (X = C1 or B T ) . ~These contrasted with that of Bodenheimer (Chem. Plrys. Letters, 1970,6,519) for ruthenocene itself, to a band at 1 1 1.5 cm-’. Characteristic i.r. frequencies have been listed and partly assigned for the carbamoyl complexes Co(CO),(PPh,)(CONMe,) and Co(CO),(PPh,)(NH,)(CONH2).6Q The vibrational spectrum of (h3-C3H5)Co(CO), has been The internal .rr-ally1 modes were very similar to those of (h3-C3H5)Mn(CO), - see above, Table 1. Local symmetry of C,, sufficed in the assignment of the Co(CO), modes, in contrast to the situation for the Mn complex, where overall symmetry had to be used. Thus, no splitting of the v(C0) mode (E) at 2025 cm-l (vapour phase) could be detected. Clarke and Fitzpatrick have obtained i.r. spectra for a series of .rr-ally1 cobalt complexes (XC3H4)C~(C0)3, where X = H, 1-Me, 2-Me, 1-Cl, or 2-C1.06 Some splitting of the E mode v ( C 0 ) band was detectable for X = 2-Me or 1-Cl. Assignments were proposed, and trends in CO force F,”

uL By

CA

u4 uL

L. H. Ali, A. Cox, and T. J . Kemp, J.C.S. Chem. Comm., 1972, 265. E. W. Neuse and R. K. Crossland, J . Orgattometallic Chetn., 1972, 43, 385. (a) R. A. Zelonka and M. C. Baird, J . Organometallic Chem., 1972,44, 383; (b) D. M . Adarns and W. S. Fernando, J.C.S. Dalton, 1972, 2507. D. N. Hendrickson, Y . S. Sohn, W. H. Morrison, jun., and H. B. Gray, Inorg. Chem., 1972, 11, 808. W. H. Morrison jun. and D. N. Hendrickson, Zttorg. Chem., 1972, 11, 2912. H. Krohberger, H. Behrens, and J. Ellerrnann, J . Organometallic Chem., 1972,46, 139. D. C. Andrews and G . Davidson, J.C.S. Dalton, 1972, 1381. H. L. Clarke and N. J . Fitzpatrick, J . Organometallic Chem., 1972, 43, 405.

372

Spectrosc*opic Properties of Inorganic and Organornetallic Cotnpoiinds

constants compared with the results of Self-Consistent Charge and Configuration MO (SCCCMO) calculations. 2-Acetyl-.rr-allylcobalt tricarbonyl can be protonated in concentrated H2S04 solution, giving the trimethylenemethane-cobalt derivative (25), c

(25)

which gives CO stretching bands at 2125, 2084 cm-l (the shift to higher frequency compared to the initial complex is consistent with cation forrnati~n).~? 1.r. maxima have been listed for (h4-cyclobutadiene)(h6-cyclopentadienyl)cobalt.88Those associated with the four-membered-ring were similar to those in (C,H,)Fe(CO),. Unassigned i.r. spectra have been listed for (26a) and (26b), where L = SiMe, or Si2Me,.6e

&I PI1

I'll

Q

L

v ( C = O ) ~is~ ~ assigned ~ to a weak i.r. band at 1655-1670cm-l in [NEt,][Rh,(CO),(COR)], R = Et or Pr.70 Wavenumbers of v(C=O) were also listed (2080-1 724 cm-l). v(C=O), v(C=O), and u(C=C) have been assigned7' in Rh(C0)(PPh3)2L, where L = C(CO,Me)= CH(CO,Me), C(CO,H)=CH(CO,H), or CPh=CHPh. No co-ordination of C=C or C=O to the metal was indicated, hence these are four-co-ordinate complexes (27).

O7 88

70

S. Otsuka and A. Nakamura, Znorg. Chem., 1972, 11, 644. M. Rosenblum, B. North, D. Wells, and W. P. Giering, J . Amer. Chem. Soc., 1972, 94, 1239. H. Sakurai and J. Hayashi, J. Organometallic Chem., 1972, 39, 365. P. Chini, S. Martinengo, and G. Garlaschelli, J.C.S. Chem. Cornm., 1972, 709. B . L. Booth and A. D. Lloyd, J . Organomerallic Chem., 1972, 35, 195.


373 v(C=C) was found in the region 2128-2092 cm-l for all of the following: (Ph,P),Rh(C=CPh),L (L = CO or SnMe,), (Ph,P),Ir(C=CPh),CO, (Ph,P),Ir(C=CPh),(SnMe,)CO, (Ph,P),Pt(C=CPh)SnR, (R = Me or Et), and (Ph,MeP),Pt(C=CPh)SnMe,.7za The new carbene complexes L(Ph,P)RhCI(C[N(R)CH2],} show v(C-N) at 1498cm-l (L = PPh,, R = Ph), 1495cm-l (L = COYR = Ph), and 1513 cm-l (L = PPh,, R = p - t ~ l y l ) . ~ ~ ~ In [Rh(C,H,),(MeCN),]+ (28), the i.r. spectrum of the bound C2H4 is very similar to that in Zeise's salt, except that no strong bond is seen at ca. 400 ~ m - l . ' ~

(28)

A number of new complexes have been prepared from the cation [Rh(vp),]+ [vp = (o-~inylphenyl)diphenylphosphine].~~ Thus : [Rh(CO)(VP)~]+,which is five-co-ordinate, gives v ( C 0 ) at 2035 cm-'; [Rh(O,)-

,o

(vp),]+, v(Rh' I ) at 849 cm-l; [Rh(CO,)(vp),]+, v(C0,) at 1358, 1480 cm-l

'0

(typical of co-ordinated CO,); and [Rh(SO2)(vp),]fYv(SOz) at 1060 cm-l (symmetric), 1140, 1161 (antisymmetric), i.e. the SO, is S-bonded. For tris-o-vinylphenyl-phosphine(tvpp) and -arsine (tvpa) and phenyl(bis-o-viny1phenyl)phosphine (dvpp) complexes of Rh', v(C= C) frequencies (ca. 1250 cm-l) have been listed.75a The structure of the ligand in the complexes [RhX(tvpa)(AsPh,)], [RhX(tvpa)(py)], and [RhX(tvpa)CO] is different from that in RhX(tvpa): v(C=C), at 1270cm-l (vs) in RhCl(tvpa), is of only medium intensity (at 1251 crn--l) in RhCl(tvpa)(AsPh,). The change in v(C=C) frequency is attributable to the use by the rhodium atom of different orbitals in forming the two different bonding arrangements. Powell and Leedham have investigated the vibrational spectra of a series of isoelectronic d8 ions complexed to l,5-cyclo-octadiene.766 A lowering in frequency of two ligand bands [to which v(C=C) character is attributed] is found, and the order is that of the expected metal-olefin 72

74

75

(a) B. Cetinkaya, M. F. Lappert, J. McMeeking, and D. Palmer, J. Organometallic Chem., 1972,34, C37; (b) D. J. Cardin, M. J . Doyle, and M. F. Lappert, J.C.S. Chem. Comm., 1972,927. F. Maspero, E. Perrotti, and F. Simonetti, J . Organornetaffic Chem., 1972, 38, C43. P. R. Brookes, J. Organometallic Chem., 1972, 43, 415. (0)D. I. Hall and (the late) R. S. Nyholm, J.C.S. Dalfon, 1972, 804; (bj D. B. Powcll and T. J. Leedham, Spectrochitu. Acta, 1972, 28A, 337.

374

Spectroscopic Properties of Inorganic and Organometallic Compoirnds

bond strength, viz: [(cod)RhCI], (1476, 1241 cm-l) > (cod)PtCI, (1500, 1267 cm-l) > (cod)PdCl, (1522, 1271 cm-l). The values in free cod are 1644, 1280 cm- l . v(C=O) is in the region 1651--1701 cm-l for several cyclo-dienone complexes of Rh, uiz. [(dp)RhCI],, [(dp)Rh(n-C,H,)], [(cq)RhCI],, [(cq)Rh(acac)], and [(cq)Rh(7r-C,H5)] (where dp = tricyclo[5,2,1 ,O2p8]deca4,8-dien-3-one ; cq = tricyclo[6,2,1 ,02~7]~ndeca-4,9-diene-3,6-dione).76 In [(dp)Rh(.rr-C,H,)], there is no band attributable to v(C=C) of an uncomplexed C=C bond, and the structure is believed to be (29). 0

v(C=C) has been assigned as follows in a series of alkynyliridium(r) Ir(C=CPh)(CO)(PPh,), 2091 cm-l; Ir(C=CPh)(O,)(CO) (PPh,)* 2133 cm-l; Ir(C=CPh)(PPh,), 1988 cm-l. The structure (30) is consistent with the absence of bands due to noncomplexed C=C, and with the presence of v(Ir--1) at cn. 250 cm-l in the i.r. spectrum of this complex.78

ON

The reaction of hexafluorobut-2-yne with Ir(NO)(PPh,), affords a complex whose identity has been established by X-ray crystallography as (31), i.e. di-p-hexafluorobut-2-enyl bis[cis-triphenylphosphinenitrosyliridium(~)]. This shows v(N0) at 1780 ~ m - - l . ~ @ The following assignments have been made for the tcne complexes (32) : v(C=N) 2233, 2220; v,(N=C=C) 2168; v ( C ~ 0 )2080; v,(N=C=C) ''I

B. F. G . Johnson, H . V. P. Jones, and J . Lewis, J.C.S. Dalfon, 1972, 463. R. Nast and L. Dahlenburg, Chem. Ber., 1972, 105, 1456. G. Pannetier, P. Fougeroux, and R. Bonnaire, J . Organometallic Chem., 1972, 38, 421. J. Clemens, M . Green, M.-C. Kuo,C . J. Fritchie, jun., J. T. Mague, and F. G . A. Stone, J.C.S. Chem. Comm., 1972, 5 3 .


375 1355 cm-l, and (33): v(CN) of tcne 2230; v(C==O) 2080; v(CN) of Ir-CN not observed.80 v(C=O) and v(C=N) have been listed for IrH(CO)(X)L,, where X = fumaronitrile, cinnamonitrile, benzylidenemalononitrile, fumaric acid, or dimethyl fumarate and L = PPh,, e.g. (34).81

C"

CN Ph,P ... I

CN

CN

Ph3P... I ph3,,41/C=C( bonds in (41; L = PMe,Ph) give stretching modes at 1650, 1610 ~ r n - l . ~ ~

R'

A series of complexes (42) has been prepared, having v(0H) in the range 3 170-3286 cm-l, indicative of hydrogen-bonding. Trends in the OH stretching frequency, X = I > Br > CI, and v(CO), X = C1 > Br > I, are consistent with known inductive effects.96 Complexes in which allylammonium groups are co-ordinated to Pd include Na[C12PdCIzPdC1(CH2=CHCH2NH3CI)]and Pd(CH,= CH- CH 2NH,)CI,. The i.r. and Raman spectra of the latter indicate considerable mixing of the v(C=C) stretch and 6(CH2) modes.g7 The extent of interaction can be examined qualitatively by reference to the free CH2=CHCH2NH; ion. v(C=C) in (43) is found at 1845 cm-l (i.r., KBr disc).08 A characteristic ally1 vibration is found at 1485--1490 cm-l in the following complexes

[mdp = methylenebis(diphenylphosphine), Ph2PCHzPPh2]: [(r-C3H6)PdCl,(mdp)l, [(.rr-C3H,)PdCl,(mdp)21, [(.rr-C,H,)Pd(mdP)zI[A~C~B~31, [(.rr-C3H6)PdCH(PPh,)2]2,[(.rr-C3H5)PdCH(PPh2)2,(mdp)].BB O*

O6

'' "li

W'

T. G . Appleton, H. C. Clark, R. C. Poller, and R. J. Puddephatt, J . Organometallic Chem., 1972, 39, C13. H. Onoue, K. Nakagawa, and I. Moritani, J . Organomefallic Chem., 1972, 35, 217. F. R. Hartley and J . L. Wagner, J.C.S. Dalton, 1972, 2282. T. Ito, S. Hascgawa, Y . Takahashi, and Y .lshii, J.C.S. Chenr. Cornnt., 1972, 62Y. K . Issleib, H . P. Abicht. and H. Winkelmann, %. nnorg. Cheni., 1972, 388, 89.


379 No bands due to free C=C can be detected in (44), but weak features near 1500 cm-l can be assigned to v(C=C) of the complexed double bond.loo Complex ( 4 9 , on the other hand, gives v(-CCCI=CH2) at 1640 cm-l in the i.r. spectrum.lol t

C'H,

(44)

I CH2 I CCI

II

CH, (45)

Some new n-allylic complexes of Pd have been prepared; thus the 'free' C=C bond gives stretching frequencies at 1661 cm-l (46) and 1662 cm-l (47).'02

Solid PdC12(cod) (cod = cis,trans-l,3-cyclo-octadiene)gives an i.r. band due to co-ordinated >C=C( bonds only (1475 cm-l), but in CHCl, solution a further band is seen, at 1640cm-l, suggesting that the equilibrium

is established. Solid PtCl,(cod) shows bands due to both free and coordinated double bonds (1640, 1510 cm-l, respectively).lo3 v(CF) modes have been assigned in a wide variety of complexes containing the Pt-CF, unit. v, occurs at ca. 1080-1100cm-1, with the degenerate stretch (for isolated CF,) split, at ca. 980-1000, ca. lOl& 1050 cm-'.lo4 In [48; (a) Ri = Ph2Me, R2 = H, X = BF,; (b) Ri = Ph,Me, R2 = Me, X = BF,; (c) Ri = Ph,, R2 = H, X = ClO,], v(C=O) is at Y. Takahashi, S. Sakai, and Y . Ishii, Znorg. Chent., 1972, 11, 1516. D. J. S. Guthrie and S . M. Nelson, Co-ordination Chem. Reo., 1972, 8, 139. C. Agami, J. Levisalles, and F. Rose-Munch, J . Organometullic Chem., 1972, 35, C59. l o 3 H. A. Tayim and A. Vassilian, Znorg. Nuclear Chem. Letters, 1972, 8, 659. I u 4 T. G. Appleton, M. H . Chisholm, H. C. Clark, and L. E. Manzer, Znorg. Chern.. 1972, 1 1 , 1786,

loo Io1

380


1575 cm-l, compared with a value of 1755 cm-l in the parent ligand CH2= CHR2CH20COMe.lo5 Some i.r. and Raman data have been reported for trans-[PtCH,(R1C=CR2)Q2]+PF; [R' = Me, Et, or Ph; R2 = Me, Et, Ph, or CPh,(OH); Q = PMe,Ph or AsMe,]. All give v(C=C) in the range 2024-21 16 cm-l.lo6 In the tcnq adducts [(RiP)2Pt(C=CR2)2]tcnq(R' = Me or Et; R2 = H or Me), the i.r. spectrum due to the tcnq is rather similar to that of the free ligand, except for the presence of a strong band at 1600cm-l due to v(C=C). This is i.r.-forbidden in free tcnq (&), and its presence here suggests a lowering of symmetry to C2t.,for example. The postulated structure is (49).lo7

ci.s-Pt(PPh,l,(

\o/

-C-CMe

B,oH1o

1

Rip' (49)

(i.e. containing a-bonded carbaborane units)

shows bands in the i.r., characteristic of the Bloc, cage, at 740, 2550 cm-l.lo8 The complex (50) has an i.r. band at 1500 cm-l, assigned as v(N-C--N) [with a contribution from 8(NH)]. Compound (51) has a similar band at 1495 cm-l.loB

H. C. Clark and H. Kurosawa, J.C.S. Chem. Comm., 1972, 150. M. H. Chisholm and H. C. Clark, Inorg. Chem., 1971, 10, 2557. lo' H. Masai, K. Sonogashira, and N. Hagihara, J . Organometallic Chem., 1972, 34, 397. lULIR. Rogarski and K. Cohn, Inorg. Chem., 1972, 1 1 , 1429. lUu A. L. Balch, J . Organometallic Chem., 1972, 37, C19. lo6

log


38 I v(NH) and u(N=C) have been recorded for the Pt" carbene complexes where car bene is trans- [Pt(CNC, HS){P(CH,),C,H,) ,(carbene)] P F,, C(OEt)NHEt, C(NHPh)NHEt, C(NHCBH,Me)NHEt, or C(SCH,Ph)NHEt, and for a number of other Pt" cyano-complexes.llo Barriers to rotation of ethylene in complexes PtXYL(C,H4) (X = CI, Br, or CFsC02, trans to C2H4; Y = C1 or Br, cis to C2H4; L = phosphine, arsine, phosphite, or primary amine) have been measured by n.m.r. techniques.lll Comparison of the derived AG* values with v(C0) for analogous PtXY L(C0) demonstrates a significant steric contribution to the rotational barrier. The Pt-cyclopropenone complex (52; L = PPh,), which gives no band assignable to v(C=C), and v(C=O) at 1750 cm-l, isomerizes at - 30 "C to give the Pt insertion product (53). This complex gives v(C=C) at 1675 +

cm-l, v(C=O) at 1640 cm-l. The analogous reactions with cyclopropenones (54; R', R2 = Me or Ph) gave only the latter type (the 7r-complexes could not be isolated).112 Complexes of thiiren 1,l-dioxide ( 5 5 ) with L,PtX [L = PPh,; X = C2H4,CS,, or (PPh,),] and tran~-Ir(CO)Cl(PPh,)~show that the >C=C< Me I

c=o I

bond is co-ordinated [no v(C=C) in complexes; 1614cm-1 in the free 1igand].", Compound (56) gives v(C=O) at 1615 cm-l (X = CI), 1620 cm-l (X = Br), with v(C=C) at 1510 cm-' (X = C1 or Br).ll4 The hex-l-en-5one ligand can also give rise to 7r-ally1 complexes from the form (57). 110 ll1

11* llS 114

H. C. Clark and L. E. Manzer, Znorg. Chem., 1972, 11, 503.

J. Ashley-Smith, I. Douek, B. F. G . Johnson, and J. Lewis, J.C.S. Dalton, 1972, 1776. J. P. Visser and J. E. Ramakers-Blom, J . Organometallic Chem., 1972,44,C63. J. P. Visser, C. G. Lehveld, and D. N. Reinhoudt, J.C.S. Chem. Comm., 1972, 178. B. T. Heaton and D . J. A. McCaffrey, J . Orgariornetallic Chem., 1972, 43, 437.

382 Spectroscopic Psoperties of Inorganic arid Orgarlometallic Cornpourids Dimeric complexes of this ligand give no identifiable v(C=C), and a v(C=O) at ca. 1680 cm--l (i.e. the >C=O group is not complexed). v(C=C) is in the range 1880-1904 cm-l for a series of complexes P t ( a ~ )where ~, (ac) is one of six disubstituted acetylenes with highly complex substituents, e.g. (CH,)(C,H,,)C(OH)-C=C-C(OH)(C,H,,)(CH,).116 The 5-methylenecycloheptene complex (58), in which two double bonds perpendicular to one another are both co-ordinated to Pt, gives v(C=C) ca. 100 cm-' lower than in the free ligand.l18

PtC12(1,4-cod), has v(C=C) at 1500 and 1480 c n - l in the i.r., suggesting that both olefinic bonds are co-0rdinated.l" v(C=C) in complexes of a series of allylic alcohols with Cu' perchlorate is decreased by ca. llOcm-l compared to the value for the free alcohol. This indicates a stronger co-ordination than to CuCl (where the drop is cu. 95 cm-').ll* An i.r. study (1 300-3500 cni-l) has been made l l a a of the absorption of butenes on to a C u 2 0 catalyst. Evidence was presented for the initial fortnation of, for example, a but-l-ene n-complex with Cuf ions. CuCl,(cis,truns-1 $cod) has v(C=C) at 1505 cm-l (i.r.); both double bonds are, therefore, c ~ - o r d i n a t e d . l ~v(C= @ ~ C) wavenumbers were also (1 625, reported for [RhCl(1,5-cod)], (1 480 cm-l), AuC13(cis,trans-l,3-cod) 1530 cm-l), and AgNO,(cis,trans-l,3-cod) ( I 580 cm-l). v(C=C) has been quoted for CuL,(OTf), where OTf = trifluoromethanesulphonate, and n = 1, L = cyclo-octa-1,3,5,9-tetraeneor n = 2, L = endo-dicyclopentadiene.120 v(C=C) in two isomers of (PhC=CAg),,AgNO, is 40cm-' lower than in PhC=CAg.121'z Raman spectra of aqueous solutions of some silver-olefin complexes AgR+ (where R = C2Ha, cis-2-butene, rrms-2-butene, or cyclohexene) and the i.r. spectrum of the new complex [PtC12(Me,C=CMe,)], have been llb

110

117 11*

119

150 lX1

F. D. Rochon and T. Theophanides, Canad. J. C'hem., 1972, 50, 1325. C . B. Anderson and J. T. Michalowski, J.C.S. Chem. Comm., 1972, 459. H. A. Tayim, A. Bouldoukian, and M. Kharboush, Inorg. Nuclear Chem. Letters, 1972, 8, 231. Y. Ishino, T. Ogura, K. Noda, T. Hirasliima, and 0. Manabe, Bull. G e m . Soc. Japan, 1972,45, 150. ( a ) S . V. Gerei, E. V. Rozhkova, and Ya. B. Gorokhvatskii, Doklady. Phys. Chem., 1971, 201, 968; (b) H. A. Tayim and A. Vassilian, Inorg. Nuclear Chem. Letters, 1972, 8 , 215. R. G. Solomon and J. K. Kochi, J.C.S. Chem. Comm., 1972, 559. (a) T. G. Sukhova, 0. L. Kaliya, 0. N. Temkin, and R. M. Flid, Russ. J . Inorg. Chenz., 1971, 16, 816; (b) D. B. Powell, J. G . V. Scott, and N. Sheppard, Spectrochim. A d a . 1972, 28A, 327.

Vibrationd Spectra c!f'some Co-ordinntecl Liguricls

383

examined in detail.121b It was concluded that while a band at 1240 cm - l in the Pt-ethylene complex can be assigned mainly to C=C stretching (as has been suggested previously), a further band at 1500 cm-' should be assigned mainly to v(C=C) for substituted olefins. The degree of interaction between fundamentals with wavenumbers ca. 1240 cm-' and CN. 1500 cm-' for the complexed olefins was discussed. v(C=N) in R1R2C(Br)-C=N is shifted about 30cm-' to lower wavenumbers on forming compounds of the type RRC(ZnBr)- C=N.lZ2 This shift is inconsistent with the alternative formulation R1R2C=C=N-ZnBr. A detailed vibrational assignment for diallylmercury (CH,= CH- CH,),Hg suggests a symmetry of Ci for the molecule in the liquid stafe.lz3 A similar detailed assignment has been proposed for the vibrations of the allylmercuric halides CH2=CH-CH2HgX (X = CI, Br, or I).124 I n solution, the only rotational isomer present possesses Cl symmetry. Unassigned listings of i.r. bands have been made for fluorenylmercuric chloride and bis(fluorenyl)mercury,126and for (59)

(59)

1.r. and Raman spectral data have been listed for bis(cyc1o-octatetraenyl)thorium, Th(CsH&, and some tentative assignments given.12i These data, together with electronic spectra and X-ray powder patterns, were compared with those for U(C8Hs)2,and it was concluded that the thorium compound has a sandwich structure, with rings having aromatic character. Unassigned i.r. bands have been listed for Ce(C8H8)2128 and tetrafluorenylcerium(iv), (C1SHs)aCe.12s Assignments of 8,(CHs) (1045-1 106 cm-l) and p(CHs) (694--750 cm-') have been proposed for the Li+, Na+, Kf, Rb+, and Cs+ salts of InMe,.130 Assignments of characteristic .rr-cyclopentadienylbands have been made for In(C,H,), In(C&6)s, and In(C,H,Me)3.131 1.r. spectra have been assigned (without discussion) for CHS(C~H~)TIX (X = OCOPr', OCOMe, OCOEt, tropolonate, or 4-isopropyl tropololZa

'z3 124

lZ6 la6

129

lJo l.ll

N. GoasdouC and M. Gaudemar, J. Organometallic Chem., 1972, 39, 17. C. Sourisseau and B. Pasquier, J . Organometallic Chem., 1972,39, 65. C. Sourisseau and B. Pasquier, J . Organometallic Chem., 1972, 39, 51. E. Samuel and M. D . Rausch, J . Organometallic Chetn., 1972, 36, 29. D. Seyferth and D. L. White, J . Organometallic Chem., 1972, 34, 119. J. Gordrt, J. Fuger, B. Gilbert, B. Kanellakopulos, and G . Duyckaerts, Inorg. Nuclear Chem. Letters, 1972, 8, 403. B. L. Kalsotra, R. K. Multani, and B. D. Jain, Chem. andInd., 1972, 389. B. L. Kalsotra, R. K. Multani, and B. D. Jain, J . Inorg. Nuclear Chetn., 1972, 34, 2679. K. Hoffmann and E. Weiss, J . Organometallic Chem., 1972, 37, 1 . J . S. Poland and D. G . Tuck, J . Organortrrtnllir Chem., 1972, 42, 307.

384


nate).132 For X = OCOMe, the following were proposed: v(Tl-CbH6) 318; v(TI-CHs) 513; 6(CH) 648; n(CH) 752; p(T1-Me) 785; ring def. 820; G(CH)C,H~ 990; G(CH)C,R,1021; v,(COO) 1420; vas(COO) 1530 cm-l, and several v(CH) bands. A normal co-ordinate analysis has been performed on the hypothetical system (60). Using force fields of free ethylene and HzO, a predicted set of H2C=CH,

I

TI I (60)

frequencies was calculated. Significant shifts from free-ligand values were found in a few modes (e.g. CH, rocking), and this was ascribed to kinematic coupling effects. It should be pointed out, however, that very variable frequencies have been calculated for these modes in free ethylene by numerous workers in the An adduct of Ph3P with tcne has been prepared.ls4 The presence of a single v(C=N) band at 2190cm-l is consistent with (61), appreciable negative charge being shifted on to the tcne. CN I

C-CN Ph,,P: :I C-CN

I CN

61)

2 Carbonyls A simplified model has been described for dealing with interactions between

carbonyl groups, especially those bonded to different metal atoms.135a A consistent interpretation was given of solution and solid-state spectra for a series of binuclear metal carbonyl complexes. Kettle and co-workers have described the application of Wolkenstein's bond polarizability approach to Raman intensities of the terminal v(C0) vibrations for some metal carbonyl species. General intensity formulae were given and discussed in detail for M(CO), (M = Cr, Mo, or W), RM(CO)3 [RM = (C,H,)Mn or (arene)Cr], and RM(CO), (RM = BrMn or Ph,SnRe).ls6* It was concluded that not only do totally symmetric 132 133

134 135

T. Abe and R. Okawara, J . Organometallic Chem., 1972, 35, 27. L. Schafer, J. D. Ewbank, S. J . Cyvin, and J. Brunvoll, J . Mol. Structure, 1972, 14, 185. J. E. Douglas, Znorg. Chem., 1972, 11, 654. (a) J. G . Bullitt and F. A. Cotton, Inorg. Chim. Acra, 1971, 5 , 637; (b) S. F. A. Kettle, I. Paul, and P. J. Stamper, J.C.S. Dalton, 1972, 2413; ( c ) J. H. Darling and J. S. Ogden, ibid., p. 2496; ( d ) M. J. Cleare, H. P. Fritz, and W. P. Griffith, Spectrochim. Acra, 1972, 28A, 2019; (e) S. Cenini, 3. Ratcliff, A. Fusi, and A. Pasini, Gnzzetta, 1972, 102, 141.

Vibrational Spectra of some Co-ordinated Ligands 385 v(C0) modes frequently give rise to weak Raman bands, but that nontotally symmetric v ( C 0 ) modes can be of comparable band intensity to totally symmetric non-carbonyl vibrations. v(C0) band patterns to be expected for binary metal carbonyls produced from C160-C180 mixtures in matrix-isolation experiments have been calculated.13sc In the complexes Cs,M(CO)X, (M = Os, Ru, Ir, or Rh, X = Cl or Br; M = Ir or Rh, X = I), the values of v ( C 0 ) and v(M-C) may be rationalized on the grounds of more effective M-C .rr-overlap from thirdrow transition elements. A close comparison of these data with those from related nitrosyls is consistent with more effective 7r-accepting properties for NO than for C0.136d Solvent (CH2C12,MeCN, CS,, or C,H,,) effects on v(C0) in the i.r. [(?r-Cp)Fe(CO),],SnR,-,, [Co(CO),L],spectra of [Mn(CO),],SnR,-,, SnR,-,, and [(.rr-Cp)Mo(CO),],SnR,_, (where n = 1 or 2; L = CO, phosphines, or arsines; R = Cl, Br, I, Ph, Et, or Me) are interpreted 135e in terms of direct dipole-dipole interactions with the solvent. These are dependent upon R and L. Coupling of CO groups across the M-M'-M system (M = Mo, Mn, Fe, or Co; M' = Sn or also Hg) was confirmed and discussed. Transition-metal carbonyls in which the oxygen is also co-ordinated to an acidic centre (e.g. AIR3) have been reviewed, and the use of v(C0) data in this field has been v(CO), and some lower-frequency bands, have been assigned for the following:137 [V(CO),(NH,)]- [C,,, v(C0) 1979 (Al), 1785 ( E ) cm-l; S(VCO), 649 cm-l; v(VC) 460 cm-'1; [V(CO),(CN)l2- [C,,, v ( C 0 ) 1852 (Ai), 1793 ( E ) , 1744 (-41) cm-'l; [V(C0)4(C"I4- [ D z h , v ( C 0 ) 1794 (Bid, 1748 (Bzu)cm-'1. In matrix-isolation experiments, bands have been observed at 1855, 1852, and 1838 cm-l, assigned to v ( C 0 ) of Cr(C0); [CdU; produced by co-condensation of Na and Cr(CO),].138 Using an approximate MO calculation, the CO force constants of M(CO)6-zL, (M = Cr, Mn, or Fe; L = C1 or Br; x = 1 or 2), have been correlated with calculated occupancies of the carbonyl 50 and 27r Back-bonding to the 27r and a-donation to 50 affect the force constant. Also, direct donation of electron density from a halogen a-orbital to the CO 27r orbital is the most important mechanism by which a change in halogen effects a change in the carbonyl force constant, v(C0) and v(N0) have been listed for (C,H,)Cr(CO)(NO)L, where L = cyclo-octene, ethylene, acetylene, C,(CO,Me),, acenaphthylene, norbornene, or maleic anhydride.14o0" D, F. Shriver and A. Alichi, Co-ordination Chem. Rev., 1972,8, 15. D. Rehder, J. Organomerallic Chem., 1972, 37, 303. lsn P. A. Breeze and J. J. Turner, J . Organometallic Chem., 1972,44,C7. 1 3 8 M. B. Hall and R. F. Fenske, Znorg. Chem., 1972, 11, 1619. 140 (a) M. Herberhold and H. Alt, J . Organometallic Chem., 1972,42, 407; (b) R. Pince and M. Poilblanc, Spectrochim. Acra, 1972,28A,907;(c) R.T.Jernigan, R . A. Brown, and G. R. Dobson, J . Co-ordinarion Chem., 1972, 2 , 47.

386

Spc~c'troscopicP i w p w t ies qf' Itiorgutiic

ciiid

Orgunotnetullic Conipontid~

Raman spectra of liquid M(CO)6 ( M = Cr, Mo, or W) have been recorded and assigned in relation to earlier data. An automatic computational method for the assignment of harmonics and combinations was described, and valence force constants were Two C-0 stretching force constants and three CO-CO stretch-stretch interaction constants have been determined from the four v(C0) wavenumbers of 26 complexes cis-L,M(CO), (L2 = bidentate chelating ligand with N, P, As, or S donor atoms, M = Cr, Mo, or W).l4OCNo relationships among the interaction constants were assumed. The results were in good agreement with force-constant data previously derived from isotopeenrichment studies. v(C0) has been listed for a series of pentacarbonyl complexes M(CO),L (M = Cr, Mo, or W ; L = 0-,m-,or p-tritolylphosphine). All show a medium-intensity i.r. band at ca. 2070 cni-l. In addition, the complexes containing rn- or p-tolyl groups also gave a sharp singlet at ca. 1950 cm-*, while the o-tolyl complexes gave a doublet in that region, due to the steric effects of the ortho-methyl groups.141 v(C0) values were also listed for a variety of cis- and trans-M(CO),L, complexes of similar type. In [C6H6(C0)3M~-SnCl,(S2CNMe2)], v(CN) occurs at 1525 cm-', indicative of partial C-N double-bonding. In addition, five v(C0) bands are seen in CS, solution, suggesting that isomers (62a) and (62b) are present

clg CI

oc

R

co

(62a)

oc'

co

Cl (62h)

(R = S,CNMe,, the third CO on the Mo atom is staggered), i.e. there is hindered rotation about the Mo-Sn bond.142 Knox et al. have shown143that earlier reports (A. N. Nesmeyanov, C. G. Dvoryantseva, Yu. N. Sheinker, N. E. Kolobova, and K. N. Anisimov, Doklady Akad. Nauk S.S.S.R., Ser. khim., 1966, 169, 843) of v(C0) modes in MnRe(CO),, and (h6-C,H,)W(CO),Mn(CO), included a number of bands due to decomposition products of Mn,(CO),, with the CCI, solvent. M~no-~~CO-substituted Mnz(CO)lo and Rez(CO),,, have been studied by i.r. and Raman spectroscopy in the v(C0) ~ e g i 0 n . lThe ~ ~ spectra and assignments of the all-12CO-speciesagree with those of earlier workers, When one 13C0 is placed in an axial position, one A l mode (in C4J drops from 1983 to 1950 cm-l (Mn), from 1978 to 1943 cm-l (Re), whereas the 'equatorial' spectrum is unaffected. Substitution in the equatorial position 14%

Id4

J. A. Bowden and R. Colton, Austral. J . Chem., 1971, 24, 2471. W. K. Glass and T. Shiels, J . Organometallic Chem., 1972, 35, C64. S. A. R. Knox, R . J . Hoxmeier, and H. D. Kaesz, Inorg. Chem., 1971, 10, 2636. W. T. Wozniak and R. K . Sheline, J. Inorg. Chrm., 1972, 34, 3765.

Vibrational SpecIra af some Co-ordinated Ligcrrtcls

387

affects the spectrum more profoundly and the symmetry is now only C,. Using the frequencies so assigned, sets of wavenumbers were computed for all-12CO- and m~no-'~CO-species (13C0 axial or equatorial). The i.r. spectrum of crystalline Mn(CO),NO has been obtained using polarized radiati011.l~~ In conjunction with solution, liquid-, and vapourphase data this gives additional support to the view that the molecule belongs to the point group Czu. A probable space group for the crystal of C'; (Cc) was also indicated. Exchange of 13C0 with Mn(CO),Br has been studied by following intensity changes in the v(C0) region in hexane solution. The results were only consistent with a CO dissociative mechanism, with a slight preference for loss of radial C0.146 (h6-ChH,)Mn(CO), is produced by photolysis of (h5-C,H6)Mn(C0),.l4' The C s O stretching frequencies are decreased on the removal of one carbonyl group: CpMn(CO),: v(A,) 2026, v (E) 1938; CpMn(CO),: v8 1955, v, 1886 (all cm-l). Very similar figures were found for the (MeC,H,) derivatives. 1.r. intensities of v(C0) bands for a series of olefin and Group V donoratom complexes of the type ( T - C ~ ) M ~ ( C O )have ~ L been measured.14* The ratio of the i.r. intensities for v,, vantbrm is rather insensitive to changes in the donor ligand, which suggests that the T-bonded ring acts as a buffer to the vibronic contributions which the ligand L can make to the CO groups (,'jMn n.q.r. measurements support this observation). The interaction bet ween (T -MeCp)M n(CO),, [(n-Cp)Fe(CO),] 2, or ( T - C ~ ) C ~ ( N O )with ~ C ~organolanthanides (C5H5),Ln (Ln = Sm, Er, or Yb), or their C,H,Me analogues, in CHzClz solution has been studied by i.r. spectroscopy in the v(C0) and v(N0) regions. Decreases in v(N0) and v(C0) indicate co-ordination of the Ln compound to the oxygen lone pairs. No, or very little, adduct formation was found with (C,H,)YbCI or (C,H,Me)Y bCI, supporting the supposed dimeric structures of these species.lQ9 (h6-C,H,)Mn(CO)(NO), gives i.r. bands (in C8Hl8 solution) at 1993, 1970 Cm-' [v(CO)terminal], 1813 Cm-' [v(co)brl&e], 1732 Cm-' [v(NO)termii~~~l, and 1534 cm-l [~(NO)b~i&~l. This is explained by the presence of cis- and trans-isomers (63a) and (63b), with overlapping of the bridging (CO) and terminal and bridging v(N0) bands.lsoa Solid-state i.r. and Ranian studies on Ph,SnMn(CO),, Ph,SnMn(CO),PPh3, and PhSSnFe(h6-C6H6)(CO)2 in the carbonyl-stretching region have 140

l*e 147

14@ 14a

160

A. Poletti, G. Paliani, R. Cataliotti, A. Foffani, and A. Santucci, J. Organometallic Chem., 1972,43, 377. A. Berry and T. L. Brown, Znorg. Chern., 1972, 11, 1165. P. S. Braterman and J. D. Black, J. Organometallic Chem., 1972, 39, C3. W. P. Anderson, T. B. Brill, A. R. Schoenberg, and C. W. Stanger, J . Organometullic Chem., 1972,44, 161. A. E. Crease and P. Legzdins, J.C.S. Chem. Comm., 1972, 268. (a)T. J. Marks and J. S. Kristoff, J. Organometallic Chem., 1972, 42, C90; ( b ) H. J. Buttery, S. F. A. Kettle, G . Keeling, I. Paul, and P. J. Stamper, J.C.S. Daltorr, 1972, 2487.

38 8

Spectroscopic Properties of Inorganic arid OrganornetaNic Compounds 0

been interpreted using a new type of symmetry group, called the situs group. This represents a modification of the crystallographic unit cell for vibrational purposes, and the relationship between the symmetry properties of the two was discussed.lSob Shifts in v(C0) bands have been used to detect formation of M-(CO)AIR, adducts.161 Stepwise interactions of tri-isobutylaluminium with both bridging carbonyls of [(~-Cp)Fe(C0)~1~, all four bridging carbonyls of [(r-Cp)Fe(CO)],, but with only one of the two carbonyls of (n-Cp)Ni3(CO), were observed. The following orders of relative affinities for AIR, were established : [(n-Cp)Fe(CO),12 > [(T-Cp)NiCO],; (rr-Cp)Ni,(CO), > [(~-Cp)NiCOI2; [(n-Cp)Fe(CO)I, > [(.~-CP>F~(CO)~I,. A study of the temperature dependence of the relative intensities of the two v(C0) bands at ca. 1980 cm-l for (.rr-Cp)Fe(CO),SiCI,Me has shown that the entropy difference between the symmetric and unsymmetric isomers is 1.4 & 0.5 e.u., with the sign favouring the unsymmetrical isomers. The enthalpy difference suggests a lower limit to the barrier to rotation about the Fe-Si bond of ca. 0.8 kcal m ~ l - ' . ' ~ ~ The new pentanuclear carbidocarbonyl of iron [Fe,C(CO),4]2- gives v(C0) bands at 2021 (vw), 1966 (vs), 1930 (mw), 1897 (w), and 1773 (mw) cm-I. These are consistent with the structure (64), having terminal and edge-bridging CO groups.lS3 (CO),

Phenylpentacenedi-iron pentacarbonyl gives v(C0) bands at 2040, 2010, It was not possible to distinguish between the structures (65a) and (65b).154a 1975 (terminal), and 1785 (bridging) cm-I.

161

l~.'

A. Alichi, N. J. Nelson, D. Strope, and D. F. Shriver, Znorg. Chem., 1972, 11, 2976.

J. Dalton, lnorg. Chem., 1972, 11, 915. A. T. T. Hsieh and M. J. Mays, J . Organometallic Chem., 1972, 37, C53. ( a ) D . F. Hunt and J. W. Russell, J . Organometallic Chem., 1972, 46, C22; (b) D. A. Duddell, S. F. A. Kettle, and B. T. Kontnik-Matecka, Specfrochim. Acfa, 1972, 28A, 1571 ; (c) 0. A. Gansow, D. A. Schexnayder, and B. Y. Kimura, J . Amer. Chem. SOC., 1972,94, 3406.


(6Sa)

3 89

(65b)

The vibrational spectrum of (butadiene)tricarbonyliron has been investigated in the 2000 cm-' region.154bA simple factor-group analysis, which gives an inadequate description of the solid-state i.r. and Raman spectra, was modified by a detailed study based on the crystal structure. Thus, the absence of one A,-derived v(C0) band can be related to the symmetry properties of the crystal structure. 13Cn.m.r. spectra of 18 monomeric derivatives of the (h5-C,H6)Fe(CO), unit have been Interdependence of 13C chemical shifts and v(C0) frequencies indicates that 6(CO) values are determined by changes in the paramagnetic screening term. Benedetti et al. have shown that earlier workers' reports on the i.r. spectrum in the v(C0) region for [ R U ( C O ) ~ X(X ~ ] ~= C1 or Br) in CHC13 solution, which showed a time-dependence for the spectrum, were invalidated by the reaction of the bridged complex with stabilizing agents in the chIor~form.~~~ cis-Ru(CO),(SiCI,), has been shown to exchange with lSCO in a manner which is completely stereo~pecific.~~~ Both equatorial CO groups exchange, while the axial CO groups are unaffected. The persistence of stereospecificity as the second 18C0 group was introduced established that the initially axial and equatorial CO groups are at all times differentiated in the proposed five-co-ordinate intermediate (see Figure 1). ' T O enrichment is not observed in the i.r. when (Me,Si),Os(CO), is treated with 13C0 at 55 "C for 165 minufes.l6' Os6(CO)la,Os,(CO),,, Pyrolysis of Os,(CO),, gives O S ~ ( C O )OSS(CO)16, ~~, O S ~ ( C O and ) ~ ~os~(co)~~c~.158 , All show relatively simple v ( C 0 ) spectra, with no evidence for bridging CO groups. Vibrational spectra have been reported and assigned for M [Co(CO),], (M = Zn, Cd, or Hg).lS9 Symmetries of DBdwere adequate to explain the spectra, although some near-coincidences between i.r.- and Raman-active frequencies were observed, because of the very weak interactions across the Co-M-Co bridge. The metal-metal force constants were all almost E. Benedetti, G . Braca, G . Sbrana, F. Salvetti, and B. Grassi,J. Organometallic Chem., 1972, 37, 361. lK6 R. K . Pomeroy, R. S. Gay, G . 0. Evans, and W. A. G . Graham,J. Amer. Chem. Suc., 1972, 94, 272. lb7 R. K. Pomeroy and W. A. G. Graham, J. Amer. Chem. SOC.,1972, 94, 274. 168 C . R. Eady, B. F. G . Johnson, and J. Lewis, J . Organometallic Chem., 1972, 37, C39. 16@ R. J. Ziegler, J . M. Burlitch, S. E. Hayes, and W. M . Risen,J. Inorg. Chetn., 1972, 1 1 , 702.

16&

390

Spectroscopic Properties of Inorganic and Orgnnometallic Compounds

equal (1.30-1.26 mdyn A-l), with a slight but definite trend: k(Zn-Co) 2 k(Cd--0) 2 k(Hg--0). The proportion of bridged-CO isomers in [(Et3M)Co(CO)J2 increases in the sequence M = P < As < Sb 160 [monitored by i.r. observations in the v(C0) region].

'I

1001

- 0

I

I

2150

2050

cm'

r

2050

2150 cm'

Figure 1 1.r. spectra (in n-heptane solution) of cis-Ru(CO),(SiCI,),. At left, before exchange, showing major bands assigned to the all-12C0 species at 2150, 2103, 2084, and 2094 cm-l; weaker bands at 2140, 2054, and 2057 cm-l assigned to mono-13C0 species in natural abundance. At right, after exchange with 95.5% 13C0 for 18 h at room temperature, bands at 2140, 2084, 2064, and 2046 cm-l assigned to equatorially di-lsCO-substituted moleciile; bands at 2 145, 2 100, and 2054 cm-l assigned to equatorially rn~no-~~CO-substituted molecule (Reproduced by permission from J . Amer. Chem. Soc., 1972, 94, 272)

The i.r. spectrum (together with mass spectral, magnetic, and llB n.m.r. measurements) of C O ~ ( C O ) ~ ( C O B C ~ ~isNconsistent E ~ ~ ) , with the structure (66; L = BC12NEts). v(C0) bands are seen at 2092, 2054, 2040, and 2022 cm-l, with v(B-0) at 1224 crn-l.l6l The complex (67; Y = C1 or Br) gives v(C0)terlnillalat 2045, 2002, and 1985 cm-l, with v(CO)bri&ille at 1799 cm-1.162 v(C0) bands have been assigned for MCo(CO), (M = Mn or Re) and M ~ C O ( C O ) ~ ( P P and ~ , ) ,(arene)Co,(CO), ~~~ (68) (of C,,symmetry ; arene = toluene, tetrahydronaph thalene, or mesi tylene).164 lRo

lG1

Ie3

D. J. Thornhill and A. R. Manning, J . Organometallic Chem., 1972, 37, C41. G . Schmid and B. Stutte, J . Organometallic Chenr., 1972, 37, 375. P. A. Elder and B. H. Robinson, J . Orgnnometallic Chem., 1972, 36, C45. G. Sbrignadello, G . Bor, and L. Maresca, J. Organometallic Chem., 1972, 46, 345. G. Bor, G. Sbrignadello, and F. Marcati, J . Orgarioritetallic Chem., 1972, 46, 357.

Vibrational Spectra of some Co-ordinated Ligands 0' I

39 1

L

Y I

(arcnc)

I co

The reaction [Rh(CO),CI],

+ CO +

H,O

+ NaHCO,

-

Rh4(C0),2

proceeds via a new (possibly bridging) carbonyl species, having v ( C 0 ) at 1886 cm-1.1650 On cooling a liquid paraffin-heptane solution of Rh,(CO),, under 490 atm pressure of CO, the i.r. spectrum of a new Rh carbonyl species is It is proposed that this is the bridged isomer of the previously unsubstantiated parent carbonyl Rh2(C0)8 (see Figure 2). On decreasing the pressure of CO (400, 300, and 200atm) the new i.r. frequencies are observed but are weaker; at temperatures above - 7 ' C , reversible disappearance of these bands occurs, consistent with the stability of the Rh2(CO)8species only at low temperature and high CO pressure. A careful examination of changes which occur in the v(C0) region of the i.r. spectrum of a solution of [Rh(CO),Cl], upon addition of PPh, (1 : 2 molar ratio) provides evidence that the product should be reformulated as the dimeric complex [Rh(CO)CI(PPh,)]2.166This is formed ziia an initial reaction to give cis-[RhCl(CO),(PPh,)],, where n is probably 2, followed by CO loss. 1.r. intensities of CO and CN stretching modes in a number of planar Rh', Ir', and Pt" complexes have been used le7 to calculate the following (a) P. E. Cattermole and A. G. Osborne, J . Organometallic Chem., 1972, 37, C17; (b) R. Whyman, J.C.S. Dalton, 1972, 1375. la* D. F. S t e l e and T. A. Stephenson,J.C.S. Dnlron, 1972, 2161. l C 7 R. Schlodder, S. Vogler, and W. Beck, Z . Naturforsch., 1972, 27b, 462. lR6

392


scales of donor ability for anionic ligands: trans-RhX(CO)(PPh,) X C1 (O.OOO), NCO (0.15), or N, (0.33) ; trans-IrX(CO)(PPh,), X = CN =E

(-0.15) < --N

?=I \N-N

c F3 s o , (CH,),(+O.Ol)

-

"Cd

(-0.12)

< I (-0.05) < Br (-0.03) < C1 (0.00)
CH,P(CF,), (2105, 2046) x EtP(CF,), (2103, 2058) > Me,P(CF,) (2081, 2004) > Me,P (2064, 1982); and for L,Ni(CO), L = (CFa),P (2100, 2065) > MeP(CF,), (2076, 2034) x EtP(CF,), (2074, 2031). Two groups of workers have studied the co-condensation of Pd and/or 173 Darling and Ogden 172 observed Pt atoms with CO in inert the following i.r.-active v(C0) bands of isotopic species of Pd(CO),: T,, Pd(C"0)d 2070.3, A1, Pd(C1sO)(C180), 2047.5 ; Al, Pd(C160)~(C180)~ 2037.0; Al, Pd(C1sO)3(C180)2029.0; T,, Pd(Cl8O), 2022.0 cm-l. Kundig et ale1', obtained Ni(CO),, Pd(CO),, and Pt(CO), by similar means, and investigated i.r. and Raman spectra of the matrices. The CO wavenumbers and Cotton-Kraihanzel force constants derived from them are listed in Table 3.

Table 3 Compound Ni(CO), Pd (CO), WCO), lil li2

vibrational assignments for M(CO), (M = Ni, Pd, or Pt) Al, wavenumberl cm-l 2130 2122 21 19

T2,wavenumberl cm2043 2066 2049

kcol mdyn A-' 17.23 17.48 17.25

kCO-COl

mdyn k1 0.37 0.24 0.30

D.-K. Kang and A. B. Burg, Inorg. Chem., 1972, 11, 902. J. H. Darling and J. S. Ogden, Inarg. Chem., 1972, 11, 666. P. Kundig, M. Moskovits, and G . A. Ozin, J . Mu/. Structure, 1972, 14, 1371.

394

Spectroscopic Properties of Inorganic und Organometallic Compounds

3 Nitrogen Donors Molecular Nitrogen, Azido-, and Related Complexes.-For a number of M-N, Complexes, Darensbourg has obtained a straight-line relationship between v(N,) and the absolute integrated i.r. intensity of the a b ~ o r p t i 0 n . l ~ ~ Thus, the i.r. intensity is largely determined by the extent of rr-electron charge transfer from M to N, during the N2 stretching motion. The dinuclear complex (~-Cp)~TiN~Ti(rr-Cp),, isolated from the nitrogenfixing system (rr-Cp),TiCl MeMgI N,, shows v(N,) at 1280 cm-' in the i.r. (which shifts to 1240cm-l in the 15N2 This is by far the lowest value so far reported for a dinitrogen complex, and a structure of the type (72) is suggested to account for the i.r. activity of v(N,).

+

Cp,Ti

+

,N=N, (72)

TiCp2

(Benzene)chromiuni dicarbonyl dinitrogen, (C,H,)Cr(CO),N,, is prepared by the peroxide oxidation of (CBH,)Cr(CO),N,H,.17s v(N2) is found at 2145 c n r l , with v(C0) at 1941 (Al), 1898 (B,) c n - l . [Note the decrease compared to (C,H,)Cr(CO),]. An analogous hexamethylbenzene complex, together with the dinuclear (hmb)Cr(CO),-N=N-(C0)Cr(hmb) [the latter shows no v(N2) in the i.r.1, were also reported, A more complete tabulation of similar data has been published by the same workers 177 (benzene, mesitylene, and hexamethylbenzene complexes mononuclear and dinuclear for the last two). v(N,) frequencies have been listed for Mo(N*)~(L-L), [L-L = (Ph2PCH2),, (Ph,AsCH,),, or P ~ , A S C H ~ C H ~ P P ~ A , ]weak . ~ ~ ~band is found at ca. 2040 cm-l, and a strong absorption at ca. 1970 cm-l in the i.r. The diphos compound is known to possess a trans-structure, and the others are believed to be the same, the weak, higher-frequency band being the Raman-active mode. Although the v(N,) values are all rather similar within this series, the chemical stabilities differ markedly. A rather similar series of complexes has been studied by Hidai et ul., viz. M O ( N ~ ) , [ P ~ ~ P ( C H , ) ~ Pwhere P ~ ~ ] ,n, = 1, 2, or 3.179a v(N,) moves to lower wavenumber as the chain length of the chelating ligand increases (1995, 1970, 1925 cm-l for n = 1, 2, and 3 respectively), possibly suggesting increased electron-donating power with increased n. Dinitrogen complexes of Mo' have been prepared by the oxidation of Mo(N,),(diphos),, e.g. in [Mo(N,),(diphos),]+ I;, v(N=N) is found at D. J. Darensbourg, Znorg. Chem., 1972, 11, 1436. Yu. G. Borodko, I. N. Ivleva, L. M. Kachapina, S. 1. Salienko, A. K. Shilova, and A. E. Shilov, J.C.S. Chem. Cornm., 1972, 1 1 78. D. Sellmann and G . Maisel, 2. Nuturforsch., 1972, 27b, 465. D . Sellmann and G. Maisel, 2. Nnturforsch., 1972, 27b, 718. T. A. George and C. D. Seibold, Inorg. Niiclenr Chem. Letters, 1972, 8, 465. li0 (a) M. Hidai, K . Tominari, and Y. Uchida, J . Amer. Chem. Soc., 1972, 94, 110; ( 6 )T. A. George and C. D. Seibold, ibid.,p. 6859.

Vibrational Spectra of some Co-ordinnted Lignncls

395

2043 cm-', c - 1976 cm-l in the neutral precursor. This increase is consistent with an increased formal oxidation state of the Mo.l7Ob [B(pz)J(.r-Cp)Mo(CO),, where B(pz), = tetrakis(pyrazoly1) borate, gives four v(C0) bands in solution (at 1950, 1935, 1865, 1845 cm-' in C,D,CD, This is explained on the basis of the presence of two conformers (73a) and (73b).

N

The complex WCl(diphos),(N,COR), prepared from trans-[W(N,),(diphos),] by successive treatment with the RCOCl and Me,N, gives v(N,) at 1338 cm-l (1298 cm-l in the 15Naderivative).lsl Series of compounds [WX,(N,H,)(diphos),], X = C1 or Br, and [WX(N,H,)(diphos),]+Y--, X = Cl or Br, Y = ClO, or BPh,, have been prepared, with N-deuteriated, 16N,EtaPCH2CH2PEt2, and Mo analogues.la2 v(NH), and v(ND) were listed. The cations [WH(N,),(diphos),]+ and [WH(16NB)(diphos),]+gave v(N,) at 1995, 1935 cm-l, respectively. The di-imine complex (74) is assigned the trans-structure on the basis of the non-observance of v(N=N) in the i.r. v(NH) (3250 cm-l) and 6(NH) (1338 cm-l) were seen, however, with v(C0) at 1880 and 1915 cm-l (in benzene solution). n-cP, H OC/yn--N,'

CO

co

/

N-Mn-CO H \ 7PCp (74)

(rr-Cyc1opentadienyl)rhenium dicarbonyl dinitrogen, (h5-C,H6)Re(CO),(Na), gives v(N2) at 2141 and v(C0) at 1970(A,) and 1915(B1)cm-1.184u Interaction of a dinitrogen complex of Re', Re'(PhMe,P),(N,)CI, with Re'(O)Cl,(OMe)(PPh,), in solution yields an equilibrium mixture containing the bridged species R ~ ' - N N = N - R ~ ~ .In ~~ the ~ *initial complex v(N,) is at 1921 crn-', and this drops to 1837 cm-l in the adduct. AIMe, forms adducts with transition-metal carbonyls via the oxygen atom-Chatt et a/. have shown that a similar process can occur with dinitrogen complexes, leading to a lowering of v(N2).ls5 Thus in transJ. L. Calderon, F. A. Cotton, and A. Shaver, J . Organometallic Chetn., 1972,37, 127. J. Chatt, G. A. Heath, and G. J. Leigh, J.C.S. Chem. Cornm., 1972, 444. J. Chatt, G . A. Heath, and R. L. Richards, J.C.S. Chem. Comm., 1972, 1010. lH3 D. Sellman, J . Organometnllic Chem., 1972, 44, C47. Iy4 (a) D. Sellmann, J . Organoniefnllic Chem., 1972, 36, C27; (b) D. J. Darensbourg, Inorg. Chim. Acta, 1972, 6 , 527. Ih* J. Chatt, R. H . Crabtree, and R . L. Richards, J . C . S . C h e r ~Comm., . 1972, 534.

IXo In]

396 Spectroscopic Properties of Inorganic arid Organometallic Compounds [ReC1(N2)(PMe2Ph)J, v(N2) falls from 1923 to 1894 cm-l on the formation of an AIMe, adduct. [ReCI,(NCOPh)(PPh,),] has v(C=O) at 1520 cm-l.lBR Assignments for v(N==N) have been proposed as FeH,(l4N=l4N)(PPhs), 2074; FeH,(14N=15N)(PPh,)3 2042; FeH,(15N=16N)(PPh,), 2008; FeH,(14N=14N)(PPh,Et), 2047; FeH2(l4N=I4N)(PPhEt2), 2020 cm-l. In [FeH(N,)(diphos),]+, as BPh; or C10; salts, v(N,) occurs in the 21 20 2130 cni-l region.1R7b The product (75) of the first reported insertion of chlorosulphanyl isocyanate into a transition-metal-carbon bond has v(C=O) at 2075, 2028 cm- l ; v(C-0) at 1670 cni- l ; v ( S 0 ) at 1353, 1 133 cm-

(Ph,P),Ru(N,)H, gives v(N=N) at 2147 cm-l.l*@ The i.r. spectra of trans-[RuC1(NO)(das),12+, trans-[R~I(NO)(das),]~+, trans- [RuCl(N,)(das),] +,and trans- [RuCl(CO)(das),] +, das = 0-phenylenebis(dimethylarsine), have been obtained (250-4000 cm- l).lgoa 15N substitution of the N 0 , N 2 ligands assisted in the assignment of RuXY modes. Force constants (using a three-body model) for Ru-X-Y were calculated, and on the basis of these the band at ca. 490 cm-l in the N, complex bend (not a Ru-N stretch). All of the was reassigned as a Ru-N-N results are consistent with Ru-(XY) dmp,,-bonding. The osmium dinitrogen complex ~~S-[C~(NH,)~OSNNOS(NH~)~]~+ gives v(N=N) at 2000 cm-l (i,r.), 1999 cm-l (Raman), while cis-[(Cl(NH,),Os},NJ3+ has no i.r. band in this region (1995 cm-l in the Raman), showing the equivalence of the two 0 s atoms on the vibrational time-scale.l@Ob Pentacyanoni trosylcobal t(m), once considered as containing NO-, was shown by J. B. Raynor [J. Chem. Suc. (A), 1966, 9971 to be [(NC),Co(N202)Co(CN)6]6-,with a bridging hyponitrite group. This work has now been repeated,'@' with no acknowledgement, and only minor additions. K2[Rh2(OH2)(N0,),(NH,)2(N,)] shows a Raman line at 2070 cm-l [which shifts to 2045 cm-l when (16NH4),S04 is used in the preparation], J. Chatt and J. R. Dilworth, J.C.S. Chem. Comm., 1972, 549. (a) Yu. G. Borodko, M. 0. Broitman, L. M. Kachapina, A. K. Shilova, and A. E. Shilov, J. Struct. Chem., 1971, 12, 498; (b) P. Giannocaro, M. Rossi, and A. Sacco, Co-ordination Chem. Rev., 1972, 8, 77. l R a Y. Yamamoto and A. Wojcicki, J.C.S. Chem. Comm., 1972, 1088. I R @ W. H. Knoth, J . Amer. Chem. SOC.,1972, 94, 104. l R n ( a ) M. S. Quinby and R. D. Feltham, Inorg. Chem., 1972,11,2468; (b) R. N . Magnuson and H. Taube, J . Amer. Chetn. Sor., 1972, 94, 7213. I y 1 B. Jezowska-Trzebiatowska, J. Hanuza, M . Ostern, and J. Ziolkowski, Inorg. chi^. A d a , 1972, 6 , 141.

Vibrational Spectra of some Co-ordinated Ligancis

397

while there is no significant i.r. absorption at this position.lB2 Hence a linear Rh-NSN-Rh group is present. v(N=N) in IrX(N2)(PPh3)2is a 2095 cm-l (X = CI, Br, or I), and v(N0) in [1rX(NO)(PPh3),li is at 1902 (X = CI or Br) or at 1895 (X = I) crn-l.lB3 The complex (76) shows v(N,) at ca. 1415 cm-l, substantially lower than the value (ca. 2300 cm-l) in the corresponding diazonium salt.lg4 A wider

X

(77)

range of this type of complexlB5gives very similar results, while (77; X = F or Br) possesses v(N=N) at 1450 cm-l. Ni(CO),(N,), produced by photolysis of Ni(CO)* with N2 at 20 K in a N, matrix, gives the following i.r. wavenumbers : Ni(C0)3(14N2), v ( C 0 ) 2027/2031 (E), 2098 (A,) cm-l, v(N,), 2266 (A,) cm-l; Ni(CO),(l6N2), v(C0) 2027/2031 (E), 2096 (A,) cm-l, v(N,) 2193 (A,) cm-*.lg8 The intensity of the v(N2) band is consistent with the structure (78), although the decrease from free N2 is rather small, i.e. the Ni-N2 bond is weak, N

111

N I

ocPi\ I co co Diazoalkane-nickel(o) complexes (R2CN2)NiL2,where R2C = fluorenylidene, Ph2C, or (NC),C and L = ButNC; R2C = fluorenylidene, L, = cod, show a strong i.r. band at 1520-1540cm-1 due to v(C=N=N). This excludes linear end-on co-ordination involving a lone pair on the terminal nitrogen (which would give a band at ca. 2000-2200 cm-l).lB7 Co-condensation of Pd atoms with 14N2at 4.2-10 K leads to formation of a binary complex, believed to be Pd(N,),. Using isotopic variants of L. S. Volkova, V. M. Volkov, and S. S. Chernikov, Russ. J . Znorg. Chem., 1971, 16, 1383. 193 R. J. Fitzgerald and H. M. W. Lin, Znorg. Chern., 1972, 11, 2270. l Q 4 A. B. Gilchrist, G . W. Rayner-Canham, and D. Sutton, Nature, 1972, 235, 42. lU6F. W. B, Einstein, A. B. Gilchrist, G . W. Rayner-Canham, and D. Sutton, J . Amer. Chem. SOC., 1972,94,645. l y e A. J. Rest, J . Organometallic Chem., 1972, 40,C76. l V 7 S. Otsuka, A. Nakamura, T. Koyama, and Y . Tatsumo, J.C.S. Chem. Comm., 1972,

*03

1105.

398

Spectroscopic Properties of Imrgciriic cirid Orgnnonietullic Cotnpoitnd~

Nz,shifts in v(N=N) were observed, and shown to agree closely with those calculated for Pd(N2)3.10R Unassigned i.r. data have been listed for Eeveral 1,2,3-benzotriazole (79) complexes of Pd".19y

v(Nz) data have been reported

for the following complexes: 15N=14N analogue, 2009 cm-l) ; K [Pt z(C104)z(N02),( (2065 cm - l ) ; and N H ,)J,2 KCIO, K2[Pt2(C10,)2(N02),(NH3)2(Nz)],~(K2S04) (2055 cm-l). All are believed to contain a linear Pt-NEN-Pt grouping. The reaction of Pt(Ph,P), (n = 3 or 4) with NO gives a monomeric hyponitrite complex (80), Pt(N,O,)(Ph,P),. It shows i.r. bands at 1285, 1240, and 1062 cm-1.201

K2[Pt2(0H),(N02)4(NH3)2(N2)],2H20 (2034 cm-l;

Ph,PY

,Nir

0

p, I1

Ph3P

N,

0

v,(N,) has been reported (in the range 2053-2090 cm-') for M(PPh,),N,, M = Cu, Ag, or Au, and Cu(diphos),(N,),, together with v,,(NCS) in M(PPh3)2(NCS), M = Cu, Ag, or Au, and Ag[P(OEt)Ph,]2NCS.202 The i.r. spectra of a number of transition-metal azide complexes have been studied by AgreL203 These include Cu(N,),, [Cu(N,),(NH,),], [Cu(Ndz(pY)21, [Zn(N3)2(NH&], [Zn(N3)2(py)zl, and [Cd(N&dPY)2]. Assignments were proposed, where appropriate, for the NH, and py vibrations, and a correlation was found between the value of v3 of the N, group and the degree of asymmetry of that group - increased asymmetry (determined crystallographically) gave rise to a higher value of v3. Wavenumbers for the azido-group vibrations in four new diarylthallium(rr1) azides are listed :204 va8(N3) 2000-2200 cm-l; v,(N,), 13251330 cm-l ; 6(N,) 648-652 cm-l. G. A. Ozin, M . Moskovits, P. Kundig, and H. Huber, Cnnad. J . Chem., 1972, 50, 2385. IYp Y. Watanabe, I. Mitsudo, M. Tanaka, K . Yamamoto, and Y. Takegami, B U N . Chem. Sor. Japan, 1972, 45, 925. V. M. Volkov and L. S. Volkova, Russ. J . Znorg. Chem., 1971, 16, 1382. S. Cenini, R. Ugo, G. LaMonica, and S. D. Robinson, Inarg. Chim. Acru, 1972, 6 , 182. * 0 2 R. F. Ziolo, J. A. Thich, and 2. Dori, Znorg. Chent., 1972, 11, 626. 203 I. Agrell, Acta Chem. Scand., 1971, 25, 2965. 2 0 4 T. N. Srivastava and K . K . Bajpai, J . Iiiorg N d e n r Chem., 1972. 34, 1458. IBR

Vihrntioital Spectra qf' sotue Cci-or~tlitzcrtetiLigatitls

399

The i.r. spectrum of bis(benzalhydrazono)tin(iv) chloride is consistent with the structure (81).205

Amines and Related Ligands.-v(NH) has been reported as follows : LiClO,(cyclam) 3295 ;(LiBr),(cyclam) 3250; (LiI),(cyclam) 3250; (LiCIO,),(cyclam) 3275, 3155 (the latter being due to hydrogen-bonded species); free cyclam 3260, 3 185 (all wavenumbers/cm- l) 20aa (cyclam = 1,4,8,11tetra-azacyclo-tetradecane). The i.r. and Raman spectra of LiN03,2NH3 and LiN03,4NH, at - 180 "C can be interpreted in terms of [Li(NH,),J+ complex ions with different Lie . N distances in the crystalline structure.206b v(Li+- . 'N) are in the range 460-570cm-' (NH,), 400-500cm-1 (ND,). Similar data were also reported on the closely similar systems NaX,nNH, (X = Br or I).2o6c The complexes MX4L,MX4L2 (M = Ti or Sn; X = C1, Br, or I ; L = N-allylthiourea) involve co-ordination via N to the metals. Wavenumbers were listed for v(NH), v(C=C), and several skeletal bands of the ligand.207 1.r. wavenumbers have been listed (down to 400 cm-l) but not assigned for CrCI,L,, where L = 2-, 3-, or 4-~yanopyridine.~~*" The i.r. spectra of tris-(2,2'-bipyridyl) complexes of Cr, V, and Ti in low oxidation states have been reported.2o8b Trends in ligand fundamentals with changes in metal formal oxidation states were discussed. In the complexes fac-M(CO),T and [M(CO),(T)I]+, where M = Mo or W; T = bis-(2-pyridylmethyl)amine, bis-(2-pyridylmethyl)methylamine,or bis-(2-pyridylethyl)amine, the presence of just two bands in the 1 5 5 0 1650 cm-l region ( v ~ Ygb ~ , of the pyridine ring) indicates that both pyridine v(C0) values were also listed. rings are co-ordinated to the Approximate assignments have been proposed by Behrens et al. for the following complexes: Mn(CO),(NH,)(CONH,), Mn(CO),(PPh,)(NH,)(CONHI), and Mn(CO),(NH,),(CN).210

-

*05

2ou

408

201)

2*n

C. H. Stapfer, R. W. D'Andrea, and R. H. Herber, Inorg. Chem., 1972, 11, 204. (a) D. E. Fenton, C. Nave, and M. R. Truter, J.C.S. Chem. Cumm., 1972, 1303; (b)A. Regis and J. Corset, J . Chim. phys., 1972, 69, 707; (c) A. Regis, J. Limouzi, and J. Corset, ibid., p. 696. R. P. Singh and 1. M. Pande, J . Inorg. Nuclear Chem., 1972, 34, 1131. ( a )J. C. Chang, M. A. Haile, and G. R. Keith, J . Inorg. Nuclear Chem., 1972, 34, 360; (b) E. Konig and E. Lindner, Spectrochim. Acra, 1972, 28A, 1393. J. G. Dunn and D . A. Edwards, J . Organornetallic Chem., 1972, 36, 153. H. Behrens, E. Lindner, D. Martens, P. Wild. and R. J. Lampe, J . Organornetallic Chem., 1972, 34, 367.

400

Specfroscopic Properties of Inorgonic and Organometallic Compounds

Some amine ligand vibrations have been assigned in Mn(acac),L,, where L2 = en or L = propylamine, allylamine, methylallylamine, or trans-cro t ylamine. Mn", Fe", and Nil' complexes of the onium ion of (82) show i.r. spectra which contain, in addition to free ligand bands, a number of intense

(82)

absorptions due to v(N+-H) (3000-2250cm-l) and to N+-H deformations (probably coupled with CH2 deformations etc.) (1 600-700 cm-1).2L2 A 1 : 1 adduct of Mn(acac), and allylamine is shown to be a dimer in Et20 1.r. bands associated with the NH2 group are at 3340, 3240, 3160, and 1553 cm-l. These represent shifts to lower wavenumbers of ca. 40cm-l compared to the free-ligand values, showing that the NH2 group is co-ordinated. v(C=C), however, is unshifted, and a singlecrystal X-ray study confirms the presence of bridging acac ligands and unidentate allylamines. The i.r. spectra of ResClQ(bipy),.,or a and Re,C18(bipy), are all very similar.214 In addition to characteristic bands of co-ordinated 2,2'bipyridyl, bands due to the 2,2-bipyridinium cation were seen at 1528, 990, and 887 cm-l. trans-ReCI,(NMe)(PPh,R),, where R = Me, Et, or Ph, have an i.r. band at ca. 1310cm-' which appears to be associated with the NMe group.21a Unassigned i.r. spectra have been listed for [(MeCN),Fe(transtetramine)I2+, [Fe(truns-tetramine)l2+,[(MeCN),Fe(trans-tetrarnine)l4+, and [HFe(trans-tetramine)]+,where trans-tetramine = (83).216 The complex (84) gives v ( C ~ 0at) 2082, 2046, 2002, 1991 cm-l, v(C=O) at 1729 cm-l (R = n-C,H,); v(C=O) at 2082, 2045, 1998 cm-l, Y(C=O) at 1716 cm-l (R = CMe,).217 1.r. bands have been listed for the purpose of the characterization of Fe(mephen),X,, where X = NCS, N3, or CN and mephen = 2-methyl1,10-phenanthroline.218 811 Y.Nishikawa, Y. Nakamura, and S. Kawaguchi, Bull. Chem. SOC.Japan, 1972, 45, 212

113

*I4 *I6

*I7

*lm

155. L. M. Vallorino, V. L. Goedken, and J. V. Quagliano, Znorg. Chem., 1972, 11, 1466. S. Koda, S. Ooi, H. Kuroya, Y. Nishikawa, Y. Nakamura, and S. Kawaguchi, Inorg. Nuclear Chem. Letters, 1972, 8, 89. D. G. Tisley and R. A. Walton, Znorg. Chern., 1972, 11, 179. J. Chatt, R. J. Dosser, and G . J . Leigh, J.C.S. Chem. Comm., 1972, 1243. D. C. Olson and J. Vasilevskis, Inorg. Chern., 1972, 11, 980. H. Alper, Znorg. Chem., 1972, 11, 976. E. Konig, G. Ritter, K . Madeja, and A. Rosenkranz, J . Znorg. Niiclear Chem., 1972, 34, 2877.

40 1

Unassigned i.r. bands have been listed for [M(pccbf)] 'RFi, where M = Fe, Ni, or Zn and pccbf = fluoroborotris-(2-aldoximo-6-pyridyl)phosphine. The cations are believed to possess trigonal-prismatic coordination about the cis-Geometry is deduced for the complexes [Co(en),(RNH,)Cl]CI,, where R = Burl, Bu', or Bus, from the observation of two CH, rocking modes in their i.r. spectra (at 879--871, 899-890 cin--1).220n Bands in the 600-4400cm-1 region of the i.r. spectra for trans-[CoX,(en),]X (X = CI, Br, or I) have been attributed to v(Co-N) and chelate deformation modes.220b 1.r. data were recorded for o-aminophenylarsenic acid complexes of Co, Ni, Cu, Zn, and Cd.220c I t has been shown that i.r. spectra in the 800-950cm-l and 2800-3000 cm-l regions are useful for differentiating fac- and mev-co-ordination of dien in octahedral Co(dien)i +.221 v(NH) is at ca. 3220 cm-l (cf 3272 cm-l in the free ligand) and v(CN) is iinshifted (ca. 2260 cm- l) in CoLt+, NiLt+, and NiL:+, where L = hydrogen cyanamide, H,NCN.222 Selected i.r. wavenumbers have been listed for the characterization of the amino-complexes Co(oxalate)L,, where L = py, aniline, isoquinoline, or 4(phen). 83 Co", Ni", and Zn" complexes of NN'N"-tris-(2-picolyI)-cis,cis-l,3,5triaminocyclohexane [ = (pcc),tach] are basically octahedral. They give v(NH) in the range 3205--3275 cin-', with the acyclic CH, bending mode between 1455 and 1465 1.r. spectra have been listed for 7 isomeric forms of [Co(tmd)(dien)CI]ZnCl,,xH,O and 6 of [Co(tmd)(dpt)Cl]ZnC1,,xH20, where tmd = 1,3"Iw ""O

2LZ

L'23

224

J . E. Parks, R. Wagner, and R. H. Holm, Inorg. Chem.. 1971, 10, 2472. ( a ) S. C. Chan and K . M. Chan, Z . anorg. Chem., 1972, 389, 205; (b) M. Nakahara and M. Mitsuya, Bull. Chem. SOC.Japan, 1972, 45, 2209; (c) I. S. Maslennikova and V. N. Shemyakin, Zhur.fiz. Khim., 1972, 46, 1004. F. R. Keene and G. H. Searle, Inorg. Chern., 1972, 1I , 148. W. C. Wolsey, W. H . Huestis, and T. W. Theyson, J . Inorg. Nucleur Chern., 1972, 34, 2358. G. P. Singh, P. R. Shukla, and R . N. Srivastava, J . Inorg. Nuclear Chem., 1972, 34, 3251. R . A. D. Wcntworth, Inorg. Chent., 1971, 10, 2615.

14

402

Spectroscopic Properties of' Irioi.gnnir atid Orgaiiomeiallic Conipountls

diaminopropane; dpt = dipropylenetriamine; dien = diethylenetria~nine.~~~ The i.r. spectra of [Co(dli),(sam),]r\jO,, where dh =: dimethylglyoximato and Sam = p-NH,-C,H,.SO,NHR (various R), are said to indicate that the sulphanilaniide ligands are co-ordinated via the p-NH, group.226 The shifts in u(NH) on co-ordination of allylamine with MSO, ( M = Co", Nil', Cu", or Zn") have been correlated with the heats of formation of the crystalline complexes, and related to the Irving-Williams series.,,' A listing has been made of free- and co-ordinated-ligand i.r. wavenumbers for Co", Ni", and Cu" halide derivatives of 6-methyI-2,3-di-(6methyl-2-pyridy1)quinoxaline (85; R1 = Me, R2 = H) and 6,7-dimcthyl2,3-di-(6-methyl-2-pyridyl)quinoxaline(85 ; R1 = R 2 = Me).228

1.r. wavenumbers (to 250 cni l ) have been reported for MCI,L2 ( M = Co, Ni, Cu, Zn, or Cd) and M(SO,)L, ( M = Cu or Cd), where L = p-aminoazoben~ene.~'~ N o attempt at assignment was made. Some ligand vibrations have been assigned for RhCI3L3, where L = 4-CN-, 3-CN-, 4-Et-, or 3-Et-py, and for [RhCI,L,]+-, where L = 4-NH2or ~ - N H , - ~ Y .These ~ ~ O are all consistent with unidentate co-ordination of the pyridine ligand via the ring nitrogen. v(NH) wavenumbers for about 20 coniplexes of Rh"' with C-rac- and C-rneso-5,5,7,12,12,14-hexaniethy1-1,4,8,1l-tetra-azacyclotetradecanehave been ion, produced by the reduction of the chloraniine The Ir(en),(NH,)! complex Ir(en),(NH,Cl)i+, is the trans-isomer, since only one i.r. band due +

A. R. Gainsford and D. R. House, Irrorg. Chim. Arta, 1972, 6, 227. V. N. Shafromskii and J. L. Fusii, R N S SJ. . Inorg. Chern., 1971, 16, 1171. x7 M. S. Barvinok, Yu. B. Kalugin, and L. A. Obozova, Russ. J . Inorg. Chern., 1971, 16, 1617. 228 D. F. Colton and W. J. Geary, J.C.S. Dalton, 1972, 547.

226

22E

229

L. V. Kinovalov, I. S. Maslennikova, and V. N. Shemyakin, R u m . J . Itiorg. Cherrr.,

2s1

1971, 16, 1528. C. McRobbie and H . Frye, Austml. J . Chenz., 1972, 25, 893. N. F. Curtis and D. F. Cook, J.C.S. Dulfon, 1972, 691.

Vibrational Specttx of some Co-orditioted Ligands

403

to the N H 2 symmetric deformation, and one due to CH2 rocking, were Some i.r. data have been published relating to [Ni(en),]Xz (X = CI , Br-, I-, or gS20:-),232*to y-picoline complexes obtained from Ni(C104)2,232C and to Ni(diethanolamine),X, and [Ni(diethanolamine)(H,O)X], (X = C1, Br, or 1.r. spectra have been shown for [Ni(acac)(tetramen)]+, [Ni(acac)(tetramen)(OH,)]+, and [Ni(acac)(tetramen)NOJ, where tetramen = N N N ' N ' tetrameth~lethylenediamine.~~3 Negative shifts in the wavenumbers of v(NH2) and v(NH) of triethylenetetramine upon formation of Ni" and Cu" complexes show that all of the amino-groups of this ligand are co-ordinated to the A partial assignment has been proposed235 for ligand vibrations in [Ni(pyDPT)X]X and [Ni(pyDPT)Y]PF6 {X = C1, Br, I, NO,, or S C N ; Y = C1, Br, NO,, or SCN; pyDPT = (2-C6H4N)CH=N(CH2),NH(CH,),N= CH(Z-C,H,N)}. + The trimethylhydrazinium cation H,NNMe, co-ordinates to Nil', forming yellow, paramagnetic complexes NiCl(H2NNMe3), with tetragonally distorted octahedral geometry. On heating to 145 "C, the coordination number changes reversibly, with formation of [H,NNMe&+[NiCl4I2-. The NH2 vibrations change markedly on co-ordination to the metal, e.g. v(NH,) is lowered by cn. 100 cm-l, 6(NH,) is lowered by 10-20 cm-l, pt(NH2) is raised by 20 cni-l, and pw(NH,) is raised by cci. 100cm-l. In addition, p,(NH2) appears as a new, medium-strong i.r. band (cn. 600 cm-l), although v(Ni-N) could not be d e t e ~ t e d . " ~ Analysis of i.r. bands attributable to Vibrations of co-ordinated primary and secondary amino-groups has proved useful in studying complexes of Nil1 and Cu" with polydentate nitrogen-containing ligands produced by the reaction of acetone with bis(diaminoethane)M" (M = Ni or C U ) . ~ ~ ' Determination of the crystal structure of [Ni(en)2(H20)(B F4)]BF, confirms the presence of a unidentate co-ordinated BF; unit. 1.r. evidence was ambiguous, however, although features not attributable to free BF; are v1 at 765 cm-l, v4 (split) at 516, 521 cm-l, and v, at 1050 cm-1 (signs of splitting). v2 could not be Unassigned i.r. data have been given for two isomeric forms of Pd(2chloropropane-1,3-diamine)C12.239

233 p34 236 23B 237

238

( a ) T. R. Weaver, B. C. Lane, and F. Basolo, Ittorg. Chem., 1972, 11, 2277; ( b ) J. Cshszar, Magyar KPm. Folydirat., 1972, 78, 219; (c) V. M. Bhatnagar, Rev. Roumiiie Chiin., 1972, 17, 477; ( d ) M. N. Hughes, B. Waldron, and K. J. Rutt, Iiiorg. Chim. A m , 1972, 6 , 619. Y . Fukuda and K. Soue, J . Inorg. Nuclear Chem., 1972, 34, 2315. E. Cara, A. Cristini, A. Diaz, and G. Ponticelli, J.C.S. Dalton, 1972, 527. C. T. Spencer, Inorg. Chem., 1971, 10, 2407. V. L. Goedken, L. M. Vallarino, and J. V. Quagliano, Inorg. Chent., 1971, 10, 2682. N. F. Curtis, J.C.S. Dalton, 1972, 1357. A. A. G . Tomlinson, M. Bonarnico, G. Dessy, V. Fares, and L. Scaramuzza, J . C . S . Dolton, 1972, 1671. T. G . Appleton and J. R. Hall, Inorg. Chein., 1972, 11, 112.

404

Spertt*osc.opir Properties of Irtorgniiic arid Orguiiotnetnllic Cornpout~d~

The i.r. and Kaman spectra of a number of Pt" and Pd" complexes with triniethylamine { t r a n s - M X , ( N Me,), and [Pr;'N][MX,NMe,], where M = Pd, X = C1; M = Pt, X = C1 or Bri have been listed and discussed.240 All of the wavenumbers identified with v(M-N) and v,(NC,) modes are substantially lower for the Pd complexes than for the Pt analogues, despite the smaller mass of Pd. This is similar to the behaviour of M-P and M-As modes, and suggests that the weakness of NMe, as a ligand, by comparison with PMe, or AsMe:,, is not obviously attributable to differences in the orbitals available for bonding to the metal. Some i.r. data on Pt and Pd complexes of 1,3-diaminopropan-2-01, NH2CH2CH(OH)CH2NH,(tnOH), and of 2-chloropropane-l,3-diamine, NH,CH,CHCICH,NH, (tnCI), have been For the complexes [M(en),lX, (M = Pd or Pt; X = CI, Br, or I), the preparation and vibrational examination of: (a) normal, C-, N-perdeuteriated chlorides, (6) normal bromides and iodides, (c) N-deuteriated Pd(en),Br, and Pd(en),12, and ( d ) C-deuteriated Pt(en),I,, has made possible quite a complete analysis of the vibrational fundamentals of these complexes.241b Identification of only two i.r. bands due to v(Cu-N) has been taken to imply a cis-geometry for solid bis(glycinamidato)copper(ii) (85a).241r

Partial i.r. assignments have been given for CuL,Cl,, CuL,,(OH)CI, CuL,CI,, Cu,OBr,L,, CuL,(OH)Br, CuL,Br,, CuL,(OH)NO,, CuL,(NO,),, CuL,(OH)CIO,, and CuL,(OH)CIO,, where L = cyclohexylamine.2J1d 1.r. spectra (550-200cm-l) were presented for fifteen Cu" and Cu' complexes of bipy and phen. Empirical spectral correlations could be made for distinguishing octahedral, tetragonal, trigonal-bipyramidal, tetrahedral, pseudo-tetrahedral, and square-planar ~ o - o r d i n a t i o n . ~ ~ ~ Six new mixed Cu" chelates with NNN'N'-tetramethylenediamine (tmen) have been prepared.243 They are [Cu(tmen)(en)](CIO,),, [Cu(tmen)(en)]S0,,4H20, [Cu(tnien)(en)](NO,),,H,O, [Cu(tmen)(gly)]CIO,, [Cu(tmen)(ox)],4H,O, and [Cu(tmen)(aca)]ClO,. The i.r. spectra show that there is no significant interaction of the anions with the complexes. 2Jo

:.I: 24J

P. L. Goggin, R. J. Goodfellow, and F. J . S. Reed, J.C.S. Dalfon, 1972, 1298.

(a)?'. G . Appleton and J . R. Hall, Inorg. Chem., 1972, 11, 117; (b) R. W. Berg and K. Rasmussen, Spectrochitn. Acfu, 1972, 28A. 2319; (c) G . R. Dukes and D . W . Margerum. J . Amer. Chew. Soc., 1972, 94, 8414; ( d ) G. Ondrejovid, L. MachSkovri, and J . GaZo, 2. anorg. Chem., 1972, 393, 173. C i . C. Percy and D. A . Thornton, J . Mot. Sfrucfrire, 1972, 14, 313. Y. Fukuda and K . Soue, Bull. Cliern. Soc. Jrrpan, 1972, 45, 465.

Vihrntionrd Spectrrr of some Co-orditintcd Li OH- > C(0Me)NMe- z C(OCH,CH=CH,)NMe- z C(NHC,H,NO,)NMe- > C(NHCGH,Me)NMe- > Ph- > Me-. For the complexes [Pt(L)(CN Me)(PPh3)J2+it lies between 2280 and 2263 crn I , with the order L = PPh, 2 MeCN 2 P(OMe), 2 Me,S z py > MeNC > C(OCH,CH=CH,)NHMe > C(NHC,H,Me)NHMe > NMe3.30H A number of NCBH; complexes have been prepared, e.g. (R,M),Cu(NCBH3), M = P, As, or Sb, and (R3P)3Ag(NCBH3).30Q These show an increase of v(NC) by comparison with the free ion (1-24 cm- l), indicating M-N bonding. The BH3 frequencies are all very similar to those of the free ion. 1.r. spectra (350-400cm-*) have been listed for 2CuX,L [X = C1 or Br; L = Me,C=C(CN), or (CD3),C=C(CN),].310 The increase in v(CN) and decreases in v(C=C) on co-ordination are apparently consistent with the formuIation (loo), although a dimeric structure involving bonding of the C=C bond to Cu cannot be completely excluded.

(100)

(101)

The complex (101) has v(N=C) of the isocyanide ligand at 2146 ~ m - l . ~ " v(CN) has been listed for all the lanthanide complexes (r-Cp),Ln(CNC6Hl1),and the variation in this with 4f-orbital occupancy interpreted in terms o f f -> r* b a ~ k - b o n d i n g . ~ ~ ~ In ThCI4,2CNCl and UC14,2CNCI, v(C=N) is found at 2242cm-l (2219 cm-l in free CNCI). Thus, bonding of CNCl occurs via the nitrogen atom.313 Papers reporting v(CN) data, with little or no comment, are listed in Tables 4 and 5.314-32s P. M. Treichel and W. J. Kuebel, Inorg. Chem., 1972, 11, 1289. S. J. Lippard and P. S. Welcker, Inorg. Chern., 1972, 11, 6. S. K. Smirnov, 0. G. Strukov, S. S. Dubov, A. M. Gribov, and E. L. Gal'perin, Russ. J . Inorg. Chetn., 1971, 16, 1159. 311 G . van Koten and J. G. Noltes, J.C.S. Cliem. Conim., 1972, 59. 312 R . von Ammon and B. Kanellakopulos, Ber. Brrtrsengesellschaft. phys. Chem., 1972, 76, 995. 318 J. MacCordick and G . Kaufmann, Bull. SOC.chint. France, 1972, 23. 314 P . M. Treichel, G . E. Dirreen, and H. J. Mueh, J . Organometallic Chcnr., 1972, 44, 339. 316 K . A . Bailcy and E. N. Balko, J . Inorg. Nuclear Chem., 1972, 34, 2668. 316 S. Papp, S. Kovacs, and I. Liszi, J . Inorg. Nuclear Chem., 1972, 34, 3 1 1 1. 317 H . Alper and R. A. Partis, J . Organonietallic Chem., 1972, 35, C41. s i n H . Brunner and M . Vogel, J . Organometnllic Chem., 1972, 35, 169. 818 J . A. Ferguson and T . J. Mayer, Inorg. Chem., 1972, 11, 631. 320 A. L. Ralch and J. Miller, J . Anrer. Chem. SOC.,1972, 94, 417. 821 B. E. Prater, J . Organometallic Chem., 1972, 34, 379. References continued on facing page. 508 so0

31 0

Vibrtrtionnl Spectm of some Co-orcfinnterlLigntids Table 4

41 5

Cyartide atid isocyanide complexes of Mn, Fe, arid Ru for- which v(CN) data kme been pith fished Conipountl [Mn(CO),(CNMe),_,,]+( n = 0 - 5 ) [MnBr(CO),(CNMe),_,&] (n = 1-4) K,[Mn(CN),(H,O), KCNI [Fe(CN),],-, [Fe(CN),]", [Fe(CN),(NO)]'(as phosphonium salts) [Fe(CO),(CNAr)l [Fe(CO),(CNAr),] (Ar = 0-,m-,or p-Me.C,H,) (rr-Cp)Fe(CO)(CNC,H,,)I (rr-Cp)Fe(CO)[CNCH( Me)Ph]I (rr-Cp)Fe[CNC,H,,],I (n-Cp) Fe [C N C H (M e)P h],I

)

{ [(rr-Cp)Fe(C0)(NCMe)l2(Ph,PCH,CH,PPh,)J+ (MeNC)4Fe(C,H,RN,)2+(R = H, Me, or Ph)

cis- and ~ ~ ~ ~ s - R u ( C N E ~ ) ~ ( M P ~ ~ ) , X , (M = P, As, or Sb; X = CI or Br)

ReJ.

314 315 316

317 318 319 320 321

Table 5 Cyanide and iso-cyanide complexes of Co, Rh, Ir, Ni, Pd and Pt for which v ( C N ) data have been published Compound Et,"Co(CN),(Co),(P(c,H,,),) 1qH2O Et4N [Co(CN)dCO)( PPh,),l,2 H2O K[Co(CN),(CO),L2],3H2O (L = MePPh, or Me,PPh) K[Co(CN),(CO)L,],(Me,CO or H,O) (L = PEt,) K[C0(CN)~(C0)(diphos)],H,0 [Co(dpe),(CN),] +C10; Co(dpe),(CN),MX,(M = Co; X = CI, Br, or NCS; M = Mn, Fe, Ni, or Zn; X = C1) [(ArNC),Rh(tcne)]+ (Ar = p-Me. C,H4, p-MeO. C,H4, or 0-Me C8H4) IrL(CO)(MPh,), (M = P or As) IrL(CO)(PPh,),L' (L' = tcne, fumn, or SO,) RhL( CO)(PPh,), RhL( CO)(PPh,),(tcne) Pt E t( L)( PP h3), PtH(L)(PPh,), PtH(L)(PEt,), [Pd(L)( Me,dien)] + (L = dicyanoketeniminato, C,N,) [Ir( CO)( MeNC),]+ [Ir(diphos),(MeNC)] + [IrY(diphos),(MeNC)]?+ (Y = CI, I, H, or HgCI) [Ir(MeNC)J2 +

-

152

3'J3 32p

3*6

326 sa7 32n

329

1

1

Ref. 322

323 324

325

3 26

J. Halpern, G. Cuastalla, and 5. Bercaw, Co-ordination Chem. Rev., 1972, 8, 167. P. Rigo, B. Longato, and G. Favero, Inorg. Chem., 1972, 11, 300. K. Kawakami, T. Komeshima, and T. Tanaka, J. Organometallic Chenr., 1972, 34, c21. M. Lenarda and W. H. Baddley, J. Organometallic Chem., 1972, 39, 217. W. M. Bedford and G. Rouschias, J.C.S. Chem. Comm., 1972, 1224. B. Corain, Co-ordination Chem. Rev., 1972, 8, 159. B. Crociani, T. Boschi, M. Nicolini, and U. Belluco, Inorg. Chem., 1972, 11, 1292. P. M. Treichel and W. J. Kuebel, Inorg. Chem., 1972, 11, 1285.

4 16

Spectrwscopic Piwper.ties qf Irrot-garlic rid Ot-gnnometcillic Conipoiniils

Table 5 (corti.) Cot,lpourld [ N i( CN ), L 12

Ni(CN),L, .5 Ni(CN),(PPr,), [L = Ph,P(CH,),PPh2] PdLL'CI, ( L = PPh,, L' = p-Me.C,H,NC, p-MeO.C,H,NC, C(NH Ph)N H C, H, * 0 Me, C( N HPh),. C(N HPh)N HC,H, - CI, etr.; L = AsPh,, L' = C(NHPh)NHC,H,-Me) [ Pt(OH)(CN Me),] [Pt(CSNH Me)(CN Me)(PPh,),]+ { Pt[C(NC,H,. Me)NHMe](CNMe)(PPh,),1 {Pt[C(NPh)NHMe](CNMe)(PPh,),J ' { Pt(NCMe)(CN Me)( PPh,),} +

327

328

+

329

Nitrosyk-v(C0) and v(N0) have been listed for a number of transitionmetal complexes, containing CO and NO groups, which are bonded to a triphenylphosphine substituted on to a resin substrate, (polymer)-CC,H,-PPh,, where (polymer) is a cross-linked polystyrene.330a The previously unknown mononuclear nitrosyl Cr(NO), has been prepared 330b by slowly streaming NO through irradiated Cr(CO), in hydrocarbon solution. Only three bands were found in the i.r. spectrum of the black-brown solid product, at 1721 cm-l [vas(NO)],650 cm-l [v,,(Cr-N)], and 496cm-l [8,,(NO-Cr-N0)]. v(N0) has been for a large number of rr-cyclopentadienylmolybdenum nitrosyl complexes. The following v(N0) wavenumbers were reported for molybdenum- and tungsten-nitrosyl [Mo(NO)CI,,], 1590 cm-l; [W(NO)Cl,],, 1590 cm-' (both bridging); Mo(NO)CI,(P~,PO)~ 1710 cm-l [with .(PO) at 1 180 cm-l and 1 1 3&1140 cm-l]; Mo(NO)Cl,(bipy) 1705 cm-l; W(N0)CI,(Ph,PO), 1650 cm-' [,(PO) at 1170, 1140 cm-'1. In (v-Cp)ReX(CO)(NO), v ( C 0 ) is at 1972cm-' (X = Me) and 1979 cm-' (X = H); v(N0) is at 1715 cm- I , 1722 cm-l, respectively.332 The variations of v(N0) in neutral radical anion, dianion, and radical cation tetrahedral derivatives related to Co(CO),(NO) and Fe(CO),(NO), have been discussed in terms of the electric charge distribution in these complexes, and have been related to data obtained by other techniques (especially e.s.r. and n.m.r.).,,, v(CO), v(NO), and v(CN) have been listed for a variety of isocyanide complexes and carbonyl-nitrosyl derivatives related to { Fe(CO),[S,C,(CF3)21)n.334 330

3y1

y33

3y4

( a ) J. P. Collman, L. S. Hegedus, M. P. Cooke. J. R. Norton, G . Dolcetti, and D . N . Marquardt, J . Anier. Chem. Soc., 1972, 94, 1789; (b) M. Herberhold and A. Razavi, Atigew. Cheni. Infernat. Edn., 1972, 11, 1092; (c) J. A. McCleverty and D. Seddon, J.C.S. Dalton, 1972, 2526, 2588. R. Davis, B. F. G . Johnson, and K . H. Al-Obaichi, J.C.S. Dalton, 1972, 508. R. P. Stewart, N. Okamoto, and W. A. G . Graham, J . Organotnetallic Chem., 1972, 42, C32. R. E. Dessy, J . C, Charkoudian, and A. L. Rheingold, J . Amer. Cheni. Soc., 1972, 94, 738. C. J . Jones, J . A . McCleverty. and D. G . Orchard, J.C.S. Dolton, 1972, 1109.

Vibr~itioti~I Spcc t 1 u of some Co-ordiiiat ell L igaiicls

417 Table 6 shows the assignments proposed by Schrciner ct ul. for v(Ru-N)/S(RU-N-O) and v(N0) in a series of complexes trans[Ru(NH,),(NO)L]'+.~~~ These figures suggest the existence of a vibrational trans-effect series: NH, < NCO- < N, < MeCO, < C1- < Br- < OH-.

Table 6 Sonie vibrational assigirmetits cr.niienumber-.Flcm-'

iti

Cornplex 1(Ru-N) ~ ~ u ~ I s - [ R u ( N H ~ ) ~ ( l+3)]Cl:l NO)(N ~~U~~-[RU(NH.J,(NO)(NCO)]I~ trans-[Ru(NH,),(NO)(N,)]I, trans- [ Ru(N H3)4(N0)(0Ac)] I, fr~ns-[Ru( N H3)4(NO)CI]CI, trans-[Ru( N HJ4( NO)Br]Br, Irntts- [ Ru(N H3)4( NO)( 0H )]Cl,

tl.ans-[Ru(NH,),(NO)L,]" oj or ~ ( R L I - N - O ) 602 615 595 595

608 59 I 628

v(N0) 1 YO3 1890 1884

I882 I880 I870 I834

Ru,(CO),,(NO), and O S ~ ( C O ) ~ ~ ( Ngive O ) , v ( C 0 ) absorptions in solution characteristic of terminal carbonyls in trimetallic carbonyls of CzVsymmetry. Their similarity suggests that they are isostructural. v(N0) is found in the solid-phase spectra at 151 7, 1500 cm-' (Ru), 1503, 1484 cm(Os), together with peaks at 723 (Ru), 739 (0s)cm-', believed to be associated with the double nitrosyl bridge (lO2)?

(102)

v(N0) in a variety of tertiary phosphine- and arsine-nitrosyl halide derivatives of Ru and Os, mostly of the form MX3(NO)(ER&, spans the range 1829--- 1876 cm-' (M = Ru), 181 1-1853 cm-' ( M = O S ) . ~ " ~ Vibrational spectra have been assigned for M1,[M'(NO)Xs] (MI = K or Cs; M' = Os", Rul', or Irl'l; X = CI, Br, or I ) with some assistance from 16N-substituted The NO stretch increases in wavenumber in the order 0s" < Ru" < Ir'", while v(M-N) decrease in the same sequence (for constant X). This is explicable on the basis that the M'-N bond has more n-character in the 0 s complex, and that the higher oxidation state in Ir"' decreases the M'-N bonding. In Table 7 are listed v(N0) for some neutral and cationic osmium nitrosyl carbonyl~.~~* A. F. Schreiner, S. W. Lin, P. J. Hauser, E. A. Hopous, I). J. Hamm, and J. D. Gunter, Itiorg. Chem., 1972, 11, 880.

J . R. Norton, J. P. Collman, G . Dolcetti, and W. T. Robinson, Inorg. Chem., 1972, 11, 382.

D. Robinson and M. F. Uttley, J.C.S. Dtrlfon, 1972, 1 ; (b) M. J. Cleare, H. P. Fritz, and W. P. Griffith, Spectrochim. Acra, 1972, 28A, 2013. G . R. Clark, K. R. Grundy, W. R. Roper, J. M. Waters, and K . R. Whittle, J.C.S. Cltem. Cotnm., 1972, 119. ( 0 ) S.

4 18

Spectroscopic Properties of Itrorgonic mid Organometaliic Comporuids

v(N0) in Co"(dmgH),(NO) is at 1641 crn--l (shifted to 1615 cni-l o n 16N Co111(dmgH),(N0,),0H2 gives the follow4ng wavenumbers associated with the nitro-ligand: v,,(NO,) 1453; v8(NOz) 1321 ;

Table 7 Nitrosyl stretching wat..enirmbers/cm-l for some osmiiim nitrosyl carbonyls

Coniplex OsH(CO)(N 0)(PPh,), [Os(CO),(NO)(PPh,),l+ [Os(CO)(NO)(PPh,),l+ [Os(CO)( N O)( PPh, Me),] + [Os(CO)( NO)( Ph,PC H,CH,PPh,)( PPh,)] [Os(CO)(NO)(RNC)(PPh,),1+

v(NO) 1620 1750 1705 1700 1700 1700 (NC 2150)

S(ON0) 819; pw(NO,) 615 cni--l (at 1416, 1300, 812, 604cni-' in the I6NO, complex). I n [(.rr-Cp)Co(NO)(PPh,)]+PF;, v(N0) is at 1848 cin-l, in [(v-Cp)Co(P(C,Hll),}]+PF; 1840 cm--l, and in [In-Cp)Rh(NO)(PPh,)]+PF, at 1831 v(N0) wavenumbers have been listed for a range of oxidative-addition products obtained from M(NO)L,, (M = Co, Rh, or I r ; L = PR,), typically C O I ~ ( N O ) ( P P ~ ~ ) , . ~ * ~ ~ The nitrosyl stretching frequency in RhCI(NO)(PPh,),, RhCI(N0)(AsPh,),, RhCl,(NO)(PPh,),, and RhCl,(NO)(AsPh,), is at 1629 k 1 cm-', i.e. it is independent of the EPh, ligand and of the oxidation state of the Rha3*l The cationic nitrosyls [IrCI,(NO)L,]+ (L = PPh, or AsPh,) react with alcohols to give neutral Ir"' complexes containing bound alkyl nitrates, with characteristic absorptions at 1550, 1400, 1100, 970, 880-835 cm--l [IrC1,( RONO)L2].342 [Ni(tep)NO]+BF, [tep = (103)] gives a nitrosyl stretch at 1760 cm -l, together with characteristic tep and BF, bands.343 hl e

339 34a

341 34a

343

M. Tamaki, I. Masuda, and K . Shinra, Bull. Chern. SOC.Japan, 1972, 45, 171. (a) N. G. Connelly and J. D . Davies, J . Urganometallic Chern., 1972, 38, 385; (b) G. Dolcetti, N. W. Hoffmann, and J . P. Collman, Znorg. Chim. Acra, 1972, 6, 531. Yu. N. Kukushkin, L. I. Danilina, and M . M. Syngh, Russ. J. Znorg. Chem., 1971, 16, 1449. C. A. Reed and W. R. Roper, J.C.S. Dalton, 1972, 1243. D. Berglund and D. W. Meek, Inorg. C h ~ n i .1972, , 11, 1493.

Vibrational Spec trtr of some Co-ordincrtecl Ligunds

419

A study has been made of v(N0) in the complexes trurrs-[PtX(NO)A,1X, (X = CI, Br, H S 0 4 , or NO,; A = NH,, MeNH,, PrnNH,, or ?en). v(N0) increases when C1-- o r Br- are replaced by HSO; o r NO;, as does the ease of hydrolysis of the complex. The NO was said to bc acting as a one-electron ligand. 344 A number of other papers reported v(N0) data (see Table 8).345-349

'

"i(NO)(PPh,XI INi(NO)(CO)(PPh,),l+ {Ni(NO)(PPh,),[P(OPh),I} Co(NO)(PPhJ3 Co(NO)(CO)(PPh,), [Co(NO),(PPh3)2] [Co(NO),(diphos)] Co(NO)(diphos)(THF) Fe(N0)2(PPh3)2 Fe(N O),( di phos) [ Mo(NO)(CO),( diphos)]* [W( NO)(CO),(dip hos)] [ Fe(CO),(NO)L2]'PF; [L = P(OPh),, P(OMe),, PPh3, PPh,Me, PMe,Ph, PEt,, AsPh,, erc.] [Fe(CO)(NO)L,] 'PFg [L = P(OMe),, PMePh,, or PMe,Ph] { [Fe(Co)(No)(dPPe)I2(dPPe)l(PF,), [F~(NO)(~PP~)I~BP~, Fe(CO)(NO)(PPh3)2(C02Me) Fe(CO)(NO)(dppe)(CO,Me)

\

+

'

>

+

+

345

346

2

4 Phosphorus and Arsenic Donors v(PF) [and v(C0) where appropriate] have been listed for (n-Cp)V(CO),(PF,NC,H,,),, (n--Cp)Mo(CO),(COMe)(PF,NMe,), (n-Cp)Mo(CO)(C,H5)( PFaNEt2)2, (r-cp) (C0)2( PFBNC5H i o ) a 7 (r-Cp)Mn(CO)(PF,N C ,H lo), (rr-Cp),Fe,(CO),(PF,NEt,), (n--Cp)Fe(PF,NEt,)l, and related complexes.35o 344

348

347 3 4

y49

360

A. I. Stetsenko, N. V. Ivannikova, and V. M. Kiseleka, R i m . J . Inorg. Clirm., 1972, 16, 865. B. F. G. Johnson, S. Bhaduri, and N. G. Connelly, J. Orgnnometallic Cheni., 1472, 40,C36. B. F. G. Johnson and J. A. Segal, J.C.S. Dalton, 1972, 1268. H. Buttner and R. D. Feltham, Inorg. Chern., 1972, 11, 971. ~J. T. Mague and J. P. Mitchener, Inorg. Chem., 1972, 11, 2714. T. S. Srivastava, L. Hoffmann, and M. Tsutsui, J. Amer. Cheni. Soc., 1972, 94, 1385. R. B. King, W. C. Zipperer, and M. Ishaq, Itrorg. Chem., 1972, 11, 1361.

420 Spectroxopic Properties of' Itrorgnnic mid Or~Tcrnc,mc.rnllit.C70t?ipoutrds P-H stretching wavenumbers are found between 2295 and 2420 cm I in (n-Cp)Fe(CO),L, [(n-Cp)Mo(CO),L'li-, [(n-Cp) Mo(CO),L]+, Mn(CO),L'(Br), PhMn(CO),L', Cr(CO),L,, and Mo(CO),L, ( L = PPhH,; L' = PPh,H).351 Some assignments have been made of i.r. bands of Mo(NO),(dpm)X, (dpm = bisdiphenylphosphinomethane; X = CI, Br, or I), M(NO),(dam),X,, and M(NO),(dam)X, ( M = M o or W ; X = CI, Br, or I ; dam = bisdiphenylar~inomethane).~~~ The complex Mn,(CO),(PH,) has been prepared and the position of the PH, ligand, determined by i.r. spectroscopy in the v(C0) region, is that of an equatorial substituent on a dimanganese decacarbonyl The following i.r. data have been reported 354 for (n-Cp)Mn(CO),(PF3)3-n (n = 2, 1, or 0): n = 2, v ( C 0 ) 1993, 1930 cm-l, v(PF) 846 cm-I; n = 1, v(C0) 1953 cm-l, v(PF) 846cm-'; n = 0, v(PF) 910, 836cm I, 6(PF3) 560, 545 ern-'. v(PF) wavenumbers are found to increase as shown in the series of iron-PF, complexes: Fe(PF,):- < Fe(PF,), < Fe(PF3),X2 (X = C1, Br, or I).355 This can be explained in terms of changes in Fe basicity, leading to less Fe -+ PF3 back-bonding, with a consequent increase in the P-F bond order. The complex (104) gives v(PF) at 867 and 853 cm-l, with v(C0) at 2104, 2065, 2042, 2031, and 2018 c1n-l (C,, symmetry requires the presence of five C O

v(PF) wavenumbers have been listed 3 5 6 b for (h2-C5HB)Fe(PF3)3,(/PC,H,)Fe( PF3),H , and K +[(h5-C5H,)Fe(PF312] -. v(C0) and v(PF) bands in the series of con~plexesKu(PF,),(CO),.,, In each where x = 1 - - 5 , have been reported by Lldovich and case there are more bands than could be explained by the presence of only one isomer. Yellow [cis; 2v(CO) at 2001 cin-l] isomers have been isolated for the complex R u ( C O ) , ( P P ~ , ) , I , . ~ ~ ~

3s2 3s3 554

355

366 yb7 36w

P. M. Treichel, W. K . Dean, and W. M . Douglas, J . Orgarrometullic Chem., 1972, 42, 145. J. A. Bowden, R. Colton, and C. J. Commons, Austral. J . Chern., 1972, 25, 1393. E. 0. Fischer and W. A . Herrmann, Chenr. Ber., 1972, 105, 286. T. Kruck and V. Krause, Z. Naturforsch., 1972, 27b,302. T.Kruck, R. Kubelt. and A. Prasch, 2. Nuturforsch., 1972, 27b, 344. ( a ) W. M. Douglas and J. K. Ruff, Inorg. Chem., 1972, 11, 900; (b) T. Kruck and L . Knoll, Chern. Ber., 1972, 105, 3783. C . A. Udovich and R. J. Clark, J. Organometallic Chem., 1972, 36, 353. J. Jeffery and R. J. Mawby, J . Organorneta(1ic Chem., 1972, 40,C42.


421

In CoX2[Me2NPF21, (X = Br or I ) the i.r. spectra show359that the absorptions in the region 300&--2700crn-' are almost identical to those in the free ligand. This is believed to indicate the presence of uncoordinated N, and therefore co-ordination to the Co via the P atom. This conclusion is supported by the increase in wavenumbers of v,(PF,) on complexing (from 770 cni-' to 812, 805 cm-l for X = I or Br, respectively), which is known to be associated with the presence of M-P bonds. An unassigned i.r. spectrum has also been reported360 for the closely related complex Co{[Me,N]2PF},12. The presence of an intense i.r. band at ca. 522 cm- in the i.r. spectra of [CoX(hdf),(PPh,)] complexes (where X = C1, Br, I , or NO,; hdf = benzildioximato) is said to be characteristic of the co-ordinated PPh, group.361 An analogous band at 455 cm-l is found in [CoX(hdf)(SbPh,)]. Ligand-exchange reactions occur in solution between the dimeric complexes [RhCI(L),], (L = PF3 or CO), to give Rh,Cl,(PF3),(CO),-T (x = 1, 2, or 3) as shown by changes in the i.r. spectrum in the v(C0) region.362 The series of complexes (105; Y = I , CF,, C2F5, n-C,F,, or n-C,Fl5) all show bands characteristic of complexed PF, at 891 L- 8 cm-l and

The same authors have also reported v(PF) data on the 873 k 3 following:364 (h5-C5Me5)Rh(PF,),, (h5-CSMe5)IrF(PF2)(PF3),Re(CO),(PF,),Br, (h5-C5H,),Mo2(CO),(pF3), (h5-C5H5)Mo(CO),(PF,),, (h6-C,H,)Fe(CO)(PF,)I, MeMo(CO),(PF3)(h6-C5H5),and MeW(CO),(PF,)(h5-C6H5). In the series [RhX(PF,),],, where X = C1, Br, or I, v(PF) falls in the order C1 > Br > I, a trend paralleling that generally found in transitionmetal carbonyl halides.365 Similar data were also reported for IrCl(PF3),, II-CI(PF~)~, Rh(acac)( PF3),, I r(acac)(PF,),, HRh(PF3)4, H 1r(PF3l4, Rh2(PF,),, IT~(PF,)~, Rh,(PF,),, efc. J - ' ~T. :Itio

:Iu1

Nowlin and K . Cohn, Iirorg. Chenz., 1971, 10, 2387. T. Nowlin and K . Cohn, Inorg. Chem., 1972, 11, 560. A . V. Ablov, A. M . Gol'dman, and 0. A . Bologa, R i m . J . Inorg. Chem., 1971, 16, 937.

3et 369 :'lkd .Iti5

J . F. Nixon and J . R . R. King and A. R . H. King and A. bl, ..\. Bennett and

R. Swain, J.C.S. Dolron, 1972, 1044. Efraty, J . Orgatrometallic Chem., 1972, 36, 371. Efraty, J . Atner. Chem. Sor., 1972, 94, 3768. D. J . Patmorr, Inorg. Chem., IY71, 10. 2387.

422

Spectroscopic Properties of Inorganic and Organometaltic Compounds

The olefinic C H deformation has been assigned to an i.r. band in the range 971-91 5 cm-l in the following:36s RhCl(bdps),CH,Cl,; RhBr(bdps); JrCl(bdps),CH,CI, ; Ir(CO)(bdps),CH,Cl,; and IrCl(bdps)(PPh,), where bdps = 2,2'-bis(dipheny1phosphino)stilbene (106).

Ni(PH3)4 has been prepared and a low-temperature solid-phase Raman spectrum was This shows v(PH) at 2299cm-I, 6(PH) at 1057 cm-l, and v(Ni-P) at 296 cm-l, characteristic of co-ordinated PH,. Internal vibrations of the PMe, ligand have been assigned in Ni(PMe,);+ and Ni(PMe3)2X2.3sa The following assignments have been proposed for Nil,(CO)(PMe,),: v(CH) 2975, 2912, 2905 cm-l; v(C0) 2020, 1974 cm-l; 6(CH,) 1416, 1408, 1403, 1386, 1297, 1285, and 1279cm-l; p(CH3) 941, 856, 849cni-'; v(P-C) 738, 679 cm-l; 6(CPC) 374, 277, and 266 ~ m - ~ . ~ ~ ~ Some approximate assignments have been given for the PPh, bands in (Ph,Y)2Pt,SiF4,370and (107).,'l Ph,P,

Ph,P

BC13

1

, Pt-PPh3 I BCI,

( 107)

1.r. bands in [PtCI,(P(OEt),),] at 800, 980, 1050, and 1165 cm are assigned to vibrations of the P-0-C group.372 Unassigned i.r. spectra have been listed for a number of Pt" and Pt" complexes of cis- and ~ ~ u ~ s - P ~ , P C H = C H P P ~ , . ~ ' ~ Assignments have been made to the so-called v(As-Ph) and v(P-Ph) modes, together with v(CN), v(CS), and v(C0) as appropriate, for [Ag(AsPh,),]X (X = NO3, C104, or BrO,) and [Ag(EPh,),X] (X = SCN or NCO; E = P or

3R7 9eH

ae8 370

371 s7s

s74

M. A. Bennett, P. W. Clark, G . B. Robertson, and P. 0. Whimp,J.C.S. Chem. Corrm., 1972, 101 1 . M . Trabelsi, A . Louterlier, and M. Bigorgne, J . Organometallic Chem., 1972,40, C45. A . Merle, M . Dartiguenave, and Y . Dartiguenave, J . Mol. Structure, 1972, 13, 413. M. Pankowski and M. Bigorgne, J . Organometallic Chem., 1972, 35, 397. T . R. Durkin and E. P. Schram, Inorg. Chem., 1972, 11, 1048. T. R. Durkin and E. P. Schram, Znorg. Chem., 1972, 1 1 , 1054. A. D. Troitskaya and Z. L. Shmakova, Russ. J . Inorg. Chem., 1971, 16, 872. R. B. King and P. N. Kapoor, Znorg. Chem., 1972, 11, 1524. R. N. Dash and D. V. Ramana Rao, 2. anorg. Chem., 1972, 393, 309.


423

5 Oxygen Donors Molecular Oxygen, Peroxo-, and Hydroxy-complexes.-The potentially terdentate ligand thiodiethanol forms I : 1 complexes with the chlorides of Cr"', Mn", Ni", Co", and Cu", for which i.r. data show that all the hydroxy-groups are co-ordinated to the metal. 1 : 2 Complexes are also formed, in which the presence of i.r. bands as low as 2680 cm-l shows that two of the hydroxy-groups are not co-ordinated to the v(0H) wavenumbers and several bands in the 840-1000 cm-l region have been listed for FeL;+ and RuL;+ (where L = phenanthroline or bathophenanthroline) and for Cu(neocuproin),f. It is claimed that water is co-ordinated to the metal cations, in addition to the three bidentate ligands, although this conclusion appears to be open to question.37s The ClO; ion is believed to be co-ordinated to the Fe in Fe(pq),(CIO,),, in a unidentate fashion [vl = 1040, v2 = 925 cni-I; pq = (108)].377

The main i.r. absorptions of [RuOj(py),], [Ru(OH),(py),(bipy)], and [Ru(OH),(py),(phen)] have been listed.37BThe characteristic bands of py were assigned, and for the OH complexes v ( 0 H ) at 3380, 3390cm-l, respectively. The dioxygenyl complexes Ru(O,)(CO),(PPh,), and OS(O,)(CO)~(PP~,), give bands assignable as v(M-02) at 849cm-' (M = Ru), 820cm--' ( M = O S ) . The ~ ~ ~ closely related complex Ru(PhC=CPh)(CO),(PPh,), possesses an i.r. band assigned to v(C=C) at 1776 cm-'. Alkyldioxycobaloximes (109; L = py or H,U), prepared by the irradiation of some alkyl(pyridinato)cobaloximes in the presence of oxygen, give

B. Sen and D. A. Johnson, J . Irzorg. Nuclenr Chem., 1972, 34, 609. S. Burchett and C. E. Meloan, J . Inorg. Nuclear Chem., 1972, 34, 1207. w7 C. M. Harris, S. Kokot, H . R . H . Patil, E. Sinn, and H . Wang, Austrczl. J . Chern., 1972, 25, 1631. T. Ishiyarna and Y . Koda, Itiorg. Chern., 1972, 11, 2837. 3 7 8 B. E. Cavit, K . R . Grundy. and W. R. Roper, J.C.S. Chem. Comrri., 1972, 60. 376 378

424

Spectroscopic Propcrties of Inorganic arid Organometallic Compoitnds

a characteristic i.r. band due to the peroxy-grouping, in the 8W-- 900 cm 381

In the dioxygen complexes RhX(O,)(PPh,),L, where X = CI, Br, or 1 and L = an isocyanide, v ( 0 - 0 ) and v(Rh-0) (presumably strongly coupled) are found at ca. 890cm I , en. 580cm-', respectively. These assignments are based upon the use of 180-substitution,and the spread in the values over all the complexes studied was very v ( 0 - 0 ) in lrX(OOBut),(CO)L,, where X = C1 or Br, L z= PPh, or AsPh,, is between 880 and 890 ~ m - ~ . ~ ~ ~ ~ [Ir(02)(dp)2]CI, where d p = cis-vinylenebis(diphenylphosphine), gives an i.r. band assigned as v(1r-0,) at 843 ~ 1 n - l . ~ ~ ~ A band described as v ( 0 - 0 ) is seen at 838 c m - I in the solid-state i.r. spectrum of [Ir(O,)(AsMe,Ph),] BPh, . The proposed structure of the cation is ( I 10).3H4rL +

L

L ... I .:o ,1r; I L l O L A review of compounds of the Pt metals containing chelating dioxygen includes data for and discussion of the 8-900 c m - l i.r. band assigned to V ( ~ - 0 ) . 3 ~ 4 b Partial i.r. data are given for the complexes MCI3,7H,O ( M = La, Ce, o r Pr) and M'CI3,6H20 (M' = Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y) and discussed in terms of the extent of hydration of the M 3 t ionS.384C 1.r. wavenumbers have been listed for La(1O3),,3Hz0, La(103),, and I~alO,,nH,O (where n = 1, 2, or 3). The only suggested assignments were to v ( 1 - 0 ) (ca. 800cm-'), 141-0-1) (cci. 550cm-'), and t o S(1-0) (ca. 450

Acetylacetonates and Related Complexes. --1.r. data, for the purposes of characterization, have been listed for a number of Crll' /3-diketonates.3*6 The i.r. spectra of the dimeric 8-diketonate complexes [(/I-dik),Fe(OR)], ( 1 1 1 ; R = Me, Et, or Pr') have been listed, and bands characteristic of the C. Fontaine, K . N. V. Duong, C. Merennc, A . Gaudemer, and C. Ciiannotti, J . Orgrrtrotttetdlic*Chetri., 1972, 38, 167. C. Giannoti, B. Septe. and D. Benlian. J. Org-gnmt~terrrllic* Chem., 1972, 39, CS. :IxL ( a ) A. Nakamura, Y. Tatsuno. and S. Otsuka, fnorg. Chem., 1972, 11, 2058; ( h ) B. L. Booth. R . N. Haszeldine, and G . R . H. Neuss. J.C.S. Chem. Cotrtnt., 1972, 1074. ;IM S. Doronzo and V. D. Bianco, f m r g . Chem., 1972, 11, 466. :IH4 ( a ) L. M. Haines and E. Singleton, J.C.S. Dcrltott, 1972, 1891; (6) V. J. Choy and C. H. O'Connor, Co-ordination Chent. Rev., 1972, 9, 145; (c) S. E. Kharzeeva and V. V. Serebrennikov, Tr. Tontsk. Gos. Uttir?.,1971, 204, 350. yH6 M. Odehnal, Motrcttsh.. 1972, 103, 1615. y"B A . 1). Tanejn. K . 1'. Srivastava, a n d N . K . Agar\val, J . ftwrg. h'rrtlfwr C'/rvtu,, 1072. 34, 3573.

:w'' :In1

Vihrntionnl Spectra of some Co-ordinnted Ligands r O

0,I

Fe:

0'1

LO

435

R 0I 0 0 I 0 R' 0

>Fee

0

(1 1 1 )

various -OR groupings identified [/3-dik dpm (2,2,6,6-tetramethylheptane-2-5-dione) or a ~ a c ] . ~ ~ ' The following complexes have been prepared which contain acetylacetone as a neutral ligand 3L19 CoCl,(acacH), CoBr,(acacH), ZnCl,(acacH), Ni Rr,(acacH),, CrCl,(acac)(acacH), CrBr,(acac)(acacH), and M nBr,(acacH),. The Co, Zn, and Ni complexes gave ketonic v(C=O) bands at [a.1720 cm-' and ca. 1700 cm- l ; the Cr species gave these and others due to the a m - - chelate, while the Mn complex gave bands only at 1627 and 1564 cm I , assigned to v(C=O) and v(C=C) of the enolic form of acacH. The preparations of CoCI,(L), CoBr,(L), and ZnCI,(L), where L = ethyl acetoacetate (etacH) or ethyl malonate (etmalH), and of MnBr,(ettnalH) have been reported. Small shifts in the keto v(C:=O) were observed on co-ordination, and v(C=O) of the enolic tautomer of etmalH was also seen (1618-1658 cm-l), although this is not present in the free ligand. For the etacH complexes, the keto/enol ratios were similar to those in the free ligand."O The i.r. spectra of (L)Co(salen), where 1, = /3-diketonates such as acac, bzac (benzylacetonate), or tfac (trifluoroacetylacetonate) and salen = NN-ethylenebis(salicylaldimine), are all consistent with the presence of oxygen-chelating /3-diketonate l i g a n d ~ . ~ ~ ~ Some i.r. data have been listed for a number of Co" and Co"' complexes of 1,5-dialkylpentane-2,4-dione~,~~~ and for a closely related series of Ni" complexes [NiL,( H20)J2. (L = heptane-3,5-dionato, nonane-4,6dionato, 2,6-dimethylheptane-3,5-dionato, 2,8-dimethylnonane-4,6-dionato, and tridecane-6,8-dionat0).~~~ In the latter, co-ordinated water was detected by the presence of a sharp, strong i.r. band in the range 3350-3400 cm-l ; the electronic spectra were consistent with six-co-ordination at the Ni, hence the dimeric formulation (two bridging oxygens). A number of hexafluoroacetylacetonato complexes of silver(i), of the general type Ag(hfacac)(olefin), have been prepared.3g4 In all cases the /3-diketonate ligand was acting as an 00'-chelate [giving bands due to v ( C - 0 ) in the region 1630 - 1670 cm-l]. This behaviour is in contrast to =;;

:38R1

C.-H. Wu, G . R. Rossman, H . B. Gray, G. S. Hammond, and H . J. Schugar. Inorg. Chem., 1972, 11, 990. :iHn Y . Nakamura, M . Gotani, and S. Kawaguchi, Bull. Chem. SOC.Jclprin, 1972, 45, 457. :IHH Y . Nakamura, K . Isobe, H . Morita, S. Yamazaki, and S. Kawaguchi, Inorg. Chem., 1972, 11, 1573. :IHn H. Morita, Y . Nakamura, and S. Kawaguchi, Bull. Chern. SOC. Japnn, 1972, 45, 2468. :'01 R. J. Cozens and K . S. Murray, Austral. J . Chem., 1972, 25, 911. : 4 Q 2 I. Yoshida, H. Kobayashi. and K. Ueno. Ritll. Chetn. SOC. Japan, 1972, 45, 2768. '8'' 1. Yoshida, H . Kobayashi, and K. Ileno. Bit//. ( ' h e m . SOC.Jcippnn. 1972, 45, 1-11 1 . W. l'artenheimer and E. H . Johnson, l / w r g . Chevi., 1972, 11, 2840.

:IH7

426

Spectroscopic Properties of Inorgmic and Organometnilic Compounds

that of Pd(hfacac),PPh, for example, in which the p-diketonate is bonded U ~ C I one oxygen and the y-carbon atoms, giving bands at 1768, 1723 cm-l [v(C=O)] and 1656, 1629 cm- [v(C=O)]. I n the complexes (1 12; R’ = R2 = H), ( I 12; R1 = Me, R2 = El), and ( 1 12; R 1 = R2 = Me), one band is found at cn. 1720 cni--l that is due to

I

R2

I

Rr

(1 12)

unco-ordinated v(C=O), with a complex pattern between 1600 and 1500cm-l due to chelate ring The dinuclear series ( I 13 ; R’ = R2 = H), and (113; R1 = H, R2 = Me) lack the former feature. 1.r. data have been listed for a number of Hg” p-diketonate complexes.39s Raman (M = La, Pr, or Gd) and i.r. ( M = La, Ce, Pr, Nd, or Gd) spectra have been obtained and assigned for the complexes M(dpm),, where dpm = (1 14).397Detailed assignments were proposed for internal

0

0 ( 1 14)

ligand vibrations ( > 400 cm-l), with ‘v(M-0)’ at 392 -403 cni-l and G(o.o.p.)(OMO) at 245---248 cm l . 1.r. spectra were published (with no lists of assignments, or even frequencies) for Nd(thd),, Nd(thd),,DMF, Pr(thd),, Er(thd),,DMF, and Er(thd), (thd = the anion derived from 2,2,6,6-tetramethylheptane-3,5dione, i.e. the ‘dpm’ of the previous reference).398 v(C=O) wavenumbers for (C,F,),TIX, (C6F,),(Ph3PO)TIX, and (C,F&(Ph,AsO)TIX [X = CH,COCHCOCH, (acac), CF,COCHCOCHB (tfac), CFJZOCHCOCF, (hfac), PhCOCHCOCH, (bzac), PhCOCHCOPh (dbm), or quinolin-8-olate] are in the region expected for chelating 3u6 3H6

: lu i

F. Sagara, H. Kobayashi, and K . Ueno, Birll. (’hem. Soc. Jupan, 1972, 45, 794. A. D. Taneja, K . R. Srivastava, and N . K. Agarwal, J . Inorg. Nuclerrr Chem., 1972, 34, 2980. H.-Y. Lce, F. F. Clcvcland, J. S. Ziomek, and F. Jarke, Appl. Spectroscopj,, 1972, 26, 251. V. A. Mode and D. H. Sisson, Itiorg. Nuclear Chem. Letters, 1972, 8 , 357.

Vibrational Spectrn of some Co-ordinnted Ligands 427 p-diketonate groups. In the second and third series, v(P=O) or v(As=O) is lowered, indicating co-ordination z-io the 0 atom.399 The anionic 2,4-pentanedionato complexes [X,Sn(C,H,O,)]- (X = CI, Br, or I) all show bands at m. 1560 cm - l and co. 1580 cm - l due to the 00'-chelated Iigand~.~OO v(C=O), v(C=C), and v(Sb-0) were listed for the monomeric dihalogenodiaryl(acety1acetonato)Sb" compounds ( p - Y C,H,),SbX,(acac), where X = F, CI, or Br and Y = NO,, CI, H, Me, or MeO.,O1 1.r. data for a series of compounds R,,SbCI, ,,(acac) [v(Sb- 0),v(C=O), v(C=C)] show that increased substitution of C1 by R leads to a weakening of the Sb-(acac) interaction [as shown by decreased v(Sb-0) and increased

-

.

v(C=0)].402

Carboxy1ates.--A

normal co-ordinate analysis has been performed to investigate the influence of ligand polarization and the strength of the M-0 bonds o n the frequencies of the in-plane vibrations of the group ( 1 15; M = C or N).403n 0 I

1.r. spectra have been reported for C1,H3,C0,H and CCI,CO,H, their Co, Fe, Ni, Mn, Mg, and Cu salts, and complexes of these salts with the Assignments have been proposed ,04 for the va8(C02) and v,(CO,) vibrations in a number of eight-co-ordinate lactates, mandelates, and isopropylmandelates of Zr'" and Hf". Some i.r. wavenumbers were listed in a paper 405 on Cr, Mn, Fe, and A1 complexes of C(OH)(CF3),C02H. The i,r. spectra of the bis(phenylglycol1ates) (PhCHOHCO,),M, where M = Mn", Co", Ni", Cu", or Zn", show bands due to v ( 0 H ) at 31 30-3270 cm- l , v ( C 0 , ) at 1545-1 585 crn-', and 6(OH) at 1003 1025 cm-'. The relevance of these data to possible modes of co-ordination was G . B. Deacon and V. N. Garg, Airstral. J . Chern., 1971, 24, 2519. D . W. Thompson, J . F. Lefelhocz, and K . S. Wong, Inorg. Chem., 1972, 1 1 , 1139. N. Nishii and R . Oknwara, J . Organonietdlic ChPm.. 1972, 38, 335. I o 2 H. A. Meinema, A. Mackor, and J . G . Noltes, J . Orgnnometallic Chern., 1972, 37, 285. I o 5 (a)B. Tardvel, G. Chauvet, P. Deiorme, and V. Lorenzelli, J . M o l . Structitre, 1972, 13, 283; ( 6 ) 0. E. Lavenevskii and E. G . Yarkova, Izzjest. Akad. Nrruk. Kirg. S.S.R., 1972, 56. E. M . Larsen and E. H . Homeier, fnorg. Chcrn., 1972, 11, 2687. .I. T. Price, A. J. Tornlinson, and C. J. Willis, Cnrrad. J . Chern., 1972, 50, 939. 4 0 8 K. N. Kovalenko, D. V. Kazachenko, V. P. Kurbatov, and L. Ci. Kovaleva, Rriss. J . friorg. Chem., 1971, 16, 1303.

Ioo

428

Spectroscopic. Properties of Inorganic arid Organometallic Compounds

Fe(02CH)L2,where L = PEtPh,, has been prepared by the insertion of C 0 2 into the Fe-H bond of FeH4L3or FeH,(N2)L3.407The presence of the formate group is indicated by the i.r. absorption at 1590cm-1 [vaS(CO,)] and 1370 cm-l [v,(C02)]. The Ru carboxylato-complexes [Ru2(HC02),CI], [Ru,(MeCO,),CI], [RU~(CH,C~CO~)~CII, and [Ru(OH)(CC1,CO2),(H,O)] all give rise to characteristic vItS(CO2),v8(C02)bands of co-ordinated c a r b o ~ y l a t e . ~ ~ ~ In (HCOO)Ru(PPh,),(H)(toluene), vns(C02)is seen at 1553 cm- l , with v8(C02) at 1310 cm-' and v(CH) (of the formate ligand) at 2895 and 2805 cm-l. In Rh,H,(CO,)(PPh,),(toluene), the co-ordinated carbon dioxide gives v,,(CO,), v,(CO,) bands at 1460, 1300 cm-l, respectively.40s The distinction, using i.r. spectroscopy, between unco-ordinated, unidentate, and bidentate carbonate ion has been examined during a study of carbonato-cobaltate complexes, e.g. in [CO(NH,),]~+(CI,CO,)~ -, v3 of free C0:- is at ca. 1380 cm-l, whereas in [Co(NH,),(CO),]Br (unidentate carbonate) this feature is split, giving absorptions at 1370 and 1450 cm-'. In [CO(NH,)~(CO,)]CI (with bidentate carbonate) this splitting is even more pronounced (1255, 1592 ~m-').~lO As part of a study of the kinetics of reactions involving p-amido-pcarboxylato-cobalt(1ri) complexes, Scott and Sykes have listed the values of v,,(C02) and vs(COz)for acetate and formate ligands, and the separations of these bands with different degrees of co-ordination *11 (see Table 9).

Table 9

Cavboxylate stretching frequertcies (waueriutnbers}cni--') in acetato- and formato-complexes of cobnit(rr1) Conip1e.y 1v,,(CO) VS(C02) 1578 1425 Na+MeCO, I603 1380 [CO(NH,)~(M~CO~)]~' 1530 1410 [(NH,),Co-p-(NH,, MeCO2)-Co(NH,),I4 1535 1440 [(NH,),Co-p-(OH, OH, MeC02)-Co(NH,),13i 1590 1355 Na+HCO; 1345 1640 [Co(NH3),(HC0,)l2 1365 1570 [(NH~),CO-/L-(NH~, HCO,)-Co(NH,),]" 1355 1550 [(NH,),Co-p-(OH, OH, HC02)-Co(NH&I3' +

S O I ~ J

A V

I53 223 I20 95 235 295 20 5 195

1.r. spectroscopy has been used to confirm that the acetato C=O group is co-ordinated to Co in the ethylenediamine-A"'-diacetato-complexes of

CollI 412 v(C-0) wavenumbers of co-ordinated carbonate ion in complexes [Co(N),CO,]+, where (N), = 4NH,, [?(en)], etc., show a linear relationship with the C-0 bond length.**, 4u7

4un 4u0

Olu

)IJ

V. D. Bianco, S. Doronzo, and M . R o w , J . Orgationietallic Chem.. 1972, 35, 337. M. Mukaida, T. Nomura, and T. Ishimori, Bull. Chern. SOC.Japan, 1972, 45, 2143. S. Komiya and A. Yamamoto, J . Orgutiotiietallic Chem.. 1972. 46, C58. R. D. Ciillard, P. R. Mitchell, and M. G . Price,J.C.S. Dalfon. 1972, 1211. K. L. Scott and A. G . Sykes, J.C.S. Daltoti, 1972, 2364. K. KurodLt,BIIII.Chenr Soc. Jopriri, 1972, 45, 2176. V. S. S d s l ~I , I I I O I ~ Cliittl. . Acttr, 1972, 6 , 264.

Vibrational Spectra qf some Co-ordinateti Ligantls

420

1.r. (4000--200cm-') spectra have been shown for the Co" and CU" salts of d-, I-, and dl-forms of mandelic acid, M(PhCHOHC02).r, and bands have been listed with some proposed assignment^.^'^ Two different forms of each of the ClOh and Br- salts of (116) have been obtained, showing different i.r. spectra. The spectra of the unprotonated compounds, of the new complexes ( 1 17), and of various deuterioderivatives in the u(C0) ranges (1 100- 1800 cin-l) were discussed in detail,

L

including the possibility of distinguishing between uni-, bi-, and ter-dentate oxala to-cobal t(m) ami nes. 415 va,(COz) of the carboxylato-groups i n the complexes [Co(RCO,)(NH3)6I2+, ~ ~ ~ Z ~ ~ ~ ~ , , and ~ ~ ~ ~~ ~~ ~ 2 ~~ ~~ ~ ~ ~ ~ z 3 ~ ~, where R = H, Me, CH,CI, CHC12,CCI,, CH,F, CHF2, CF,, or C O T , have been listed.416 I n the i.r. spectrum of [CoL(H20)],2H,0, where H,L = trimethylenediaminetriacetic acid, the presence of a strong sharp absorption at 1620 cm-' is believed to indicate that all the three carboxylato-groups of 1, are ~o-ordinated.~" Unassigned i.r. spectra have been listed for potassium cis- and transbis(oxalato)diaquorhodate( 1 1 1 ) . ~ ~ ~ The complex (118) gives bands due to u(C=O) at 2075, 2005, and 1988 cm-l, and u(C=O) of the bridging carboxylate group at 1580, 1440 cm-l [Va,,,(CO,), respectively]. The monomeric compound (1 19) gives u(C=O) at 1980 cm - I , with u(C=O) at 1610, 1470 cnir'. These are R I

(lb

4L6

A. Ranade, 2. anorg. Chetn., 1972, 388, 105. K. Wieghardt, 2. anorg. Chetn., 1972, 391, 142.

H . Siebert and G . Tremmel, Z . anorg. Chem., 1972, 390, 292. M. Tanaka, K. Sato, and H. Ogino, Inorg. Nucletrr Chem. Letters. 1972. 8, 93. N. S. Rowan and R . M. Milburn, Inorg. Chem., 1972, 11, 639.

,~

1~

"~

~ +

4 30

S p c c 1I*OSCo/Iic Propert ies of l i t orgni r ic

( Ii

r r l 0rganomet allic C nmpoi

d s

in agreement with the structure shown, i.e. the acetate is bidentate and the rhodiuin is f i v e - c ~ - o r d i n a t e . ~ ~ ~ viLs(CO2) and vs(COz) have been listed for IrCIH(PPh,),(KCO,), where R = Me, Et, Pr, Ph, H, CF3, CH3CHCI, or p-02N.C6H4, and IrCIO(PPh,),(CH,CO,) (see Table 10) and for a number of complexes of the

Table 10 Carboxyl stretching 1r CI H( P P h 3) 2( RCO ,)

R CHI C2H, C3H,

c,145

H C F3 CH,CHCI ~ I - O ~C6H4 N. IrCID( PPh,),(CH,CO,)

(wauenurnbers/cm--l) ,for. Yls(CO2) 1535 1595 I530 1590 I550 1710, I680 1547 1534 1535

VB(C0,) 1445, 1423, 1412 1438 1408 1418, 1401

1345, 1279 1410 1410

1420 1338

general formula IrCIHL,L’(RCO,), where L = PPh,, L’ = CO, py, PhCN, PMe,Ph, or p-Me.C,H,CN, and R = various ally1 groups, etr. (see Table 1 l).420 Cookson and Deacon have reported similar data for a number of nickel carboxylates (see Table 12). The separations are rather large,

Table 1 1 Cnrboxyl sti~c~rchiirg i*ihr.atioiw IrCl H(PPh,),L’( RCO,) L’

co co

R OH, CH3 (D complex)

co

co

CO

CZH, C3H7 C,Hj

co co co

cF3 c F I ,cr4ci

C,H,N C6 H6N C,H,N CBHSCN C,H,CN I’Me,Ph p-Me. C,H4CN 41D 4’20

4”1

14

CH:,

C2t%

C,Ij!, c3i3 C:,r-17

c,1-15 CH3

lJ,J

CO,) 1631 1613 1633 1618

1626 1622 1621 1612 1687 I654 I632 1636 1636 1632 I639 1626 1630 1630

()vaL.eiriirnber.s/cni--’) fiw

[v(C=O) 20261 1311 1351 1325 1335 1338

[ v ( C g O ) 20601

1362 I330 1272 1355 1356 1320 1354 I355 1323 1352

[v(C=O) 20361 [v(C=O) 20051 [v(C==O) 20251

[v(C=O) 2010,201 81 [v(C=O) 20351 [v(C=O) 20251

G. Csontos, B. Heil, and L. Mark6, J. Organoriietallic Cheni., 1972, 37, 183. S. A. Smith, D. M. Blake, and M. Kubota, Inorg. Chem., 1972, 11, 660. P. G. Cookson and G. B. Deacon, Austral. J. Chem., 1972, 25, 2095.

Vihrntionnl Spectra of sowe Co-ordiiznted Lignrirls

43 1

Table 12 Carboxyl stretcliitig uibrations (~~c7t;etiutztber.~/cm-~) fur- some Ni curbox y la t c cot nplexes

co1111)0Ill1d ( C,F,CO,),Ni(bipy),2 H,O

(C,F,CO,),Ni(bipy), H,O ( p- M e 0 - C, F4* CO,),N i(bi py),2H,O ( p- M e 0 C , F, - CO,),N i( bi py ) ( p - M e 0 * C,F, C02),Ni( phen),H,O (p - M e 0 - C,F, - C02)2Ni(phen) (p-EtO. C,F,. C02),Ni(bipy),2H,0 (p-EtO C,F,. CO,),Ni(bipy) (p-EtO C,F, CO,),N i(phen), H,O

-

-

-

-

I?as(

CO,) 1610 I620 1640 1644 1627 1620 1639 1644 1620

1

'S(C0,) 1365 1373 1370 1381 1378 1375 1370 1385 1376

A 1, 245 247 270 263 249 245 269 259 244

but the complexes appear to involve bidentate co-ordination of the carboxylates, and so it is suggested that they must be unsymmetrically bonded to the metal. v(C0) wavenumbers have been reported j 2 ? for (chel)(bipy)Pd') (at 1696, 1650 crn-'), where chel = dimethylfumarato anion. [Pt(PPh,Me),CO,] gives bands due to the co-ordinated carbonate ion at 1670, 1630, 1290, 985, and 820 cm ; [Pt( PPI~,Me),(C,O,)],EtOH gives features characteristic of the oxalate at 1705, 1680, 1660, 1370, and 790 cm-', and (Pt(PPh3),[C(O)0Et]1, gives bands due to C(0)OEt at 1630 and 1015 ~ n 1 - l . ~ ~ ~ Low-temperature, solid-phase i.r. spectra have becn obtained for copper(i1) acetate monohydrate, and also for the anhydrous Nearly all of the acetate fundamentals were observed to be split, in similar manner to those in the acetic acid dimer. Temperature-dependence studies o f the i.r. bands confirm the antiferromagnetic transitions occurring in these coin pou n ds. The only differences in the i.r. spectra of copper formate tetrahydrate i n its antiferro- and para-electric phases lie in the librational and translational modes of the crystal H,O In (C6Cl,)Hg(OCOCF3), vas(C02) is at 1684, 1675 cm-l, vy(C02) is a t 1420 cm-l, and S(OC0) is at 740 cm-I. For (C,CI,)Hg(OCOCHF,), the corresponding modes give bands a t 1647, 1635 cm-', 1426 c n - l , and 724 cm-l, re~pectively.~~' 1.r. spectra of neodymium nionoethylamine diacetate nitrate, Nd(L)NO,,1 .33H20, suggest that both unidentate [v(C=O) 1578 cm-I] and bidentate [v(C=O) 1609 cni-'1 carboxylate groups are Shifts in v(NH) on complexing are also diagnostic of Nd-N bonding. 422 423

424 426 426 427

T. Ito, Y . Takahashi, and Y . Ishii, J.C.S. C'heni. Cotnm., 1972, 629. D. M. Blake and L. M. Leung, Znorg. Chem., 1972, 1 1 , 287. A. M. Heyns, J . Mot. Structure, 1972. 11, 93. J. Hiraishi, Bull. Chem. SOC.Japan, 1972, 45, 128. R. J. Bertino, G . B. Deacon, and F. €3. Taylor, Austruf. J . Chem., 1972, 25, 1645. N. I . Sevost'yanova, K . F. Belaeva, and L. I. Martynenko, J. Sfrirct. Chem., 1971, 12, 162.

432

Spect soscopic Proper1 ies o/

ltio I xnn ic mid

Orgmioinetnllic Co171po I I I I ~ F

A few assignments of 1*(c'0,) modes have becn made, f r o m the i.r. spectra of lanthanuin iininodiacetates, LnHZ2.42g1.r. wavenumbcrs c)f thc Cog- ion in La,Cl(CO,), have been reported.429 The following assignments have been made for Nd,(C,O,),, 10H,O, Nd,(C,O,),IOD,O, and Nd,(C20,),,6D,0: v,(CO,) 1312--1310 cm I and 1355 - I340 ctn- I ; 6 ( H 2 0 ) + V ; ~ ~ ( C1603O ) ~ 1590 cm-l; S(OC0) 800 796 cm and 480 - 470 cni-'; v ( C - C ) 900 ~ m - ~ . ~ ~ ~ ~ 1.r. spectra of hydrated and anhydrous pimelates, azelates, and sebacates of La, Sm, Gd, and Lu have been Plutonium formate, Pu(O,CH),, has i.r. absorptions at 2910 cm [v(CH)], 1585 cm-' [v,,,CO,)], 1423, 1401 cm-I [6(CH)], 1350 cni [v,(CO,)], and 779cm [S(OCO)]. N o ~ ( P u - 0 ) band was found (above 200 cm- l), which is in agreement with the highly ionic In (120), the Me,NCO, group gives i.r. absorptions at 1605 and 1510 cm-l

432

A number of assignments (summarized in Table 13) have been proposed for the i.r. and Raman spectra of diethylindium acetate.433 v(C=O), v ( C - 0 ) , and 6(O=C-O) are found in the usual spectral ranges for (R,N),[MAr,(ox),], where ox = oxalato; R = Bu", M = Si,

Table 13

Vibrational assignments f u r Et,In(OOCMe) (all figures [ire wacenitmber/cm-') ?.r. 1525 vs, br 1465 vs 1176 111 644 vs 515 s 466 111s

4s1

4J2

U'

;;;;}

Assignmerit J'tiq(C0~)

J'~(c02)

s

1179s 640vvw, br 518 w 469 vs

o~,(In-CH,) p(In-CH,) vas(InC2)

+ 6(C02)

v,(InCJ

I . Badalova, G . N . Kupriyanova, N. D. Mitrofanova, L. I . Martyncnko, and V. 1. Spitsyn, Russ. J . Inorg. Chern., 1971, 16, 1556. R . Aumont, F. Gouet, M . Passaret, and hl. P. Bottorel, Coriipt. retid., 1972, 275, C , 491. ( a ) G . V. Bezdenezhnykh. E. I . Kry!ov, and V. A . Sharov, RNSS.J . Itiorg. Chctii., 1971, 16, 1563; (h) B. S. Azikov, S. E. Kharzeeva, and V. V . Sercbrennikov, T r . Tomsk (30s. Uriii... 1971, 204, 289, 294, 299. L. R. Crisler, J . Inorg. Nirclear Chem., 1972, 34. 3263. W. Pctz and ti. Schniid, J . Orgatiornetallic Chetti., 1972, 35, 321. H.-D. Hanscn, J . Orgtitioriietallic~Chetii., 1972. 39, C37.

c8 R.

4J0

R(rniun 1520 vw, br

Vihtariontrl Spectra of s o m ~Co-ordinated Ligarrch

43 3

A r = OX), Ph, p-F-C6H4,p-C1.C6H1, or p-Me.C,H,; R = Bun, M -= G e , Ar = Ph or CI; R = Et, M = Ge, A r = OX).^,^ ( - )-Ethyl-( !-naphthyl)phenylgermanecarboxylic acid gives an intense carbonyl band at 1650cm ', with a strong, unassigned band at 1210

cm-I 435 1.r. spectra have been reported 43G for the ally1 ( = R) tin carboxylates R,Sn(OOCMe), R3Sn(00CCH,C1), R2Sn(00CCH,C1),. R,Sn(OOCCHC1d2, [R2Sn(00CCH,C1)],0, [R2Sn(00CCHC1,)],0, and [R,Sn(OOCCC13)120. The solid diallyldicarboxylates are believed to be polymeric, with five-co-ordinate tin, and bridging carboxylate groups, whereas the solution data are consistent with the presence of dimers. In the distannoxane series, bands due to non-bridging (ca. 1630 cm-', ca. 1360 cm- l) and bridging (ca. 1560, ca. 1420cm-') carboxylates were present both in the solid and in solution. The trimethyltin complexes Me,SnO,CCH,OH and Me,SnSCH,CH,CO,SnMe, both show (solid-state) i.r. bands due to v,,(CO,) at CCI. 1580 cm-', i.e. due to bridging carboxylates. A number of similar dimethyltin carboxylates also gave i.r. evidence for bridging carboxylate groups.437 I n a series of organotin acrylates R3Sn02C(CN)C=CPh2(where R = Me, Et, PP, Bull, or Ph), v(CN) was found between 2215 and 222Ocin-l, with v(C=O) 1640-1650 ~ m - ' . ~ ~ * A reasonably detailed assignment has been proposed 438 for the vibrations of Me,Sn(Cl)OCOMe. In addition, va,(CO,), v,,(SnC,), v,(SnC,), and v(Sn--1) were listed for Me,SnCI(O,CR), where R = Me, CH,CI,(n = 1--3), CH,Br, CH21, CF3, C2F5, C3F7,or CF,Cl). A number of characteristic bands have been assigned in [Me,Sn(O,CR)],O, where R = CH,CI3-, (n = 0--3), CH,Br, CHJ, CF3, C2F5, C3F,, or CF2Cl.440The carboxylate CO, stretches are consistent with the presence of bidentate, bridging 0 2 C R groups. Morris and Rockett have assigned vaS(C02) and vS(CO2) for a number of organometallic carboxylates (see Table 14) [Fc = -(h5-C5H4)Fe(h5CSH~)I.~'~

Table 14 Carboxyl stretching z,ibrutioiis (M.'aileiiunzberslcm-') it1 some organo-tin and - titariiirni curboxy lu tes Coniyound Bu,Sn(SCH,CO,CH,Fc), Bu,Sn(OCOFc), Cp,Ti(OCOPh), (:I4 (.IB

417

4~icl 43n 440

O4I

Vas(C0,)

1601 1581 1630

V,(CO,) 1365 1315 1370

G . Schott and D. Lange, Z. anorg. Chem., 1972. 391, 27. C. Eaborn, R. E. E. Hill, and P. Simpson. J. Organometallic Chem., 1972, 37. 267. V. Peruzzo, G. Plazzogna, and G. Tagliavini, J . Organontetallic Chem., 1972, 39, 121. M . Wada, %-I. Sato, M. Aritomi, M . Harakawa, and R. Okawara, J. Organoriietullir Chem., 1972, 39, 99. R . A. Cummins, P. Dunn, and D. Oldfield, Austral. J . Chetn., 1971, 24, 2257. C. S.-C. Wang and J. M. Shreeve, J. Organornetallic Chem., 1972, 38, 287. C. S.-C. Wang and J. M. Shreeve, J. Organometallic Chem., 1972, 46, 271. D. R. Morris and B. W. Rockett, J. Organomefollic Chem., 1972, 35, 179.

15

434


‘v(C=O)’ and ‘v(C-0)’ were listed for the five-co-ordinate species R;Sb(OCOR2),, where R1 = Me or Ph; R2 = CHflF3-, (n = 1--3), CHnCI3-fl (n = 1 or 2), CH,Br,-, (n = 1 or 2), CD,, or CH2CN.442 1.r. data have been listed for the new trifluoroacetates NaBiL,, NaAsOL,, Na,TeL,, NH4VOL3, BiLB, IO,L, and V02L, where L = CF,CO,. The data for Bi(CF3C02), are typical: v,,(C02) 1632 cm-l; ve(C02)1444 cm-I; v(C-C) 844 cm-l; 6(C02) 733 cm-l; v,(CF,) 1207, 1120 cm-l; vs(CF,) 806 ~ m - ~ . ~ ~ ~

Keto-, Alkoxy-, Phenoxy-, and Ether Ligands.-Characteristic i .r. bands have been listed for a number of transition-metal complexes of 1,4-dioxan, 1,4-thioxan, and 1,2-dirnetho~yethane.~~~ A quantity of i.r. data has been listed for methanol complexes M(MeOH)i+, where M = Mg, Mn, Co, Ni, Zn, or Cd.446 By comparison with ?-naphthol, some of the stronger i.r. bands of 1-nitroso-2-naphthol have been both for the free ligand and its complexes with divalent metals. Some of the assignments conflict with previous work. A number of alkylchromium dichloride complexes containing coordinated tetrahydrofuran, RCrCI,(THF), have been prepared.447v,(COC) and v,(COC) shift to lower wavenumbers on complexing, with the shifts in the sequence: R = CH, > C2H6 =- n-C,H, > i-C4H9, consistent with the trend in the inductive effects of R. v(CH) of the alkyl group is found at ca. 2800cm-l. Tris-(2-acylpyrrolato)chromium(111)complexes Cr(RCOC,H,N), (R = H, Me, or Ph), have v(C=O) at ca. 1550 cm-l, compared to 1652 cm-l in the free ligand (and R = H).448 ve(COC) and v,(COC) of tetrahydrofuran shift to lower wavenumber on formation of FeCl,,THF, consistent with Fe-0 c o - o r d i n a t i ~ n . ~ ~ ~ For 9,lO-phenanthrenequinone (quon) complexes of Fe, Co, and Ni [M(quon),] (n = 2 for Co or Ni; n = 3 for Fe), co-ordination through the oxygen is clear from the fact that large shifts (ca. 215 cm-l) o f v(C=O) occur from that of the free quinone on complex formation.450 The chelates Co(chel), and Ni(chel), derived from benzoin (chelH, PhCHONCOPh) show i.r. bands due to v(C=O) at 1618 cm-’ (Ni), 1625 cm-l (Co), due to v(C-0) at 1040 cm-1 (Ni), 1050 cm-’ (Co) (both 442

445

44e 447

448 440 4b0

R. G. Goel and D. R. Ridley, J. Organometallic Chem., 1972, 38, 8 3 . P. V. Radheshwar, R. Dev, and G. H. Cady, J. Inorg. Nuclear Chem., 1972,34, 391 3. N. M. Karayannis, C. M. Mikulski, A. N. Speca, J. T. Cronin, and L. L. Pytlewski, Inorg. Chem., 1972, 11, 2330. A. D. van Ingen Schenau, W. L. Groeneveld, and J. Reedijk, Rec. Trao. chim., 1972, 91, 88. S. Gurricri and G. Siracusa, Inorg. Chim. Acta, 1971, 5 , 650. K. Nishimura, H. Kuribayashi, A. Yamamoto, and S. Ikeda, J. Organometallic Chem., 1972, 37, 317. C. S. Davies and N. J. Gogan, J. Inorg. Nuclear Chem., 1972, 34, 2791. L. S. Benner and C. A. Root, Inorg. Chem., 1972, 11, 652. C. Floriani, R. Henzi, and F. Calderazzo, J.C.S. D u ~ ~ o F1972, : , 2640.

Vibrational Spectra of some Co-ordinated Ligands 43 5 lower than in free benzoin), and probably due to v(M-0) at 514cm-l (Ni), 490 cm-l ( C O ) . ~ ~ ~ Salient i.r. wavenumbers have been listed 452 for I-amino-3,3,3-trifluoro2-propanol and its complexes with Co"', Ni", and Cu". All of the shifts which occurred on complex formation were small, but v(NH) remained in the complexes, whereas v ( 0 H ) was absent, hence the bonding is uiu the 0 atom. Oxidative addition reactions of Rh' and Ir' complexes have yielded products with o-quinones as l i g a n d ~ . ~ 1.r. ~ , bands characteristic of the o-diolato ligands have been listed for such compounds, and correlated with bands in the spectra of the free quinones. Some assignments of ligand vibrations have been proposed for Rh(ahmc)Clt-, lr(ahmc)(OH)(H20), Ce(ahmc),(H,O),, Pr(ahmc),(H,O),, Pd(hmcc),, Ce(hmcc),(H,O),, and Pr(hmcc),(H,O),, where ahmcH = 8-a1nino-7-hydroxy-4-methylcoumarin(1 2 1) and hmcc = 7-hydroxy-4methylcoumarin-6-carboxylic acid (122).4s4

w How /

MI2 (121)

HO,C

' Me' t 122)

A study of the 3-(carboxyalkyl)salicylaldehyde chelate complexes of Cu" includes some i.r. data for the co-ordinated aldehydes.46s Frequencies for Y, and vae of the carboxylate C 0 2 and the (shifted) v(C=O) of the aldehyde (near 1611 cm-l) were listed. 1.r. spectra of the glycerates Ln(C,H,O),,nH,O (n = 0 or 1; Ln = 1 of 12 lanthanides) have been assigned using the group-frequency approach, e.g. C-C-C skeletal stretches, 820-865 cm-l and 1200-1265 cm-l; v(C0) (primary alcohol) 1010-1060 cm-l; v(C0) (secondary alcohol) 1110-1 105 ~ m - l . ~ ~ * Unassigned i,r. data have been listed for some rare-earth mixed-ligand complexes of salicylaldehyde, M(sal),L,, where M = La, Pr, Nd, Sm, Eu, or Tb and L = py, quinoline, i(bipy), or l ( ~ - p h e n ) . ~ ~ , " va,(COC) (960-1 115 cm-l) and v,(COC) (850-995 cm-l) have been assigned in the i.r. spectra of ether complexes (R,O)UCI, (R = Me, Et, Pr", Bun, or n-C,HI1; or R,O = C 4 H g 0 or C4H802).467bThe dioxan adduct contains unidentate C1H802. 451 462 4b3

4b4 p66 466

K. C. Malhotra and S. C. Chaudhry, Chem. and Ind., 1972, 606. I . Yoshida and H. Kobayashi, Bull. Chem. SOC.Japan, 1972,45, 2448. Y. S. Sohn and A. L. Balch, J. Amer. Chem. SOC.,1972, 94, 1144. D. E. Rastogi, Austral. J. Chem., 1972, 25, 729. T. Tanaka, Bull. Chem. SOC.Japan, 1972,45, 2113. D. V. Pakhomova, V. N. Kuniok, and V. V. Serebrennikov, Russ. J. Inorg. Chem., 1971, 16, 1588.

467

( a ) K. K. Rohatgi and S. K. Sen Gupta, J. Inorg. Nuclear Chem., 1972, 34, 3061; (b)J. D. Ortega and W. P. Tew, J . Co-ordination Chem., 1972, 3, 13.

436

Spec t r-oscopic Propert ic.s of It ro r-ganic a i d Organo me t cillic* Coriipo iri1cl.v

Oertel has studied the Ranian spectra of aqueous solutions containing B(OH), and various polyols, c . g . 1,2-ethanediol, 1,3-propanediol, and 1,2,3-propanetri01.~~"The spectra can only be explained in terms of chelate formation, involving species such as (123), and similar six-membered

(123)

chelates. Assignments were proposed for t h e five- and six-membered rings. For example, in the monoborate-l,2-ethanediol chelate, ring stretches were found at 1134, 1065, 942, 885, and 764 cm-' (the last being the A , mode, primarily B - 0 stretching in character). In the six-membered ring system, the band analogous to this last was at ca. 710 cm-'. In (aldehyde)BF, complexes, v(CH) of the aldehyde is shifted by C ' N . 150cm-l to higher wavenumbers, and its intensity decreases upon coordination. v(C=O) is reduced by ca. 70cm-I. The aldehydes studied were CH,CHO, CD,CHO, CnH5CH0, C3H,CH0, C6H,CH0, and C6DsCH0.45B

0-Bonded Amides and Ureas. The vibrations of a number of salts and have been listed complexes of N-hydroxyurea, H,N-C(=O)NH(OH), and assigned.46o 1.r. spectra of the dimethylformamide complexes NbX,(DMF), ( X = CI or Br) and Nb14(DMF),,6DMF show downward shifts (ca. 35 cni l ) for v(C=O) and upward shifts (ca. 40 cm-l) of 6(NCO) on complexing. Thus, co-ordination cia the carbonyl oxygen is occurring.461" 1.r. spectra of the MnSO, complex with urea show that the ligand is O-b~nded.~~ 1.r. spectra of a number of complexes of the terdentate chelating agent I , 10-phenanthroline-2-carboxamide(with Fe", Co", Ni", and Cu") have been obtained.46o'In each case v(C = O ) is in the range 1660---1690cm- I , with v(CN) 1415--1425 cm-l. These data indicate co-ordination of the amide group to the metal via the oxygen atom, not the nitrogen.", The i.r. wavenumbers of [Co(urea),](NO,), have been assigned, but without any real evidence. Both bidentate and 0-bonded unidentate urea are believed to be 1.r. spectra have been given for CuCl,, CuBr,, and Cu(NO,), complexes with MeCONH,, MeCONHMe, and MeCONHMe,.463b 45L)

481

4132 463

R. P. Oertel, Inorg. Chem., 1972, 11, 544. E. Taillandier, J. Liquier, and M. Taillandier, J . M o l . Structrrre, 1971, 10, 463. R. Berger and H. P. Fritz, Z. Nururforsrh., 1972, 27b, 608. ((I) K . Kirkscy and J . B. Hamilton, Inorg. Chem., 1972, 11, 1945; (b) N. N. Rumov, Uch. Z a p . Yaroslur. Gos. Pedagog. Inst., 1970, 79, 142. H. A . Goodwin and F. E. Smith, Austral. J. Chem., 1972, 25, 37. ( a ) P. S. Gentile, P. Carfagno, and S. Haddad, Inorg. Chim. A d a , 1972. 6, 296; (b) M.A. A. Beg and M. A. Hashmi, Pakistan J. Sci. Ind. Res., 1971, 14, 458.

Vibrational Spectra of some Co-ordinated Lignnd.r

437 1.r. data have been listed for the characterization of Ln(C104),,4DA, where DA = d i a ~ e t a m i d e . ~ ~ ~ ~ Group-frequency assignments have been proposed for urea modes in the i.r. spectra of [U0,(CO(NH,),~4(H,0)]Xn(N03)2 .n (X = CI, n = 0.5; X = Br, n = 1 ; X = I , n = 1.1 or 1.7) and of [UO,(CO(NH,),),]X(NO,) (X = I or Cl).464b

Nitrates and Nitrato-complexes.-Nitrate bands are found at 1345 and 830 cm-' in a number of M(nipa),(NO,), or :3 complexes, where nipa = nonamethylimidodiphosphoramide and M = Mg, Ca, Sr, Ba, AI, Cr, Fe, or In.46a NO; spectra in M(tripa),(NO,),, where M = Mg, Co, or Ni, and M'(tripa),(NO,),, where M' = A1 or Fe, are consistent with the presence of unco-ordinated, ionic nitrate. In M(tripa)(NO,),, where M = Ca, Mn, Cu, Zn, or Cd, however, co-ordination of NO; occurs, and this is reflected in the i.r. spectra [tripa = (Me,N),P(O)N(Me)P(O)NMe,N(Me)P(O)(N Me,),, bis(methy1imido)triphosphoric acid pentaki~-dimethylamide].~~~ The i.r. spectra of Mn(NO,), and (NO,)+[Mn(NO,),]-, and the i.r. and Raman spectra of Na,[Mn(NO,),] and K,[ Mn(NO,),], have been obtained."' In each case, the nitrate vibrations could be assigned in terms of C,,, symmetry [bridging for Mn(NO,),, bidentate for the rest]. Thus, in Mn(NO,),, u , [ A , , (NO)] = 1540cm l ; u n [ A l , (NO,)] = 977 cm-l, ~4[B1, (NO,)] = 1270, 1255 cm l, and u ~ ( A Iring , def.) and v,[B,, (TIO,NO)] = 794, 768, 743 cm-'. I n Na,[Mn(NO,),], u1 = 1490 cm-l, v , = 1041, 1036cm-l, v3 = 765, 750cni l, u4 = 1280cn1-~, v6[B1, (ONO)] = 719 = 820, 812, 807 cm-l. cm-l, and cis- and trans-Isomers of Re(CO),(PPh,)(NO,) have been charact e r i ~ e d .cis-Isomer ~~~ : v(C0) 2070, 2010, 1990, and 1968 cm-1 ; u,,(NO,) 1520cm-l; v,(NO,) 1265 cm-l; u(N=O) 995 cni-l; and 6(ONO,) 790cm-l; trans-isomer: v(C0) 2100, 2012 cm-l, u,,(NO,) I505 cm-l; u,(NO,) 1270 cm-'; u(N=O) 990 cm-l; and 6(ONO,) 790 cm-l. From various pieces of physical evidence, including i.r. spectra, the presence of unidentate NO;- in N i ( e t ~ ) ~ ( N o , )and , asymmetric bidentate nitrate in Co(etu),(NO,), and Co(tmtu),(NO,), is deduced.4se The deductions were made on rather slight evidence (etu = ethylenethiourea : tmtu = tetramethylthiourea). Vibrational spectroscopy has been used to investigate the nature of the metal-ligand environment of Cu(py),(NO,), (where n = 2, 3, or 4) and PO4

406 488

407

46H JOU

( a ) C . Airoldi and Y. Gushikem, J . Inorg. Nuclear Chem., 1972, 34, 3921; (h) G. V. Ellert, I. V. Tsapkina, 0. M. Ewstaf'eva, V. F. Zolin, and P. F. Fisher, Rum. J . Inorg. Chem., 1971, 16, 1640. M. W. G. de Bolster and W. L. Groeneveld, Rec. Trar. chim., 1972, 91, 95. M. W. G. de Bolster, J . den Heijer, and W. L. Groeneveld, Z. Narurforsch., 1972, 27b, 1324. D. W. Johnson and D. Sutton, Corrad. J. Chem., 1972, SO, 3326. R. Davis, J. Orgnrromefollic Chenr., 1972, 40, 183. E. C. Devore and S. L. Holt, J . Ittorg. Nrrcletrr Chettr., 1972, 34, 2303.

438


M ( P ~ ) ~ ( N O , )where ~, M = Co, Ni, or Zn.470 Extensive use of isotopic substitution (62Ni,58Ni, 63Cu,and 65Cu)and related techniques was made, to assign low-frequency i.r. spectra. I t has been observed for the Cu(py),(NO,), system that as the covalency of the nitrate bond increases, the Cu-0 stretch shifts to higher energy, while the Cu-N stretch moves to I ower energy. The highest-wavenumber (1641 cm-l) i.r. band assigned to a v(N-0) fundamental in 1r3(N03)10indicates the presence of bridging or bidentate nitrate groups, as well as unidentate NO; [v,,(N02) 1549cm-'] in this complex.471 The complex (bipy)2Pd(N03)z,H20has i.r. bands due to the nitrate group as follows: v3 1310-1372 cm-l, v1 1025 cm-l; v2 822 cm-l, indicating, it is said, either a low site symmetry for the nitrate or interaction with the Pd or the H20.472 The i.r. spectrum of K2[Pt(N02),(N0,),] shows bands due to coordinated NO; (1520, 1290, 980, and 825 cm-l) and NO, (v,, 1510 cm- l, v, 1390 cm-l, 6 845 cm-l, p 600 Raman intensity measurements on the nitrate bands at 722 and 1052 cm-l in aqueous copper(1r) nitrate solutions have been used, after corrections due to the strong absorption of the Raman-scattered light (an A r t laser was used as excitation source), to calculate the concentration quotient of CuNO; (K,,,, = 0.07 k 0.02 at 25 0C).474 Fairly full assignments for the i.r. and Raman spectra of tetranitratoaurates(rI1) have been given [i.e. for M*Au(NO,)~,where MI = H, Na, K, Rb, Cr, NO+, or An apparently unequivocal means of distinguishing between uni- and bi-dentate nitrate co-ordination was discussed; of the three v(N0) fundamentals derived from the NO; group, in the bidentate case that at cn. 1300 cm-l [v,(N02)] gives rise to strong bands, while for unidentate NO;, v,,(N02) is found near 1300 cm-l as a fundamental which is only weakly observable. 1.r. data (including the combination band region ca. 1750 cm-l) indicate the presence of co-ordinated nitrate groups in the rare-earth complexes Ln(napy),(NO,),, where napy = 1,8-naphthyridine, and in Ln(napy),They are believed to be twelve- and ten-co-ordinate, respectively. The presence of co-ordinated NO;, both uni- and bi-dentate, in M2Sc(NO,)a (M = K, Rb, or Cs) has been inferred from i.r. Q70 471 47a 473 474 476

Q76

477

M.Chorea, J. R. Ferraro, and K. Nakamoto, J.C.S. Dalton, 1972, 2297. B. Harrison and N. Logan, J.C.S. Dalton, 1972, 1587. A. J. Carty and P. C. Chieh, J.C.S. Chem. Comm., 1972, 158. L. K. Shubochkin, E. F. Shubochkina, M. A. Golubnichaya, and L. D. Sorokina, Rum. J . Inorg. Chem., 1972, 16, 877. A. R. Davis and C . Chong, Inorg. Chem., 1972, 11, 1891. C. C. Addison, G. S. Brownlee, and N. Logan, J.C.S. Dalton, 1972, 1440. J. Foster and D. G. Hendricker, Inorg. Chim. A d a , 1972, 6 , 371. L. N. Komissarova, G. Ya. Pushkina, and V. I. Spitsyn, Russ. J. Inorg. Chem., 1971, 16, 1262.


439

The nitrato-groups in M(N03)3L3 ( M = Y or La-Yb, L = 2,7dimethyl-l,8-naphthyridine)are co-ordinated to M, but uni- or bi-dentate modes of bonding could not be distinguished. Characteristic ni trato-group wavenumbers were listed for each 1.r. bands due to the NO; (of CZVsymmetry) and H 2 0 have been assigned 4 7 e for Eu(NO,),,xH,O (x = 0 - 6 , inclusive). Approximate assignments of NO; or Cloy bands have been made48ofor Ce(NO,),,2(Ph,PO), Ce(N03),,7DMS0, Ce(N0,),,6( 1 ,lo-phen), and Ce(CIO,),,7DMSO. The nitrato-group in U(NO,)(dbp) (solid) appears to be covalently bonded to the uranium (bands at 1520, 1275 ~ m - 9 .Unassigned ~ ~ ~ i.r. spectra were given for U(NO,)(dbp), and U(dbp), (dbp = di-n-butyl phosphate). Molecular weight and i.r. spectroscopic data have been used 4 R 2 to show that in Ph4BiX (X = NO; or CC1,CO;) the X is bonded (unidentate) to the Bi, giving a five-co-ordinate complex. Thus, in Ph4BiON02,vas(N02) 1442 cm-l; vB(N02)1295 cm-l; v(BiO-N02) 1032 cm-l; 0.0.p. deformation 825 cm-l; and for Ph,BiOCOCI3, v,,(C02) 1680 cm--'; v,lCO,) 1300 cm-l. Ligands containing 0-N, 0-P, or 0 - A s Bonds.-v(N0) bands (12101225 cm-l) have been listed for a number of complexes of pyridine N-o~ide.~~~ Empirical assignments of the i.r. spectra of the cupferronates of Cu", Hg", Alli1,Fell', Gal1', Bill1, TiIV,VIV, Zr", ThIV, UIV, V", and Nb" (124) have been made.,*,

An amount of unassigned i.r. data on complexes of hexamethylphosphoramide and nonamethylimidodiphosphoramide has been v(P=O) and v(As=O) bands have been assigned (in the expected ranges) for complexes of ditertiary phosphine or arsine oxides, Ph2E(0)(CH,),E(O)Ph, (E = As or P).4ss D. G. Hendricker and R. J. Foster, J . Inorg. Nuclear Chem., 1972, 34, 1949. K. E. Mironov, A. P. Popov, V. Ya. Vorob'eva, and Z. A. Grankina, Russ. J. Inorg. Chern., 1972, 16, 1476. 4 R 0 F. Bfezina, Coll. Czech. Chem. Comm., 1972, 37, 3174. 461 E. R. Schmid and V. Satrawaka, Monarsh., 1972, 103, 442. 4R2 R. E. Beaumont and R. G. Goel, Inorg. Nuclear Chem. Letters, 1972, 8. 989. a3 C. P. Prabhakaran and C. C. Patel, J. Inorg. Nuclear Chem., 1972, 34, 3485. 4H4 A. T.Pilipenko, L. L. Shevchenko, and V. N. Strokan, Russ. J. Inorg. Chem., 1971,

47R

478

16, 1279.

4Rb tn6

M. W. G. de Bolster and W. L. Groeneveld, Rec. Trau. chim., 1972, 91, 171. S. S. Sandhu and R. S. Sandhu, J. Inorg. Nuclear Chem., 1972, 34, 2295.

440

Spectroscopic Properties of Inor-gunic and Organometnllic Comporiricis

1.r. spectra of several phosphites of Group IA and H A metals have been reported.487 Similar data have been given 4R8 for di-n-octyl phenylphosphonate, mono- and di-n-decylphosphoric acids, and some of their Ca2+ salts. In Ca(bapo),(CIO,),, where bapo = bisphenyldimethylaminophosphine oxide, the v, mode of ClOh is split, possibly suggesting that the anion is participating in the co-ordination around the Ca2+ 1.r. and Raman spectra of the complexes of MoO,CI, and SbCI, with Me,XO (X = N, P, or As) have been studied in an attempt to establish their molecular 1 .r. wavenumbers have been partially assigned for some co-ordination complexes of PH,O; with Mn and V.490 v(N0) is in the range 1205-1276cni in the i.r. spectra of Fell, Fe"', and Cuii complexes of 2-, 3-, or 4-cyanopyridine N - o ~ i d e . ~ ~ ' H Ru,(CO)~[ P(OC6H4)(OC6H5)2]2 [OP(OC6H has been shown by single-crystal X-ray studies to be (1 25).492 The bridging (C6H50)2PO group gives .(PO) at 1075 cm-l.

( 125)

v(P=O) and v(M-ha]) have been listed 493 for the Co and Ni complexes [ML,][MX,], where X = CI, Br, or I and L = Ph,P(O)(CH,),P(O)Ph, (n = 1 or 2). A listing of v(N0) wavenumbers has been made 494 (all cu. 1200 cm-l) for CoL,X,, where X = CI, Br, I, NCS, or CIO, and L = 2,6-lutidine N-oxide. v ( A s - 0 ) bands are at ca. 760 cni-' and 855 cm-l in MIi salts of phenylarsonic acid and of o-arsanilic acid (M = Co, Ni, Cd, or Zn).,05

rn9

48n 4'11

WI

*'I5 lul

M. Ebert and J. Eysseltova, Monntsh., 1972, 103, 188. G. H. Griffiths, G. J. Moody, and J. D. R. Thomas, J. Inorg. NirtIeor Chein., 1972, 34, 3043. ( a ) M. W. G. de Bolster and W. L. Groeneveld, 2. Notirrforsch., 1972, 27b, 759; (6) F. Choplin, M. Burgard. J . Hildbrand, and G. Kaufmann, Colloq. I n f . Cent. Nat. Rech. Sci., 1970, N O . 191, p. 213. J. Sala-Pala, R. Kergoat, and J. E. Guerchais, Compr. rend., 1972, 274, C , 595. G . W. Watt and W. R. Strait, J. Inorg. Nuclrar Chem., 1972, 34,947. M. I. Bruce, J. Howard, I. W. Newell, G. Shaw, and P. Woodward, J.C.S. Chem. Comm., 1972, 1041. F. Mani and M. Bacci, Inorg. Chim. Actn. 1972, 6 , 487. D. W. Herlocker. Jnorg. Chitn. Acta, 1972, 6 , 21 1. S. S. Sandhu and G. K . Sandhu, J. Itwrg. Nuclear Chem., 1972, 34, 3249.

44 I

Vibrationd Spectra of' some Co-ordinnted Lignnds

Bands in the region 1140-1205 cni-' have been assigned to ,(PO) in ethylenebis(dipheny1phosphine oxide) complexes of Coil, Ni", and C U ~ I . ~ * ~ 1.r. data for M" complexes of (126) and (127), where M = Co, Ni, Cu, or Mg, show that v(P=O) decreases by 10- -40 cm-' upon co-ordination, i.c. co-ordination occurs ria the 7\ P - 0 0 II

0

0 I1 J, ,p... Me,N0 R

II

1

1

R

NMe,

i

R.-,

Me,N

0 I1

T\

NMc.,

Bands due to v(P=O) and v(As=O) and internal vibrations of the ligand (not assigned in detail) have been reporteddBg" for NiX2L, NiBr,Ldl.5, and NiL,(CIO4),,2H,O [X = CI or NO,; L = Ph2E(0)(CH,),E(O)Ph,, E = P for n = 2 or 4, E = As for n = 41. The complexes CuL,X, [X = CIO,, NO,, or BF,; L = diethyl4-methylpyridine-2-phosphonate or diethyl pyridine-2-phosphonate ( 1 28 ; R = Me or H)] have been prepared.4BQWavenumbers purporting to be the v( P=O), pyridine modes, and anion modes have been listed.

R

The i.r. spectra of the organic phases in t h e extraction of C u 2 +from aqueous HCI (containing LiCI) using Oct",PO in benzene or kerosene have been investigated.500 A band at 1 1 10 cm-l is assigned to v(P=O) of the co-ordinated phosphine oxide. Approximate assignments of ligand vibrations have been proposed for NH4L, Cu(L,,),, Cu(L),(py), and Cu(L),(4Mepy), where L = N-nitroso-Nphenylhydroxylamine, cupferron, ( 1 29).501

n

y

=

o

( 129) 4"n 41r7

4')x 4ny

tBol'

R. J . Brisdon, J.C.S. Dalton, 1972, 2247. M . D . Joesten and Y . T. Chen, frtorg. Chrn.. 1972, 11, 429. S. S. Sandhu and R. S. Sandhu, Inorg. Chirir. Acm, 1972, 6, 383. A . N. Speca, L. L. Pytlewski, and N . M. Karayannis, J . Inorg. Nuclear Chem., 1972, 34, 3671. 7'.Sato and M . Yamatake, Z . t r m r g . Chprri., 1972. 391, 174. D. P. Graddon and C. Y . Hsu, Ai,Jtnr/. J . Chrrrr., 1971, 24, 2267.

442

Spectroscopic Properties of Inorganic and Organornetallic Compounds

Lists of unassigned i.r. absorptions have been presented for complexes of the general formula Ln(C104),,4DDPA (where Ln = Y or La-Lu inclusive; DDPA = NN-dimethyldiphenylphosphinamide) and LnCI,,5DPPA = diphenylphosphinamide).602fll * Similar data have been given for the cupferronates of La, Ce, Gd, and Y b [cupferron = (129)],503and for LnP309,xH20and Lnl(P40,2)3,~H20.504 Group-frequency assignments have been given for the i.r. spectra of glycerophosphates LnC&02PO ,H,O (where Ln = one of 12 lanthanides), e . g . v(P0C) 1120--1200 cm-l; v(C0) 1060-1 120 (secondary alcohol), 970--1030 (primary alcohol) cm-l; 6(POC) 780-800 cni- l ; iS,,(OPO) 590-660 cm-l; S,(OPO) 530-540 cm-1.60fi .(PO) is lowered by 145cm-l (compared with the free ligand) in U(C104),,5HMPA, and the ClOh ions are unco-ordinated, according to i.r. data; the complex is therefore considered to be five-co-ordinate ( H M P A =

hexamethylphosphoramide).506

1.r. and Raman spectra of (hmpt),ZnCI,, of (hmpt)'OBF,, and of (hrnpt)l1BF3 have been recorded and assigned with the aid of isotopic shifts (hmpt = hexamethylphosphotriamide): U ( O - ~ ~ B F ~921 ) cm ; v(O-11BF3) 890cm-I. Small shifts only were found in the hmpt fundamental~.~~' 1.r. spectra have been studied, over the restricted range 1300-1000 cm-l, for aqueous solutions of Na,P,O,, 1 0 H 2 0 and Na6P,010,6H20 at different pH values, and of complexes of Al"' and Gall' with these phosphates."* It was concluded that the vm(POt-) band shifts on co-ordination to A1 or G a in the same way as it does on protonation. Monomeric, four-co-ordinate, structures have been proposed for the complexes (C,F,),InL, where L = Ph,PO, Ph,AsO, Ph3P, Ph,As, or py, from their i.r. spectra.60s (C,F5)InL,, L = OSMe, or THF, are also monomeric, and five-co-ordinate; the complexes [(C,F,),In],L, L = bipy or Ph2PCH2CH2PPh2,and [(C,F,),In],(tmed) have bridging ligands, with four-, five-co-ordinate indium, The v(P=O), v(As=O) bands of the Ph,PO or Ph,AsO are lowered (to 1159, 874 cm-l, respectively) from free-ligand values, i.e. there is In-0 co-ordination. 0-Bonding is also postulated for the OSMe, complex [v(S=O) being found at cn. 1200 cm-'1. 602

603

106

606

LO7 boa

boo

( a ) G . Vicentini and P. 0. Dunstan, J . Iuorg. Nuclear Chem., 1972, 34, 1303; (b) G. Vicentini and J. C. Prado, ibid., p. 1309. N. V. Thakur, V. B. Kartha, C. R. Kanekar, and V. R. Maratke, J . Inorg. Nuclear Chem., 1972,34,2831. Y . Gushiken, E. Giesbrecht, and 0. A. Serra, J . Inorg. Nuclear Cliem., 1972, 34, 21 79. D. V. Pakhomova, V. N. Kumok, and V. V. Serebrennikov, Russ. J . Inorg. Cliern., 1971, 16, 1586. J. G . H . du Preez and H. E. Rohmer, Inorg. Nuclear Chem. Letters, 1972, 8, 921. M. T. Forel, S. Volf, and M. Fouassier, Spectrochim. Acta, 1972, 28A, 1321. I. A. Sheka, L. P. Barchuk, and G. S. Semenova, Russ. J . Inorg. Chem., 1971, 16, 1701. G. B. Deacon and J. C. Parrott, Austral. J . Chem., 1972, 25, 1169.


443 The gas-phase value for v(P=O) in SnC1,,2POC13 is at 1207 em-' (i.r.), almost the same value as reported previously for the solid.510 A number of assignments have been proposed for Ph,Sn[ON=C(CN)CN], i.e. Ph,SnX and related complexes 511 (see Table 15).

Table 15 Some vibrational assignments for Ph,Sn[O-N=C(CN),]

related complexes (all figures are watlenumber/cm-l) Vibration Ph,SnX Ph,SnX, Bun,SnX Bun2SnX,

V(CC) VS(CN 0) vas(CN0) V(CN)

1248 1120 1382 2245

1242 1123 1440 2245

1245 1150 1450 2245

and

1245 1 I40 1435 2238

The i.r. spectra of the nitrosoalkane complexes [R2Pb(RNO)2]2+(N0,)~are consistent only with the presence of ionic, i.e. non-co-ordinated, NO, ions.612 Complexes containing the pentaco-ordinated cations [(R3SbL),0I2+ have been prepared, where 1, = py0, Ph3P0, Ph,AsO, diphenyl sulphoxide, dimethylacetamide, or DMS0.613 Co-ordination of L to Sb takes place via the ligand 0-atom in each case, as shown by a significant drop in v ( X - 0 ) from the free ligand to the complex, e.g. for Ph,AsO, v(As0) is at 890 cm-l (free), 845 cm-l (complex).

Ligands containing 0 - S Bonds. Wavenumbers of Sot- have been listed for the series M:MI"(SOa),, where M[ = Na or Ag; M'" = Ga, V, Cr, Fe, or Rh.614 By i.r. spectroscopy, 1,4-dithian monosulphoxide has been shown to co-ordinate to metals (e.g. Mn, Fe, Co, Ni, Cu, Zn, Cd, Pt, or Pd) via the oxygen atom of the sulphoxide group.516 The complexes (1 30) and (131) give bands assigned to ~as(SO2),v8(S02) at 1267, 1 1 53 cm-l and 1249, 1128 cm-l,

E. K. Krzhizhanovskaya and A. V. Suvorov, R i m . J . Inorg. Chem., 1971, 16, 1355. H . Kohler, V. Lange, and B. Eichler, J . Organomefallic Chem., 1972, 35, C17. u2 K. C. Williams and D. W. Imhoff, J . Organomefallic Chem., 1972, 42, 107. 6 1 s R. G . Goel and H. S. Prasad, Inorg. Chem., 1972, 11, 2141. 614 R. Perret and P. Couchot, Compt. rend., 1972, 274, C, 1735. .5lS A. H. M. Fleur and W. L. Groeneveld, Rec. Trau. chim., 1972, 91, 317. M. L. H . Green, A. H. Lynch, and M. G. Swanwick, J.C.S. Dalton, 1972, 1445. 610 bll

444

Spectroscopic Properties of Itiorgnriic and Organomeinllic Compoirnd.7 A number of assignments have been made to fluorosulphate vibrations in exotetrakis(fluorosu1phate)W"' ( I 32), i.e. v,,(SO,) 1464, 1416 cm-1; 1dS02) 1240 cm- l ; v , ( S 0 2 , bridging) 1163, 1040 cm-l; v(S-F) 873, 853, 826, 801 c w l ; 6,,(S03, bridging) 707, 700 cm-l; v , ( S 0 3 ) 644 cm-I; &SO,, bridging) 552 cm-l; S-F wag 455 cm '; S-F deformation 421 cm Due to Jahn-Teller distortions, the Mn"' complexes MnL,, where L = DMSO, DMF, py0, or antipyrine. have tetragonally distorted This is indicated, inter d i n , by the presence of two v(E=O) absorptions - thus when L = DMSO, v(S=O) at 960, 915 cm 1; L = antipyrine, v(C=O) at 1630, 1610cm-', although when L = pyO or DMF only one analogous band is found in each case. Reactions of dioxygen complexes of Ni and Pd afford products containing, for example, co-ordinated SO,, NO3, NO, CO, or C02.619Thus, for the sulphato-complexes MSO,(ButNC),, where M = Ni" or Pd", v ( S 0 ) is at 1170-1010cm-1 (v,) and 680 --580cm-' (v4), in accord with Czo local symmetry of cis-chelated SO4. Analogous results were found for the nitrato- and carbonato-complexes. A large number of Pd" and Pt" cationic complexes of the type [PdL,](BF,), (L = DMSO; tetramethylene sulphoxide TMSO; diethyl sulphoxide DESO; di-n-propyl sulphoxide NPSO; di-n-butyl sulphoxide NBSO; or di-iso-amyl sulphoxide TASO) have been prepared,520some containing mixed S- and 0-co-ordination sites. Cationic Pd" and Pt" complexes of 2,5-dithiahexane 2,5-dioxide, (dthO,) have also been prepared and polymeric structures have been proposed. Assignments of v ( S 0 ) and v(M-S), v(M-0) were made. Gold(111)fluorosulphate gives a very strong complex Raman spectrum, and it is believed to be covalent and polymeric.621 I .r. data have been given for the characterization of La(TMSO),(NO,),, LII,(TMSO),(NO,)~, and Ln,(T M SO)6(N03), (TM SO = tetramethylene su I ph ox ide) .5 2 2 a 1.r. spectra (40&1500 cm-l) have been studied for M,SO, (M = Li, K , or Cs), M'~(S04)3(M' = Y or La), and M"Sc(SO,), (M" = Rb or Cs), and some integrated absorption intensities have been discussed in terms o f sulphate c o - ~ r d i n a t i o n . ~ ~ ~ ~ SO:- bands were assigned for LiCe(SO,),, LiPr(SO,),, and LiSm(S0,),.52'L:3 All were in the usual ranges. 517

51u

w0 5z' 822

u

R . Dev and G . H . Cady, Inorg. Chern., 1972. 11, 1134. C. P. Prabhackaran and C. C. Patel, J . Inorg. .Yirclear ChPtn., 1972, 34, 2371. S. Otsuka, A . Nakamura, Y . Tatsuno, and M . Miki, J . Anier. Chetn. Soc., 1072, 94, 3761. J. H. Price, A. N. Williamson, R . F. Schramm, and B. B. Wayland, Irzorg. Chen?., 1972, 11, 1280. W. M . Johnson, R. Dev, and G . N . Cady, Itiorg. Chetn., 1972, 11, 226. ( ( 1 ) P. B. Bertan and S. F. Madan, J . Inorg. Nuclear Chem., 1972, 34, 3081; ( 6 ) B. I:. Zaitsev. V. Ci. Remizov, M. A. Galiullin. L. G . Korotaeva, and B. N . Ivanov-Emin, I z r c ~ s t .V.U.Z. Khitn. i khim. Tekhnol., 1972, 15, 473. V. 1. Volk and L. L. Zaitseva. Rirss. J . Inorg. Chetn., 1971, 16, 1513.

Vihr-ationd Spectra o f ' some Co-ordinutd Lipndu

445

The i.r. spectra of trifluoro(fluorosu1phato)Ce'". CeO(SO,F),, have been reported.s24 That of the former is very similar to that of K+SO,F , for example, indicating a largely ionic system. The 0x0-compound gives a much more complex spectrum, and greater covalency was suggested. Several uranium(1ii) sulphates and double sulphates have been examined by i.r. spectroscopy, with some discussion of characteristic sulphate vi brat ion^.^'^ 1.r. spectra of a number of monoalkyltin orthosulphites show characteristic absorptions at 11 10, 880, and 685 cm-1.526 The fluorosulphate vibrations in SnF,(SO,F), were consistent with bridging SO,F units of C , symmetry (see Table 16).527 Similar data have

Table 16 Assignment offluorosulphute cihr-ations in SnF,(SO 3F)2 Assigiinietit

W a ~ ~ e n r o ~ hm e r- l c i.r. and Raman) 1 I10 (doublet in i.r. and Raman) 1069 859 629 590 550 43 3 279

ca. 1420 (doublet in CN.

been listed for MeSnCI(SO,F),, Me,SnCI(SO,F), MeSnCI,(SO,F), Me,Sn(S03F),, Me,Sn(SO,F), SnCI2(SO3F),, and SnF2(SO,F), (see Table 1 7).628 All contain only bridging, bidentate S 0 3 F groups, resulting in polymeric chain- or sheet-like structures. It was suggested that a greater splitting of the E mode of v ( S 0 , ) of free S03F- (i.e. the two highest bands in coordinated S0,F) corresponded to greater covalent character of the M-OS0,F bond. I n PhPb(O,CMe),,H,O,DMSO, the v ( S 0 ) of DMSO is found at 936 c n [Av(SO) = - 119 cm-' on complex formation].529 A similar position is found for PhPb(02CMe),,2DMS0. 6 Sulphur and Selenium Donors

Metal carbonyl derivatives containing the trifluoromethylthio ligand show differences in the v(C-F) region between bridging and terminal SCF, groups.63o 624 525

62H 52i

52H b2n 5:io

R . Dev, W . M . Johnson, and G . H . Cady, Inorg. Chem., 1972, 11, 2259. R. Barnard, J. 1. Bullock, and L. F. Larkworthy, J . C . S . Dalton, 1972, 964. C. H. Stapfer and R. H . Herber, J . Organometallic Chem., 1972, 35, 11 1. L. E. Levchuk, J . R. Sams, and F. Aubke, Inorg. Chern., 1972, 11, 43. P. A. Yeats, J . R. Sams, and F. Aubke, Inorg. Chem., 1972, 11, 2634. H.-J. Haupt and F. Huber, Z . Nuturforsch., 1972, 27b, 724. J. L. Davidson and D . W. A, Sharp, J.C.S. Dalton, 1972, 107.

Compound Me,Sn(SO,F), Me,Sn( S0,F) Me,SnCI(SO,F) MeSnCI(SO,F), MeSnCI,( S0,F) SnCI,(SO,F), SnF,(SO,F),

v(SO,)A” 1350 1355 1344 1361 1350 1385 1420

v(S03)A’ 1180 1207 1190 1165 1250 1130 1101

v(sO,).4’ 1076 1068 1072 1072 1080 1087 1068

4SF) 827 820 820 830 8 25 8 64 855 630 607 620 605 628 630

620

&SO,F)A’

590

588 586

S(SO,F)A” 590 596 590 590

~(SO,F)A’ p (SO,) 554 417 555 410 555 409 420 555 555 405 555 446 548 430

Table 11 Vibrational modes of the SO,F group in various tin and methykin fluorosulphates (allfigures are wavenumberlcm-l)

z.

3


447

Metal-sulphur co-ordination in complexes of the diphosphinothioyl ligands (133; R1 = R2 = Me; X = 0 or S), (133; R1 = R2 = Ph; X = CH,, 0, or S), and (133; R1 = Me, R2 = Ph; X = CH2, 0, or S) has been detected by decreases in u(P=S) observed on complex formation.

s

s

II

II

R: P- X-P R; (133)

Thus, when R1 = Me, R2 = Ph, X = CH2 [i.e. (diphenylphosphinothioyl)(dimethylphosphinothioyl)methane, pmm], ~ ( P = S ) ~ ~ tdecreases h~l from 579 to 543 cm-l, and v(P=S)phenyl decreases from 601 to 581 cm-’. The smaller effect on the P=S bond associated with the phenyl groups is expected, since the methyl-substituted thiophosphoryl group should be the better donor to a 1.r. data have been listed, and approximately assigned, for M(S2PX2),, as follows: X = CF,, CH,, or Ph; M = Fe3+, Co3+, Mn2+, Co2+,Z n Z i , Cd2+,or Hg2+:X = OEt or F; M = Co3+,Co2+,or Zn2+;X = F, M = Hg2+; n = valence of the All of the n = 2 complexes show pseudo-tetrahedral co-ordination of M by the four sulphur atoms of the two dithiophosphinate ligands. Vibrational studies of octahedral [M-(S-S),-MI cages (134) in the compounds NbSzX2 (X = C1, Br, or I) and VS4, and of the trigonalbipyramidal [M-(S-S)SM] (135) in MS, ( M = Ti, Zr, Nb, or U) show

(134)

(135)

that v ( S - S ) is i.r.- and Raman-active, and occurs in the region 56& 600 cm-1 [cf: pyrites, where v ( S - S ) is below 500 ~ m - l ] . ~ ~ ~ The complexes PbL,, COL,, MnL,, FeL,, ZnL,, CuL2, NiL,, PdL2, and PtL, (L = Et,NCS;) have been prepared and examined by i.r. spectros c ~ p y u(S2)C-N . ~ ~ ~ ~ increases from 1490 to 1538 cm-l in the order listed, corresponding to increasing double-bond character. u ( C N ) is found between 1495 and 1530 cm-l in the i.r. spectra of M(chel), (M = Fe, Co, Cr, or Mn), M(chel), (M = Zn, Cd, Pd, Ni, Cu, or Pb), 631 632 L9y

534

D. A. Wheatland, C. H. Clapp, and R . W. Waldron, Inorg. Chem., 1972, 11, 2340. R. G. Cowell, E. D. Day, W. Byers, and P. M . Watkins, Znorg. Chem., 1972, 11, 1759. C. Perrin, A. Perrin, and J. P. Prigent, Bull. SOC.chim. France, 1972, 3086. (a) D. V. Sokol’skii, L. M. Kurashvili, and I. A. Zavorokhina, Imest. Akad. Nouk Kuzakh. S.S.R., Ser. khim., 1971, 21, 10; (b) R . Heber, R. K i m s e , and E. Hoyer, 2. anorg. Chem., 1972.393, 159.

448

Spectroscopic Properties of Itiorgcitiic and Orgntrometcillic Compounds

and M(che1) (M = TI or Ag), where chel = NN-diethylthioselenocarba ma t 0, E t ,N C(S)Se- . 34 1.r. spectra of diniethylaminoethanethiol complexes of Ni", Co", Khl'l, Pd", Os", and Pt'" confirm co-ordination through S and N atoms.G35 1.r. spectra of a series of dithiobenzoato-complexes of bivalent (Ni, Pd, and Pt) and tervalent (Cr, Fe, Rh, and In) metals, and some deuterioanalogues, have been reported.536 The two stretching wavenumbers of the dithiocarboxylic acid group have been located in the range 900- 1000 cm l , with v(M-S) between 300 and 400cm The regular decrease of the highest wavenumber substituent-sensitive band of the phenyl group with the optical electronegativity of the chelated metal ion is discussed. Vanadium dithiocarboxylates VL,, where L = PhCS;, p-Me. C,H4. CS;, MeCS;, or PhCH,CSg, give i.r. spectra consistent with symmetrical bidentate bonding of the ligand, i.e. (136), e ,g. in the case where R = Ph, v,(CS,) = 945 cm-l, vu8(CS2)= 1020

\

'4

(

136)

(137)

+

The first xanthates of V"' have been prepared from (h5-C,H5),VCI, Na,SCOR (R = Me, Et, Pr', Bu", or C6H11).538They are formulated as (137). 1.r. spectra were listed and an assignment was proposed, although v ( C - 0 ) , v(C=S), and v(C0-R) are believed to be strongly coupled (all are in the range 1000-1250cm-1). Characteristic i.r. bands of the tetramethylenedithiocarbamates M [S,CN(CHZ),l4 of Mo, W, Nb, and Ta are found639as follows: v(C-N) M . 1500cm-l; v(NC2) ca. 1170cm-l; v ( C - S ) ca. 1OOOcm-l; v(M-S) ca. 330 crn-'. The i.r. spectra of the complexes VOL,, NbOL,, Mo,O,L,, and MoO,L, (L = NN'-diethyldithiocarbamate, S,CNEt,) are consistent with S,Schelation of the ligand.540 1.r. spectra have been listed and partially assigned for the following dithiophosphinate complexes : NbCI,L3, TaCI,L,, CrL,, MoL,, MoOL,, WOCIL,, and WCI2L, (L = F,PS;).541-5 4 2 536

638 6:17

638 b3B

b4n

G41 G42

P. C. Jain, D. K . Rastogi, and H . L. Nigam, Indian J . Chem., 1971, 9 , 1368. M. Maltese, J.C.S. Dalton, 1972, 2664. 0. Piovesana and G. Cappuccilli, fnorg. Chem., 1972, 11, 1543. A. T. Casey and J . R. Thackeray, Austral. J . Chem., 1972, 25, 2085. T. M . Brown and J. N. Smith, J.C.S. Dalton, 1972, 1614. A . T. Casey, D. J. Mackey, R . L. Martin, and A. H. White, Austral. J . Chem., 1972, 25, 477. R . G . Cowell and A. R. Sanger, Inorg. Chem., 1972, 11, 2011. R. G . Cowell and A. R. Sanger, Inorg. Chern., 1972, 11, 2016.

Vibtutiond Spectra of' some Co-ordinated Ligcrrrds

449 I n WCI,(Me,S), the v,,.,(CSC) is shifted from 691 cm-' (free ligand) to 667 cm-l, while v,,,,,,(CSC) shifts from 741 to 730 cm-1.543 The presence of four v(PS) bands in the 48@-640cm--l range of the spectrum of [R,PSSM(CO),], (R = Et or Ph; M = Mn or Re) suggests the structure (138) for these complexes. In the derivatives (R2PS2)M(C0),L

(L

= py or PPh,), one v,(PS,) and one vitH(PS2)band can be seen 635, cu. 490 cm-l, r e s p e ~ t i v e l y ) . ~ ~ ~ The i.r. spectrum of tris-(NN-diethyldithiocarbamato)manganese(ilI) has been compared with that of the Co"' analogue in the light of structural differences revealed by X-ray crystallographic determination^.^^^ Some of the expected broadening of C-S and M-S stretching bands is observed for the M n (distorted co-ordination) over that for Co (regular, D3, coord i na t i on). 1.r. data have been listed 6 4 6 for Mn, Fe, CO, Ni, and Cu salts of ethylidene tetrathiotetra-acetic acid, (H0,CCH2S),CH-CH(SCH2COzH),. 1.r. evidence has been used to show that hydrometallation of a C=S bond occurs when CS, reacts with cis-[MH(C0)3(Ph2PC2H4PPh,)] (M = Mn or Re).547The structure M-S-C(=S)H is suggested for the product, this group giving bands at 1245 cm-' [S(CH)] and at 1008, 780 cm-l (i.r.) and 999, 781 cm-' (Raman) [for v(C-S)] for the Re complex. Wavenumbers assigned to v(C0) and v(PS,) have been listed for the complexes (139; L = CO, py, PPh3, AsPh,, or SbPh,), (140), (141 ; L-L = bipy), and Et,PS2Re(CO),(NH3).54M ((a".

0

f'J1 5.14 545

541 G47

r,4y

/Ft

P

P. M . Boorman, M. Islip, M. M . Reimer, and K. J. Reimer, J.C.S. Dalton, 1972, 890. E. Lindner and K.-M. Matejcek, J. Orgationietallic. Chenr., 1972, 34, 195. P. C. Healy and A. H . White, J.C.S. Dulton, 1972, 1883. P. PetraS and J. Podlaha, Iriorg. Chiin. Acta, 1972, 6, 253. F. W. Einstein, E. Enwall, N. Flitcroft, and J . M . Leach, J. Znorg. Nuclear Chern., 1972, 34, 885. E. Lindner an3 H. Berke, J . Organot?ietnllic Chetn., 1972, 39. 145.

450

Spec I roscopic Properties o f Inorganic and 0rganome tallic Compoutid~

v(C-N) bands in the dialkyldithiocarbamate complexes [Fe11i(R2dtc),] and [Fe'"(R,dtc),]+ are noticeably dependent upon the oxidation state of the iron.64s Thus when R = Me, Et, Pri, or C6Hll, the v(C=N) band is found at 1560, 1520, 1500, and 1490 cm-l for the FeIVand at 1520, 1480, 1470, 1490, and 1470 cm-l for the Fell1 complexes. Some approximate assignments have been proposed for ligand bands in the complexes (142).,,O

The reaction of SO, with (A5-C,H,)Fe(CO),Na gives [(h6-C6H,)Fe(CO),],SO,, shown by single-crystal X-ray studies to be the first known molecule in which SO, alone bridges two transition-metal atoms (1 43). In the i.r. spectrum, <SO) bands are found at 1135, 993 cm-l, and v(C0) at 2027, 2015, 1965, and 1953 For the chelate complexes of diphenylselenothiophosphinate [Ph2P(Se)S]- with Crl'I, Co", Nil', Zn", Cd", Pb", and Sblll, stretching vibrations of the four-membered chelate ring MS(Se)P have been assigned by analogy with MS2P and MSe,P ring systems. The strongly coupled PS and PSe stretching modes are found at 576--548 cm-l and 525-510 cm-l, respectively.662 Selected i.r. bands for Co"' thioxanthate complexes have been given, including v(C-S) at ca. 980 and 950 cm-1.653 The complexes formulated as MH(SO,)(CO)(PPh,), (M = Rh or Ir) give va and vas(S02)at 1038, 1183 cm-l (Rh), 1037, 1175 cm-l (Ir). In M(S02)(PPh3), (M = Pd or Pt), the observed values are 1056, 1215 cm-l (Pd), 1053, 1201 cm-' (Pt).554 1.r. and Raman spectra of M'[M(CS,),] (M = Ni, Pd, or Pt; M' = various cations), (Ph2MeP),M(CS,), (Ph,MeP),M(CS20) ( M = Pd or Pt), and (Ph3P),Pt(CS,0) have been Band assignments showed that v(C=S) (ca. 1030 cm--l) and v,(C-S) (ca. 850 cm-l) remained constant, but v,(CS) and v(M-S) varied. A preliminary normal-co-ordinate analysis showed extensive mixing of modes in the low-frequency region. 660

661

663 664 666

E. A. Pasek and D . K. Straub, Inorg. Chem., 1972, 11, 259. L. H. Pignolet, R. A. Lewis, and R. H. Holm, Inorg. Chem., 1972, 11, 99. M. R. Churchill, B. G . DeBoer, K. L. Kalra, P. Reich-Rohrwig, and A. WojOicki, J.C.S. Chem. Comm., 1972, 981. P. Christophliemk, V. V. K . Rao, I. Tossidis, and A. Miiller, Chem. Ber., 1972, 105, 1736. D. F. Lewis, S. J. Lippard, and J. A. Zubieta, J . Amer. Chem. Suc., 1972, 94, 1563. J. J. Levison and S. D. Robinson, J.C.S. Dalton, 1972, 2013. J. M . Burke and J. P. Fackler jun., Inorg. Chem., 1972, 11, 2744.

Vibrational Spectra of some Co-ordinnted Ligands

45 1

A number of ligand vibrations have been assigned in the complexes M[S2PX2], (M = Ni, Pd, or Pt; X = Me, Ph, F, or CF3).556 The Nil1 complexes of the cyclic dithioethers 1,4-dithiacycloheptane (dtch) and 1,5-dithiacyclo-octane (dtco), Ni(dtch)i+Xi- and Ni(dtco)i+Xi(X = ClO, or BF;), gave spectra indicating only a very weak perturbation of the tetrahedral anions.557 These were entirely consistent with lattice force effects, suggesting a basically four-co-ordinate, square-planar structure for the complexes. The complex (144) was shown to be an S-dithiocarbamate by the absence of v(C=S), but the presence of v(C=N) at 1530

v(P0) and v(PS) in Ni(dtp),(PPh,) [where dtp = (EtO),PS;] increase slightly compared with those in the square-planar complex N i ( d t ~ ) ~as, would be expected if back m-bonding from Ni is decreased by pushing the plane of the sulphur atoms below the Ni.55@ Dithiocumate complexes [i.e. containing (145)] of Ni, Pd, Pt, or Zn give v(C-C) (of S,C-Ar) in the range 1245-1289cm-'; v(S,C) lies between 900 and 1100 cm-l; and in complexes containing (146), v ( S S ) is a t ca. 480 cm-1.660

The use of (CD,),S and (CD3),S0, as well as the hydrogen analogues, has enabled Tranquille and Forel to present 661 a very thorough investigation of the vibrational spectra of trans-PdL,X, (L = sulphide or sulphoxide; X = C1 or Br), with particular emphasis on the positions of the ligand fundamentals. Small shifts in v(Pd-S) modes for Me,S complexes were also noted, whereas similar fundamentals are virtually identical in frequency for DMSO and [2H6]DMS0. 6h6 h57 5G8

5ha

m0

R. G. Cowell, W. Byers, E. D. Day, and P. M. Watkins, Inorg. Chem., 1972, 11, 1598. W. K. Musker and N. L. Hill, Znorg. Chem., 1972, 11, 710. F. Sat0 and M. Sato, J . Organometallic Chem., 1972, 46, C63. N. Yoon, M. J. Incorvia, and J. I. Zink, J.C.S. Chem. Comm., 1972, 499. J. M. Burke and J. P. Fackler, jun., Inorg. Chem., 1972, 11, 3000. M. Tranquille and M. T. Forel, Spectrochim. A d a , 1972, 28A, 1305.

452

Spectr*o.sc*opicProperties of Inorganic wid Orgmorrietallic Cbtiipoitrrcls

The complexes (147), (148), and (149) all give v(C=C) at 1628 cm--', from the free olefinic bond.562 Vibrational spectra of dimethyl sulphide complexes of Pd", Pt", and Au' have been examined and assigned.563

3

In the following complexes, i.r. data indicate that the thioacetamide ligand (taa) is unidentate, and S-co-ordinated : Pt(taa),CI,, Pt(taa),I,, Pd(taa),CI,, Pd(taa),Br,, Pd(taa),(ClO,),, Rh(taa),CI,, and Ir(taa)3C1,.664 The reaction of Pt(OCOMe),(PPh,), with SO, at room temperatures produces a complex Pt(SO,Me),(PPh,),, whose i.r. spectrum contains bands at 1270 and 1100 cm-', assigned to vas(SOz) and v,(SO,) respectively. In addition, there is another band at 990 cm-l attributed to v ( S - 0 ) and the complex is thus formulated as Pt(SO,OMe),(PPh,),, with coordination through S.666 I n [Cu(Me,PS)Cl],, which is shown by single-crystal X-ray studies to consist of a six-membered ring of Cu and S atoms in which each Cu is co-ordinated to a terminal CI and two bridging S atoms, v(PS) is shifted ca. 50cm-l to lower frequency compared with the free ligand (compared with a shift of 15 -35 cm-l when non-bridging co-ordination to CU' occurs).566a Some assignments for characteristic ligand vibrations have been made 5 6 * 0 for Cu" complexes of 1,5-disubstituted 2,4-dithiobiuret ligands (squareplanar structures). c6z

L. Cattalini, J . S. Coe, S. Degetto, A. Dondoni, and A. Vigato, Inorg. Chem., 1972, 11, 1519.

6114

$86

WG

P. L. Goggin, R . J . Goodfellow, S. R. Haddock, F. J. S. Reed, J. G . Smith, and K . M . Thomas, J . C . S . Dnlton, 1972, 1904. Y u . N . Kukushkin, S. A. Simanova, N. N. Knyazeva, V. P. Alashkevich, S. I . Bakhireva, and E. P. Leonenko, R u n . J . Inorg. Chem., 1971, 16, 1327. D . M . Barlex and R. D. W. Kemmitt, J . C . S . Dalton, 1972, 1436. ( ( I ) J . A. Tiethof, J. K. Stalick, P. W. R. Corfield, and D. W. Meek, J.C.S. Chern. c'o))m., 1972, 1141 ; ( b ) K. P. Srivastava and N. K. Agarwal, Z . anorg. Chem., 1972, 393. 168.

Vibrational Spectra of some Co-ordinated Ligandy

453 Comparison of the i.r. spectra of 2-mercaptobenzothiazole and its complex with Cu' confirms co-ordination through S.587 Assignments of v(CN) (1420-1560 cm-l) and v(CS) (808-882 cm-') have been made for Ag(dithio-oxaniide)g and analogous complexes of substituted d i t h i o - o ~ a r n i d e s . ~ ~ ~ The i.r. spectra of Zn, Cd, Hg, and Co complexes of selenourea have been discussed in relation to earlier normal-co-ordinate calculations on urea and t h i o ~ r e a . " ~Considerable mixing of ligand vibrations is indicated, and co-ordination is through Se rather than N [v(M-Se) is in the range 245--167 cm-', and the ratio of v(M-Se) to v(M-S) in related seleno- and thio-urea complexes is near to 0.81. v(C-C) and v(C-0) have been assigned 5 7 0 to 1571-1499 cm- l , 1202 1184 cm-l, respectively, in the complexes M(OEtsacsac), (M Zn, Cd, or Hg) and M(OEtacsac), ( M = Zn or Cd), where OEtsacsac = (150a), OEtacsac = (150b). =L

yly H

s

s

( 1 5 0 :I )

H Et

h1y-JyOEt

s

o

(150b)

Group-frequency i.r. assignments have been made 571 for ((0,NO)Zn[S=C(NH,),],} and { Zn[S=C( N H2)2]4}2i(NO3):--. J.r. spectra (4000-400 cm-l) have been studied 5 i 2 for M(CN)Jtu), ( M = Zn, Cd, or Hg), and the v(C=N) and v ( C S ) wavenumbers have been discussed. S-co-ordination was proposed, and the data were said to be consistent with therniogravimetric results for the relative strengths of M-S bonds: Zn > Cd > Hg. Unassigned i.r. data were listed for Zn, Cd, Hg, Pb, and Cu" complexes of dithiolenephthalic acid ( 1 5 1).573 Raman spectra have been reported for bis(thiourea)dichlorocadrniuni and tetrakis(thiourea)dichlorocadmium.~74The bis-complex is discussed

M . M . Khan and A. U . Malik. J . Inorg. Nirclwr C h ~ m .1972, , 34, 1847. G . C. Pellacani and T. Feltri, Inorg. Nircle(ir Chern. Letters, 1972, 8 , 325. G. B. Aitken, J. L. Duncan, and G. P. McQuillan, J.C.S. Dalton, 1972, 2103. A . R . Hendrickson and R . L. Martin, Austral. J . Chem., 1972, 25, 257. P. I. Protsenko, A . G . Glinina, and G . P. Protsenko, Russ. J . Inorg. Cheni., 1971, 16, 1748. A . N. Sergecvs, L. A . Kisleva, and S. M . Galitskaya, R u m . J . Inorg. Chem., 1971. 16, 945. A . V. Pandey and M . E. Mittal, Iriorg. Chir,i. A ~ I ~1972, I , 6, 135. D. M . Adams and M . A . Hooper, J . C . S . l h ~ l t o r i ,1972, 631.

454


on the basis of a factor-group analysis, but for the tetrakis-complex a molecular mode1 is adequate. Some unassigned i.r. data were given for HgCI,L, complexes, where L = 1,5-dis~bstituted-2,4-dithiobiurets.~~~ Me,ln(dtc) and RIn(dtc), (dtc = dithiocarbamate, -S,CNMe,) all give v(CN) at ca. 1500 cm-l, with one band associated with v(CS) (1000 k 10 cm-l), i.e. the dtc ligands are bidentate, giving four- or five-co-ordinate indium, respectively. R,In(ox) (ox = oxinate) is known to be dimeric, and it shows bands characteristic of bidentate oxinate (five-co-ordinate 1n).576 The complexes R,InX,L, MeInCI,,L and InCI,,L (L = Me,SbS; R = Me or Et; X = C1, Br, or I) all contain In-S bonding of the trimethylstibine sulphide ligand.577 Thus v(Sb-S) drops from 431 cm-l (free ligand) to the range 393-407 cm-l. In N-substi t u ted N’-cyano-S-(triphenyIstannyl)isothioureas, RN= C(NHCN)SSnPh, (R = p-O2N-CeH4,Ph, PhCH,, p-EtO-C,H,, or Et), v(C=N) lies in the range 2203-2183cm-l, v(C=N) 1534-1515cm l , with v(NH) 3401-3356 ~ 1 7 1 - l . ~ ~ ~

7 Potentially Ambident Ligands Cyanate, Thiocyanate Complexes, etc., and Iso-analogues.-The complexes NbX4L2,TaX,(bipy) (X = NCS-- or NCSe-, L = bipy or 4,4’-dimethylbipy), Nb(NCS)4(py)2, and Ta(NCS),(py) all contain N-bonded -NCS or -NCSe.67Q Shifts in the CN, CS, and CSe stretches all point to that conclusion. For Nb(NCS),(OR),(bipy) and Ta(NCS),(OR),(bipy) (R = Me or Et), some characteristic vibrations of NCS, OR, and bipy have been listed and discussed briefly.580 CN stretching modes below 2100 cm-l exclude the possibility of -NCSbridging, and are consistent with the presence of N-bonded -NCS. Splitting of these bands is said to indicate that the M-NCS system is bent. N-bonded thiocyanate is indicated for K[Cr(NCS),(acen)] by i.r. bands at 2085, 785 cm-l [v(CN), v(CS), respectively; acen = NN’-ethylenebis(acetylacetone iminate)].581 v(CN) in [COC),MO(SCN),MO(CO),~~has been assigned to bands at 2132 and 2096cm-‘. The former is in agreement with the presence of bridging SCN, while the latter is ambiguous (not being in the region usually associated with M-NCS- M 6i5

b76 577 s7H

570

6Ro 6H1 LH2

K. P. Srivastava and N. K. Agarwal, J . Inorg. Nuclear Chem., 1972, 34, 3926. T. Maeda and R. Okawara, J . Organometallic Chem., 1972, 39, 87. T. Maeda, G . Yoshida, and R. Okawara, J . Organometallic Chem., 1972, 44, 237. R. A. Cordona and E. J. Kupchik, J . Organometallic Chem., 1972, 43, 163. J. N. Smith and T. M. Brown, Inorg. Chem., 1972, 11, 2697. N. VuletiC and C. DjordjeviC, J.C.S. Dalton, 1972, 2322. K . Yamanouchi and S. Yamada, Bull. Chem. SOC. Japan, 1972,45, 2140. J. F. White and M. F. Farona, J . Orgnnometallic Chem., 1972, 37, 119.

Vibrationnl Spectra of some Co-ordinated Lignnds

455

v(CN) and 8(NCS) bands have been assigned in M(NCS)i- (M = M o or W) and W(NCS); : all were consistent with M-N bonding.5n3 The complex Re2(CO),(NC0), gives v,(NCO) at 21 97 cm-I, suggesting the presence of bridging NCO groups [no v(C0) was found below 1950 cm-l]. The structure (1 52a) was therefore 0 II

II

0 ( 1 52a)

v(CN) is at 2050cm-' in [(C4He),N],[Re,(SeCN),1, but it is not known whether the bonding is via the Se or the N.585 The i.r. and Raman spectra of [(Bu*,N)],[Fe(CN),(NCX)] (X = S or Se) are consistent with Fe-N co-ordination in both c a ~ e s . ~ * ~ The complexes [Co{PhP(OEt),},(NCS)]+, [CO(P~P(OE~),},(NCS)~], and [Co{Ph,P(CH,),PPh,),(NCS)]+ all give one v(CN) band (2083-2060 cm- I ) . The position of this is characteristic of an N-bonded, non-bridging NCS group - therefore these complexes contain five-co-ordinate Co. The presence of only one band in the second complex indicates that the two NCS groups are trans.687a N- and S-bonded isomers of (4-Butpy)CoCdmg),(thiocyanato) have been form gives ~ ~ ~N-bonded ~ characterized (dmgH = d i m e t h y l g l y ~ x i m e ) .The v(CN) at 2110 cm-', with the S-form having v(CN) at 2055 cm-l, the latter band being much weaker than the former. Two isomeric bridging thiocyanato-complexes of Co have been prepared, showing the following absorptions in the 2000-2200 cm-l region (N.B. the identities of the isomers are known from their preparations; i.r. spectra cannot be used to distinguish them). (NH,)5Co(NCS)Co(CN),: 2175 cm-' [~(CO-NCS-Co)]; 2141, 2131, 21 14 cm-I [v(CN)]; and (NH,),Co(SCN)Co(CN),: 2170 cm-l [v(Co-SCN-Co)]; 2120 [V(CN)].~'' The G(NCS) or 8(NCSe) region (ca. 400--450cm-') has been used to distinguish N- from S- or Se-bonded systems, in some NCS and NCSe complexes of Co", Ni, and Cu with N-benzylethylenediamine and N N ' di ben~ylethylenediamine.~~~

686

6*7

6w8

C. J. Horn and T. M. Brown, Inorg. Chem., 1972, 11, 1970. R. B. Saillant, .I. Organometallic Chem., 1972, 39, C71. R. R. Hendriksma, J . Inorg. Nuclear Chem., 1972, 34, 1581. D. F. Gutterman and H. B. Gray, Inorg. Chem., 1972, 11, 1727. (a) A. Bertacco, U . Mazzi, and A. A. Orio, Inorg. Chem., 1972, 11, 2547; (h) L. A . Epps and L. G. Marzilli, J.C.S. Chem. Comm., 1972, 109. R. C. Buckley and J. G. Wardeska, Inorg. Chern., 1972, 1 1 , 1723. K. C. Patel and D. E. Goldberg, J . Inorg. Nircleor Chem., 1972, 34, 637.

456

Spectroscopic Properties of Irrorgcirric arid Organometallic Compounds

Ni(NCS),L, has two isomeric forms; one is red, with square-planar nickel and Ni-NCS bonding; the other is green, and polymeric, with octahedral Ni, and bridging NCS groups. They may be distinguished by their i.r. spectra (L = 4 - m e t h y l q ~ i n o l i n e ) : ~ ~ ~ ~ v(CN) and G(NCS) of the NCS ligand, and v(C=N) of L (cu. 1600 cm I ) have been listed for Ni( NCS)2Lcompounds where L = ( 1 52b) or ( 1 52c).""?'

(152b)

I
I,CIIt [SbFsI[(RU(CO),(~-C~)}~X]+[YX ] - = Br or I Y = PF, or BPh, Ku( CO),I,L, I, = py, Ph,P, or Ph,As [NEt, [ R U , ( C O ) ~ ~ ~ ] ~ -

m Ru

796 797 798

794

OC/ I “GeMc,

co

Ru(CO)(PhCH,PMe,),CI, [Ru(CO)H(MeCN),(PPh,),] Ru(CO)HI(CNAr)(PPh,),

724 795

+

PPIl,

X = S, Y Ru(CO)I,(SbPh,),

Osmium Carbonyl Complexes

=

NEt,

i

799

798

It300

7Q6

D. Cullen, E. Meyer, jun., T. S. Srivastava, and M. Tsutsui, J.C.S. C’hcm. Coinrii.,

797

R. J. Haines and A. L. du Preez, J.C.S. Dalton, 1972, 944. J. V. Kingston a n d G. R. Scollary, J. Itiorg. Nuclear Chem., 1972, 34, 227. D. F. Christian, G. R. Clark, W. R. Roper, J. M. Waters, and K. R. Whittle, J.C.S. Chem. Comm., 1972,458. R. P. Ferrari, C. A. Vaglio, 0. Gambino, M. Valle, and G. Cetini, J.C.S. Dalton,

708 700

800

1972, 584.

1972, 1998.

801

G. R. Clark, K. R. Grundy, W. R. Roper, J. M. Waters. and K. R. Whittle, J.C.S. Chem. Comrii., 1972, 119.

488


Cobalt Carbonyl Complexes Ref: [ MeOZnCo(CO),],

Hg[CO(CO)qIii XHg[Co(CO),l, Co(CO),SnCI, Co(CO),(BrC2F41 [(CO),Co,CCO] [BF,]CO,(CO),, [Co(CO),L12H g

696

X = C1, Br, o r I

L = (PhO),P, PhOP(OCH,),, (2-C1C2H,0),P, (MeO),P, PhP(OMe),, Ph,P(OMe), (Et,N),P, PhPPr',, o r Ph,MeAs L' = (Ph,PCH,), or (Ph,AsCH,),

[co2(co)6L'1 g [Co(CO),HgBrI,(Ph,As~H,), Co(CO),(Ph,MeAs)X X = HgBr or SnCl, Y = OBCI,NEt,, OBBr,NEt,, or C03(CO)9Y OAI Br,N Et, (CO),Co(CF,),Co(CO), Ph

}802 803 746 804 805

803

806

746

751

c04(co)12-- n L7&

Co( CO),Li Co(CO),Li(OC Me)

L = tertiary phosphine or tertiary phosphite: R = 1, 2, 3, or 4 L = P(OMe),, PMe,, or PEt, L' = P(OMe),

F,C-C. N=N, F3C-8--:Co/, PI1

\c/ 1 co

//

0

x = 6 , y = O ; . ~ = 5,y=O x = 5 , y = 1 ; .Y = 4, y = 0 x = 3, y = 0 ; .r = 3, y = 1 s = 3, y = 3; .Y = 2, y = 2 Co(CO),(NO)[C(OEt)NR1R2] R1 = R2 = M e or E t ; or R1 = H. R2 = M e

""I "'I5

""" #":

"'IH

8uy

}807 808

co

Co,(CO),[C6(CF3),(CH,),H,__,._,I

un:'

805

809

782a

H. L. Conder and W. R. Robinson, Inorg. Chcm., 1972, 1 1 , 1527. J. Newman and A. R. Manning, J.C.S. Dalton, 1972, 241. J . E. Hallgren, C. S. Eschbach, and D. Seyferth, J . Amer. Chern. Sor., 1972, 94, 2547. D. Labroue and R. Poilblanc, Inorg. Chim. A d a , 1972, 6 , 387. G. Schmid and V. Biitzel, J. Orgatrometallic Chern., 1972, 46,149. S. Attali and R. Poilblanc, Inorg. Chitrr. A d a , 1972, 6 , 475. M . I . Bruce. B. L. Goodall, A. D. Redhouse, and F. G. A . Stone. J.C.S. Chent. Comni., 1972, 1228. R . S. Dickson and P. J. Fraser, Austral. J. Chptll., 1972, 25, 1179.

Vihrcitiorial Spectra of some Co-oriiitiafeii Lignniis

Cobalt Carbonyl Complexes

(cotff.)

’

[Et,Nl [CO(CO),(CN),~P(C,H,~)~}I-,H,O Co(CO),(CN)L, L = PPh,, PEt,, o r P(C6Hl1), [Co(CO),L,l,Hg L = (PhO),P, PhOP(OCH,),, (2-CIC,H40),P, (MeO),P, PhP(0 Me),, Ph,POMe, Ph,MeP, or Et,P L’ = (Ph2PCH,), or (Ph,AsCH,), [Co(CO),L’I,Hg Co(CO),(Ph,PCH,),X X = HgCl or SnCI, CO(C0)[P(OMe)& [Et4NlS[CO(C~)(CN),(PP~,),I-,~H,O K + [Co(CO)(CN),L,]-,3H20 L = MePPh, or Me,PPh K i [Co(CO)(CN),( PEt,),] -,Me,CO,H,O K [Co(CO)(CN),(di phos)] -,H,O +

Rhodium Carbonyl Complexes R h(CO),(bza H)CI R h( CO),( bzm H )CI Rh(CO),CI( PhNH,) R h(CO),(azb) [Rh(CO),(azb)CIl,, [ Rh(CO),LI +

bza = benzylidenedianilinyl bzin = benzylidenemethylaminyl }arb

= azobenzene anion

L = bipy, acac, or salicylaldehyde phenylimine (sal= N Ph) L = PMe,, PMe,Ph, or PPh, n = I , 2, or 3; m = 0, I , 2, 3, or 4 X = C1 o r Br; opd = o-phenylenediamine ’ 813b Ph 1

14

PI1

++

cis-[R h(CO),CI(R,P)]

trans- [ R h( CO),CI( PhBu2P)] R h 2( CO), Cl2(bi PY)

H10 Wl1

Hll HI3

n14 HI5

P Ph X = C1 o r Hr R , = Ph,, MePIi,, or Et,Ph; or R,P = Ph,PO x = 1,

2, or 3

r3 J

815

J. Halpern, G. Guastalla, and J. Bercaw, Co-ordination Chem. Reii., 1972, 8, 167. M.I. Bruce, M. Z. Iqbal, and F. G. A. Stone, J. Organometallic Chem., 1972, 40, 393. C. Cocevar, G. Mestroni, and A. Camus, J. Organometallic Chem., 1972, 35, 389. (a) J. Gallay, D. de Montauzon, and R. Poilblanc, J. Organometallic Chem., 1972, 38, 179; (b) J. V. Kingston, F. T. Mahmoud, and G. R. Scollary, J . Zizorg. Nrirlenr Chein., 1972, 34, 3197.

L. D. Rollmann, Inorg. Chim.Acta, 1972. 6 , 137. Yu. S. Varshavskii, N. V. Kiseleva, and N . A . Buzina, Russ. J . Inorg. C h e m . , 1971, 16. 862.

490

Spectroscopic Properties of'Iriorgcrriic arid Orgariornetnllic Cornpounds

Rhodium Carbonyl Complexes

(corri.) Rl$

Rh(CO),( PPh,),( CO,Mc) 816 C, H As Ph Rh,(CO),CI( PhP( ) 679 C, H, As P h, I< h(CO)X(1. ",), X = 831 =!

L = AsPh,, PPh,, PPh,Me, PPhMe,, or PPh(OMe), L’ = PPh(OMe), or P(OPh),

>832

L = PPh, or PPh,Me L = PPh(C,H,,),, PPh,. or P(p-F.C,H,),

M. I. Bruce, G. Shaw, and F. G. A. Stone, J.C.S. Dalton, 1972, 1082. M. I. Bruce, G. Shaw, and F. G. A. Stone, J.C.S. Dalton, 1972, 1781. P . Chini, A. Cavalieri, and S. Martinengo, Co-ordination Chem. Rev., 1972, 8. 3. A. R. Manning, J. Organometallic Chem., 1972, 40,C73.

8

Mossbauer Spectroscopy BY R. GREATREX

1 Introduction Following the pattern adopted in last year's Report, the material in this chapter is organized into seven main sections. After this opening section, which lists the resonances studied and covers books and review articles, there is a brief survey of theoretical aspects followed by developments in instrumentation and methodology. The main body of the work is reported in Sections 4--6, which deal in turn with iron-57, tin-119, and other elements. Section 7 takes the form of a Bibliography and contains for the most part papers on alloys of iron and tin not discussed in the text. Four resonances have been reported for the first time during the year, namely 73Ge (13.3 keV), lsoOs (187 keV), 236U (45.3 keV), and 2:luPii (57.3 keV). In addition the following forty resonances have received attention: 57Fe(14.4 keV), 61Ni (67.4 keV), 67Zn(93.3 keV), "Kr (9.3 keV), 9 9 R ~(90 keV), l19Sn (23.9 keV), lZISb (37.1 keV), 126Te(35.5 keV), I t 7 l (57.6 keV), lz91 (27.8 keV), 1 3 T s (81.0 keV), 14*Sin (22.5 keV), 161Eu (21.7 keV), lS3Eu (83.4, 97.4, and 103.2 keV), 15%d (86.5 keV), '"'Gd (64.0 keV), lulDy (25.6 keV), Is5Ho (94.7 keV), lseEr (80.6 keV), 170Yb (84.3 keV), 171Yb (66.7 keV), l7*HHf (93.2 keV), lsoHf (93.3 keV), IH"W (104 keV), lslTa (6.2 keV), lMzW(100.1 keV), IM3W(46.5 and 99.1 keV), lA4W( I 11.1 keV), lSsW (1 22.5 keV), lHGOs( 1 37.2 keV), lHROs(1 55.0 keV), l M 9 0 s(69.6 keV), lglIr (1 29.5 keV), 19313t (1 30 keV), 1u77A11 (77.3 keV), es7Np(59.5 keV), and 23xU(44.5 keV).

Books and Reviews.- I t is convenient to group together at this point all books and review articles, and i t should be noted that these references may not be mentioned again in subsequent sections of the report. When searching for references o n a specific topic it may therefore be wise to scan this scction as well as the later pages. A book dealing with chemical applications of Mijssbauer spectroscopy has been published during the year and a uniform theoretical treatment of magnetic resonance has appeared, covering e.s.r., n.tn.r., and quadrupole resonance, in addition to the Mossbauer effect.2 The Miissbauer-effect data index covering the year 1970 is now available,:' and its authors have H. Sano, 'Miissbauer Spectroscopy. Its Chemical Applications', Kodanslia, Tokyo, 1972. C. P. I3oo1eand M. A . Farach, 'Theory of Magnetic Resonance'. Wilcy, New York, 1972. J. G . Stevens a n d V. E. Stevens, 'Miissbauer Effect Data Indcx, covering the I970 I-itcrnture', Plenum, New York, 1972.

494

Mossbnirer. Spectroscopy

495

also produced an extensive compilation of nuclear parameters for observed Mossbauer transitions, together with a survey of numerous applications of the t e ~ h n i q u e .Standard ~ substances for Mossbauer calibration have been A number of reviews covering catalogued by the I.U.P.A.C. Commis~ion.~ general principles of Mijssbauer spectroscopy and various applications of the technique i n chemistry and physics have also appeared.+ l1 A panel of the International Atomic Energy Agency met in Vienna in 1972 to review the present status of the Mossbauer technique and its applications in different fields of science and technology. The proceedings of this conference have now appeared l 2 and contain papers on instrun~entation,’~ phase analysis, site population, and lattice defects,14 atomic niotion in metals,16 implantation studies,lGcoherence effects,17the actinide elements,1x transferred hyperfine interactions in 5s -p elements,19 biological systenis,2”la1 organometallics,22 co-ordination c o m p o ~ n d s , ~ chemical ~ effects of nuclear transformations,24mineralogical applications,25 and it number of topics of a more general nature.26 2y J . G . Stevens, J. C. Travis, and J. R. Devoc, AIicrl.rr. C‘hem., 1072. 44, 384R. ‘Catalogue of physiocheniical standard substances’ ( 1 U PAC Comni. on i’hysioulieniical Measurements a n d Standards), Pure Appl. Chern., 1372, 29, 599. J . K. Sams, ‘Some applications of Mossbauer spectroscopy in chemistry and chemical physics’, ed. C. A. McDowell, in ‘MTP Review of Chemistry: Physical C‘!iemistry’, Series One, Vol. 4, Chap. 3, Butterworths, London. 1972. R. L. Cohen, ‘Mossbauer spectroscopy recent developments’, Scieiice, 1972, 178, 828. U. Gonser, ‘Mossbauer spectroscopy’, Rn(1e.u Ruiidsch, 1972, 171. ‘’ D. Barb, ‘Miissbauer effect and its applications‘, R P P . Fiz. C’hitn. ( A ) , 1972, 9, 15 I . A. Andreeff and M. Sclienk, ‘Nuclear physical methods in crystallography ;!lid solid statc physics’, Krisr. Tech., 1972, 7, 317. I’ A . Szabo, ‘Mossbauer spectrometry study of molybdenum trioxide--iroii(iii) oxide catalysts’, Rev. Rounitrine Chiin., 1972, 23, 550. ‘Mossbauer Spectroscopy and its Applications’, International Atomic Energy Agcncy, Vienna, 1972. G . M. Kalvius and E. Kankeleit, ‘Keccnt iniprovemcnts in instrumentation and methods of Mossbauer spectroscopy’, ref. 12, p. 9. 14 U. Gonser, ‘Phase analysis, site population and lattice defects’, ref. 12, p. 89. It C . Janot, ‘Mossbauer effect and atomic motion in metals’, ref. 12, p. 109. 1-1. de Waard, ‘Lattice location of implanted impurities derived from Mossbauer clfcct measurements’, ref. 12, p. 123. Yu. Kagan and A . M. Afanas’ev, ‘Cohcrencc effects during nuclear resonant intcraclion of gamma quanta in perfect crystals’, ref. 12, p. 143. G . M. Kalvius, ‘Miissbauer spectroscopy in the actinides’, ref. 12, p. 169. I H M . Pasternak, ‘Transferred hyperfine interactions in 5s-p elements’, ref. 12, p. 197. ”Ib G . Lang, ‘Interpretation of paramagnetic Miissbaucr spectra of biological molecules’, ref. 12, p. 213. H . Frauenfelder, 1. C. Gunsnlus, and E. Miinck, ‘Iron-sulphur proteins and Mlissl):tuL*r spectroscopy’, ref. 12, p. 23 I . “2 R. H . Herber, ‘Miissbauer spectroscopy of organomctallic compounds’, rcf. 12, p. 257. 2% J. Danon, ‘Mossbauer effect applications to co-ordination chemistry of transition elements’, ref. 12, p. 281. 2 4 J . P. Adloff and J. M. Friedt, ‘Mossbauer studies of chemical effects of nuclear transformations’, ref. 12, p. 301. 25 A. G . Maddock, ‘Mossbauer spectroscopy in mineralogy’, ref. 12, p. 329. 28 S. Hufner and E. Matthias, ‘Advantages and limitntions of Mossbauer spectroscopy in comparison to other methods’, ref, 12, p. 349. 2 7 A. Simopoulos and A. Kostikas, ‘Mossbauer spectroscopy in Greece’, ref. 12, p. 3x1. :* I . Dizsi, ‘Miissbauer studies in developing countries‘, ref. 12, p. 389.

496

Spectroscopic Properties of Iirorganic mid OrganometaNir Compounds

An extensive review has appeared, entitled “Mossbauer spectra of inorganic compounds: bonding and structure”. It deals critically with recent studies chosen to illustrate the use of the technique. The concepts of partial isomer shift and partial quadrupole splitting are examined in detail, but the authors have chosen not to discuss magnetic hyperfine data.29 Experimental aspects of Mossbauer spectroscopy have been covered 29rr and the interpretation of tin-1 19 spectra has been discussed at length.3o A substantial survey of applications in the study of the chemical effects of nuclear reactions in solids has appeared.31 Applications in co-ordination 3 2 a * 33 organometallic chemistry,34 and biological systems,”* 3‘i and studies of frozen spin-crossover and intermolecular interactions 30 have also been reviewed. Other areas surveyed include lattice-defect studies 40 and applications in surface science4’ and ore mining.42 Mossbauer studies have also been mentioned briefly in several general review^.^^-^^

R. H. Herber and Y. Hazony, ‘Experimental aspects of Mossbauer spectroscopy’, i n ‘Techniques of Chemistry’, ed. A. Weissberger and B. W. Rossiter, Wiley, New York, 1972, Vol. 1. 280 G. M. Bancroft and R. H. Platt, Progr. Inorg. Chem., 1972, 15, 59. R. V. Parish, Progr. Inorg. Chem., 1972, 15, 101. y1 A. G. Maddock, ‘Mossbauer spectroscopy in the study of the chemical effects ol‘ nuclear reactions in solids’, ed. A. G. Maddock, in ‘MTP International Review ol‘ Science: Inorganic Chemistry’, Series One, Butterworths, London, 1972, Vol. 8, p. 253. s2 K. Burger, ‘Co-ordination Chemistry’, Butterworths, London, 1972. 3aa K. Burger, Inorg. Chin]. Acta, Rev., 1972, 6, 31. s3 M. L. Good and C. A. Clausen, ‘Applications of Mossbauer spectroscopy in the study of coordination compounds’, in ‘Co-ordination Chemistry’, ed. A. E. Martell, V a n Nostrand, 1972, Vol. 1. M J. C. Maire, Afinidad, 1972, 29, 177. 36 A. J. Bearden and W. R. Dunham, ‘Iron electronic configurations in proteins: studies by Mossbauer spectroscopy’, in Structure and Bonding, 1972, Vol. 8. :I6 J. L. Holtzman, Methods Pharmacol., 1972, 2 , 157. 37 I. Dezsi, Kozp. Fiz. Kut. Inter., 1972, 72. y n E. Konig, Ber. Bunsengesellschaft phys. Chrin., 1972. 7 6 , 975. 38 H . Sano, Kagaku No Ryoiki, 1972.24, 5 8 . I 0 H. Ino, O y o Biitsuri, 1972, 41, 735. M. C. Hobson, Progr. Surface Membrane Sci., 1972, 5, 1 . L. Simon, Rudy, 1972, 20, 46. J. J. Zuckerman, ‘Synthesis and properties of the tin-halogen and tin-halogenoid bond’, in ‘The Bond to Halogens and Halogenoids - Organometallic Compounds of the Group IV Elements’, ed. A. G. MacDiarmid, Marcel Dekker, New York, 1972, Vol. 2. 4 4 G. G. Libowitz, ‘Solid state properties of metallic and saline hydrides’, ed. L. E. J. Roberts, in ‘MTP International Review of Science: Inorganic Chemistry’, Series One, Butterworths, London, 1972, Vol. 10, Chap. 3. J. J. Turner, ‘Physical and spectroscopic properties of the halogens’, ed. V. Gutmann, in ‘MTP International Review of Science: Inorganic Chemistry’, Series One, Butterworths, London, 1972, Vol. 3, Chap. 9. J. D. M . McConnell, ‘Binary and complex oxides’, ed. D. W. A. Sharp, in ‘MTP International Review of Science : Inorganic Chemistry’, Series One, Butterworths, London, 1972, Vol. 5, Chap. 2.

Miissbauer Spectroscopy

497

2 Theoretical This section includes only papers of a general theoretical nature. Theoretical studies relevant to a particular isotope are discussed where appropriate in later sections of the Report. The possibility of using Mossbauer radiation to create a y-laser has been discussed. The expressions derived for the cross-section of the stimulated emission of y-quanta and for the amplification coefficients show that a laser may be made using crystals containing long-lived (7 2 loss) nuclear Approximations used in the literature in the calculation of Mossbauer isomcr shifts have been discussed and compared with the results obtained using mathematically exact expressions incorporating Dirac-Slater orbitals and a three-parameter Fermi-type nuclear charge distribution. It was shown that the non-uniformity of the electronic density over the nuclear volume affects the results and that the quantities A I $(O) l2 and A(r2> are not entirely independent variables. Furthermore, A singlet ground state and the unexpected angular-independence of the relative intensities of the two components of the doublet for a single crystal was taken to indicate that the impurity sites are all equivalent and that they feature a principal axis pointing in one of three mutually orthogonal directions such as the , (OlO,, and (001) axes with equal probability. In a temperature-dependence study on the polycrystalline material there was no discontinuity in the regular decrease in both the spectrum areas and the chemical isomer shift at the lambda point, and the linewidth remained constant at 0.26 mm s-l. However, the quadrupole splitting decreased markedly from about 190 K up to the known lambda point at 242 K, as can be seen in Figure 1. In this respect it is noteworthy that recent thermal-expansion and specific-heat studies on NHICl only 138

A. J. Bannaghan, D. R. Hayman, and P. L. Pratt, Proceedings of the Seventh International Symposium on the Reactivity of Solids, 1972, p. 68.

Mossbaiier Spectroscopy

51 I

reveal effects of the phase transition in the range 234-244 K. The quadrupole splitting was analysed theoretically and the ligand-field splitting was found to be approximately 900 cm- in the low-temperature ordered state compared with 450 cm-l in the disordered No anomaly is observed in either the isomer shift or the normalized resonance intensity at the antiferroelectric transition (Tc = 148 K) for 57Fe3+doped into NH4H2P04. However, there is a sudden increase in the linewidth around T,, consistent with the expected increase in the electricfield gradient created by the onset of antiferroelectric ordering, the effect being more pronounced in single-crystal than in powder absorbers. The experiments suggest that the iron atoms do not take part in the coupled ferroelectric mode, in contrast to the observation of Brunstein for TO : KHzP04.140 The electronic properties of Fe2+ in cubic KMgF, have been studied. At room temperature the single-crystal spectra contain singlets from Fez+ and Fe3+. At temperatures below 12 K, the Fez+ line splits into a quadrupole doublet and comparison of the data with a random-strain model due to Ham yields a value of 120 cm-l for the position of the first excited spin-orbit level. Experiments in an applied magnetic field at low temperatures yield 141a value of - 495 & 30 kG for the core-polarization hyperfine field in Fez+and a value of 4.1 a.u. for . 57Fe2+in place of Ca2+in RbCaF, has been shown to have a large isomer shift relative to FeF,, owing to the decrease of the overlap-induced electron density at the iron nucleus accompanying the increase in the Fe-F distance (206 pm in FeF,, 6 = 1.41 mm s-l; 236 pm in RbCaF,, 8 = 1.55 mm s - ' ) . ' ~ ~ The magnetic hyperfine interaction of 57Fe2+in FeF,, MnF,, and ZnF, is discussed on p. 516. Experiments on the trinuclear chromium complex [Cr,(MeCO,),(H,O),]Cl,6H20 with 57Fe3+substituting for Cr3+up to 2% are described on p. 529, and an analysis of the Mossbauer hyperfine interaction data for the octahedral 3d(t2g5)iron(irr) ion in K,Co,-,Fe,(CN), are discussed on p. 504. Mossbauer spectra taken during the U.V. excitation of rutile, containing adsorbed Fe3+, suggest that the adsorbed Fe3+ions form acceptor surface states which trap holes to become Fe4+. The isomer shift of the induced Fe4+ is claimed to be more negative than any value previously reported, indicating a more ionic species.143 Preliminary data have been reported of studies of the metal-non-metal transition in the V,zO,n-l system doped with 1 at.% 57Fe. The study was undertaken to elucidate the origin of anomalies in the temperature dependence of the magnetic susceptibility for members of this system. The oxides 19@ l4l lla 143

T.C. Gibb, N. N. Greenwood, and M. D. Sastry, J.C.S. Daffon, 1972, 1896.

M. D. Sastry, So[id Sfare Cornm., 1972, 11, 1671. R. B. Frankel, J. Chappert, J. R. Regnard, A. Misetich, and C. R. Abeledo, Phys. Rev. (B), 1972, 5, 2469. A. Cruset, Chem. Phys. Letters, 1972, 16, 326. A. J . Nozik, J . Phys. (C), 1972, 5, 3147.

5 12

Spectroscopic Properties of Inorgunic arid Orgairometallic Compolrnds

v407, V6O9, VsOll, and V8OlS all have two kinks in the x us. T curve at temperatures TA and 7'13 (Ti < TB), whereas v7013, which is metallic, shows only the kink at the lower temperature, TA = 43 K . V306,which is a semiconductor, shows neither kink but shows instead a broad maximum at T = 133 K . Mossbauer spectra were obtained for Vs06, V 1 0 7 , and v@,, which were chosen as representative of the three types of magnetic behaviour. They were all antiferromagnetic at 4.2 K with effective hyperfine fields Heffof 390, 400, and 440 kG,respectively. For V407and V7OI3, Heff follows a Brillouin function as the temperature increases, and disappears near TA, which would therefore appear to be equivalent to the Nee1 point. For V 3 0 5 H,ff disappears at about 69 K, which is much lower than the temperature of the broad peak in the x us. Tcurve.144 Spectra have been obtained for 57Fein ferroelectric PbTiO, in the temperature range 3 0 0 - 1 100 K . The quadrupole interaction in the ferroelectric phase remains nearly constant up to 320 "C, beyond which it decreases gradually, to disappear at the transition temperature T, = 480 f 2 "C.The ratio of the quadrupole interaction of 57Fein PbTiO, to that in BaTiO, at room temperature is 1.41 k 0.04, in good agreement with the results of perturbed angular correlation studies. Both the centre shift and the area under the resonance show anomalous temperaturevariation in the vicinity of the transition temperature and it is suggested that the Debye temperature of the lattice decreases considerably on crossing the transition temperature. The essential validity of the suggested temperature variation of the soft mode was d e m 0 n ~ t r a t e d . l ~The ~ ferroelectric phase change in BaTiO, has been discussed e1~ewhere.l~~ Spectra have also been obtained for samples of ZnS containing 2-14.2% iron.lQ7 67 CO Source Experiments and Decay After-efect Phenomena. Experiments to test the suitability of /3-rhombohedral boron as a host matrix for a 6 7 C ~ Mossbauer source are referred to on p. 509.135The Mossbauer effect in impurity atoms of 57mFein silicon has also been Diffusion of 6 7 Cin~ InSb has been studied by means of 67Feemission spectroscopy. Two types of iron atoms are present, one of which decreases in relative concentration with increasing depth below the surface. Three different diffusion mechanisms were operative, the corresponding diffusion coefficients being 7 x 3 x 1O-l2, and 7 x 10-lo cm2s-' at 420 "C for x < 10 p, 10 < x < 50 p, and x = 50 p, re~pectively.'~~ H . Okinaka, K. Kosuge, S. Kachi, M . Takano, and T. Takada, J . Phys. SOC.Japan, 1972,32, 1148. l P 6 V. G. Bhide and M. S. Hegde, Phys. Reu. ( B ) , 1972, 5 , 3488. 146 H. G. Maguire and L. V. C. Rees, J . Phys. (Paris), Coffoq., 1972, (2), 173. IoiT. M. Aivazyan, L. A. Kocharyan, A. R. Mkrtchyan, and M. Pulatov, Izvest. Akod. Nauk Uzbek. S.S.R., Ser. fiz.-mtit. Nauk, 1972, 16, 64. l o * B. I, Boltaks, M. K. Bakhadyrkhanov, and P. P. Seregin, Sotliet Phys. Solid State, 1972, 13, 2358. l d e D. N . Nasledov, Yu. S. Smetannikova, K . 1. Vinogradov, and V. K. Yarmarkin, Phys. Lrtters ( A ) , 1972. 40, 224.

lP4

Miissbauer Spectroscopy 513 Mossbauer studies of 57Co-doped LaCoO,, combined with magnetic susceptibility data in the temperature range 4.2-1200 K, have shown that cobalt ions exist predominantly in the low-spin cobalt(ri1) state at low temperatures and transform partially to high-spin Co3+ ions up to 200 K. Above 200 K the Co3+/CoI1'ion-pairs transform to Co"/Co4 ion-pairs. At higher temperatures the proportion of Co3 decreases progressively and disappears completely above the first-order localized-electron-collectiveelectron transition temperature, 1210 K. Isomer shift data coupled with the .f-factor changes which occur at the transition temperature indicate that the transition is caused essentially by the change in entropy of the d electrons. The studies are consistent with Goodenough's hypothesis that the crystal field and band limits are distinct thermodynamic states.16o*151 The charge states of 67Featoms produced in the electron-capture decay of 6 7 Catoms ~ in solid xenon are discussed on p. 503. The chemical after-effects of electron-capture decay in 57C0and of the isomeric transition in llQSnhave been shown to be similar. Thus, the emis~ a pair of sion spectrum of C O ~ ( P O ~ ) ~ , Xdoped H ~ O with 6 7 Ccontains doublets due to Fe2+and Fe3+(the proportion of the latter increasing with increasing x ) and the emission spectrum of SnC1,,2H20 labelled with ll%n shows a small shoulder indicative of Sn4+. By contrast the higher charge states are not present in the emission spectra of Sn,(PO,), doped ~ of Sn,(PO,), doped with llBSn, indicating that Fe3+ and with 6 7 Cand Sn4+ are produced by oxidation of the decay products by OH radicals created during autoradiolysis of the H 2 0 ligands in the hydrated complexes. l6 The appearance of resonances corresponding to iron(rr) species in the Mossbauer emission spectra of 57Feformed by electron-capture decay of 5 7 Cin~ cobalt(m) compounds is difficult to explain. It was once thought that the internal pressure experienced by the newly formed 57Fe3+in sites originally occupied by the smaller 57C03+parent might be the cause, but 57Fe2+resonances have since been observed in 67Co-doped iron(rrr) complexes, rendering this explanation unlikely. It seems more probable that the emitted Auger electrons cause radiolysis of the parent compound to produce the aliovalent species. The full paper dealing with the Mossbauer study of the electron-irradiation of Fe(acac),, a prelininary account of which was published in 1970, has now appeared. The paper also describes similar studies on iron(Ir1) citrate, iron(rr1) edta, and iron(m) trisdipiperidyl perchlorate. In all cases the spectra resemble the emission spectra observed after electron-capture decay in the corresponding 67C03+-labelledcompounds, which suggests that the stabilization of the anomalous iron charge states in these compounds is due to an autoradiolysis mechanism.153 +

+

V. G. Bhide, D. S. Rajoria, Y. S. Reddy, G. R. Rao, G. V. S. Rao, and C. N. R. Rao, Phys. Reu. Letters, 1972, 28, 1133. l S 1 V. G. Bhide, D. S. Rajoria, G. R. Rao, and C. N. R. Rao, Phys. Reu. ( B ) , 1972, 6, 1021. lsz J. M. Friedt and Y. Llabador, Radiochem. Radioanalyt. Letters, 1972, 9, 237. IBs E. Baggio-Saitovitch, J. M. Friedt, and J. Danon, J . Chem. Phys., 1972, 56, 1269. ISo

5 14


Emission spectra of the 57CoZ+-doped acetylacetonates of aluminium(iii), chromium(rrr), and cobalt(ii1) consist of simple quadrupole doublets, whereas the doped acetylacetonates of manganese(m) and iron(il1) show three-peak spectra which correspond with that of 57Co(acac)3. These

1

s

$Il \

c

GO

L 3

L

5

-4

I

I

-3

-2

,

-1

,

I

0

1

2

3

4

Source velocity / (mrn s-' I Figure 2 Miissbauer spectra of (a) 7Co(CN), and (b) Co(b i ~ y )7Co( , ~ CN),,2 H,O' The component doublets are ascribed to : I , a ferripentacyanide; 2, Fe(CN),4- or Fe(CN),,-; 3, Fe(CN),3-

results are taken as evidence that cobalt(i1) exchanges readily in the solid state with the manganese and iron compounds but not with the aluminium, chromium, and cobalt compounds. Possible reasons for the differences in behaviour were The spectra of [Fe(57Co)(bipy)3](C104)3(cobalt-doped) and [57C0(bipy),][C1O4], (cobalt-labelled) both indicate the presence of Fe2 , Fe(bipy),2+, and Fe(bi~y),~+ species, which demonstrates further the unimportance of pressure effects within the lattice. The hexacyanides K,Fe(67Co)(CN),, K357Co(CN), [see Figure 2(a)], and K,Fe(57Co)(CN),,+

16'

V. Ramshesh, K. S. Venkateswarlu, and J. Shankar, J . Inorg. Nuclear Chem., 1972, 34,2121.


515

3H,O (Prussian Blue) give very similar spectra containing two doublets with intensities in the ratio 80 : 20. The first is assigned to a pentacyanide,

the formation of which argues against displacement of 57Fefrom the 5 7 C ~ site, and the second to the species 57Fe(CN)63-.In a further attempt to check whether an exchange of central atoms can occur between two complexes, measurements were also performed on two specifically 5 7 C ~ and [Co(bipy),]labelled double complexes, [s7Co(bipy)3][Co(CN)6],2H20 [57Co(CN),],2H20. The spectrum of the first compound contains only and 57Fe(bipy)3+and is distinctly different resonances due to 67Fe(bipy)32+ from the spectrum of the second compound [see Figure 2(b)], which contains only two doublets, one from a ferripentacyanide and the other from the 57Fe(CN)Bs-species mentioned earlier. There is therefore no evidence of an exchange of central atoms as a consequence of the electron-capture process.16s has been studied by Mossbauer emission The decay of 67C02+[Fer11(CN)6] spectroscopy and y-y coincidence techniques. In the time interval r = (t-60 ns both Fe2+and FeS+were detected, in the proportions 30 : 70, but for 7 = 0-160 ns only Fe3+was detected. The iron therefore appears initially in the same valence state as the parent cobalt atom, but decays rapidly to the stable FeS+state.166 The emission spectrum of [C0(phen),](ClO~)~,2H,Ohas been reinterpreted. At 4.2 K the spectrum consists of three overlapping doublets which were originally assigned to S = 0, S = 1, and S = 2 states of the iron(r1) ion. Both theoretical and experimental evidence has now been presented to demonstrate, firstly, that the existence of the spin triplet (S = 1) ground-state is most unlikely and that the doublet originally assigned to this state arises instead from the S = 2 ground-state of the intact [57Fe(phen)3(C10,)2] complex and, secondly, that the doublet originally assigned to the S = 2 state arises from a complex involving one defect phenanthroline ligand.157 ~ the complex Co"L2CI2 [L = oElectron-capture decay of 6 7 C in (Me2As)2CBH4] has been shown to produce Fe"L2CI2 complexes containing both high-spin (f2p4eg2) and low-spin (tzg6euo) iron(ii), whereas [CO"~L,C~,] gives the corresponding complexes with low-spin iron(rI1) ( t z u s e y 0 and ) low-spin iron(iv) ( ~ ~ ~ ~The e 67Fe ~ ~absorption ) . ~ ~ spectra * of these complexes are discussed on p. 538 (see ref. 241). The Mossbauer parameters for an oxygenated haeme complex, produced in a frozen solution by nuclear decay from the isomorphous 57Co-labelled compound, have been shown to agree well with those obtained by Mossbauer absorption spectroscopy of o x y h a e m o g l ~ b i n . ~ ~ ~ ls6 IKa

167

168 169

K. E. Siekierska, J. Fenger, and J. Olsen, J.C.S. Dalton, 1972, 2020. V. P. Alekseev, V. I. Goldanskii, V. E. Prusakov, A. V. Nefed'ev, and R. A. Stukan, Pis'ma Zhur. eksp. i feor. Fiz., 1972, 16, 65. E. Konig, P. Gutlich, and R. Link, Chern. Phys. Letters, 1972, 15, 302. A. Cruset and J. M. Friedt, Radiochenr. Radioanalyt. Letters, 1972, 10, 353. L. Marchant, M. Sharrock, B. M. Hoffman, and E. Miinck, Proc. Not. Acad. Sci. U.S.A., 1972, 69, 2396.

5 16

Spectroscopic Properties of’Inorganic and Organonietallic Compounds

Compounds of Iron.-High-spin Iron(11) Compounds. The configuration interaction method has been used to investigate the effects of weak covalency on the crystal-field splittings, the g-factors, the spin Hamiltonian, the spin-orbit factors, and the nuclear quadrupole splitting in the salts FeF, and KFeF,. For FeF, the method is ideal for the calculation of the energies associated with the t2# triplet, as demonstrated by the excellent agreement between the observed and calculated pressure dependence of the quadrupole splitting, which is very sensitive to these low-lying levels.1s0 Independent studies on FeF, have indicated that the splitting of the ferrous T,,, state, due to the axial component of the crystal field, decreases from Eaxial= 1300 K at 300 K to Eaxisl = 1000 K at 965 K. Thermal shift and thermodynamic data for FeF,, KFeF,, and FeCl, show that the electronic charge density at the iron nucleus is essentially independent of temperature, indicating that the expected increase in this density due to isothermal expansion must be approximately cancelled by an increase due to thermal effects at constant volume. In contrast, FeF, displays a significant decrease of electron density at the iron nucleus with increasing temperature. A model which fits quantitatively the high-pressure FeF, quadrupole-splitting data of Champion et al. below 60 kbar was also given, the new feature of the model being a method for estimating the effect of pressure on the 3d radial wavefunction.l*l Analysis of the magnetic hyperfine interaction of Fez+ in FeF,, Fez+: MnF,, and Fez+: ZnF, has yielded a value for the core polarization hyperfine field of Hc = - 514 k 3 0 kG and a value of < ~ - % ) ~=f f3.9 & 0.4a.u.lS2 FeCI, has been studied as the isolated monomer in a solid argon matrix at 4.2 K. The spectrum consists of a doublet with a quadrupole splitting of 0.62 k 0.05 mm s-I and an isomer shift of 0.88 L- 0.05 mm s-’ relative to iron at 300 K. A broad line from small amounts of impurities, possibly hydrated forms of FeCl,, is also present. When the matrix is changed to xenon there is, in addition to these features, a sharp line at +0.89 mm s-l, which is thought to correspond to monomeric FeCI, in a different environment. This line disappears when the sample is annealed.lS3 Three-dimensional magnetic ordering has been shown to occur in the linear chain compound RbFeCI, at TN = 2.55 k 0.05 K.lS4 The value of Mossbauer spectroscopy in conjunction with d.t.a. in studies of crystallization phenomena in aqueous solutions has been demonstrated by measurements on frozen solutions of FeCI,. When the transparent glass, formed by quick cooling of a 30 wt.% solution, is warmed slowly from 77 K, four temperatures are distinguished which correspond to

162

lo3 lo*

D. M. Silva and R. Ingalls, Phys. Rev. (B), 1972, 5, 3725. H. K. Perkins and Y . Hazony, Phys. Rev. (B), 1972, 5, 7. C. R. Abeledo, R. B. Frankel, and A. Misetich, Chem. Phys. Letters, 1972, 14, 561. T. K. McNab, D. H. W. Carstens, D . M. Gruen, and R. L. McBeth, Chem. Phys, Letters, 1972, 13, 600. G. R. Davidson, M. Eibschutz, D. E. Cox, and V. 3. Minkiewicz, Amer. Inst. Phys. CunJ Proc., 1972, NO. 5 (Pt. I), 436.

Mossbauer Spectroscopy 517 (i) melting from glass to undercooled liquid, (ii) crystallization of salt-free ice, (iii) crystallization of FeC1,,9H20, (iv) melting of both crystals. The third temperature increases by 22 K as the fraction of D,O in the water increases from zero to loo%, whereas the other three temperatures remain almost constant. The cause of this large isotope effect is not known.165*166 Mossbauer studies on frozen aqueous solutions of FeX, (X = CI, Br, or I)37 and propane-1,3-diol solutions of FeS0,,7H20 have also been described.ls7 It has been claimed that the Mossbauer spectra of siderite, FeCO,, show pronounced anisotropy effects in the recoil-free fraction. At 6 K the ratio of the recoil-free fraction parallel to the axis of symmetry to that in a perpendicular direction is f , , / f L = 7. This leads to a ratio for the meansquare displacements in these two directions which is unexpectedly large, especially in view of the fact that the 85 K spectrum is symmetric. The effect is too large to be explained on the basis of lattice vibrations alone and is thought to be associated with the interactions within the magnetic layers.16* Contributions to the internal field in FeCO, are discussed on p. 557. The Mossbauer spectrum of Fe(C10,),,6H20 has been studied as a function of temperature and applied magnetic field. On cooling through 243 K the quadrupole interaction changes from 1.4 to -- 3.1 mm s--l, the negative sign in the low-temperature value indicating a I z2 ) ground state, When the sample is reheated the transition does not occur until 258 K and is spread over less than 5 K. This hysteresis, coupled with the fact that thef-factor is 20% greater in the low-temperature phase, suggests that the transition is probably first order. The dependence of the effective hyperfine field ( H e f i ) on the applied field (Happ)was also studied at various temperatures and the results are shown in Figure 3. At 295 K the induced field ( H i ) , which is of opposite sign to Happ,is negligibly small, with the result that Hefi is only slightly less than HaPp. However, at very low temperatures, Hi predominates over Happand causes Heff to change sign. It was pointed out that determinations of the sign of the electric-field gradient in polycrystalline ferrous salts must be made at a temperature where either Happor Hi predominates, otherwise only broadened, unsplit lines will be obtained. For Fe(C104),,6H,0 the two should cancel exactly at 30 K.lSg New single-crystal measurements have been made on FeSiF6,6H,O and are consistent with a dzsground state for the Fe2+ion. The observed line intensities are in excellent agreement with values calculated on the basis of Vzz being negative in sign, axially symmetric, and directed along the

+

146

S. L. Ruby, A. Bernabei, and B. J. Zabransky, Chem. Phys. Letters, 1972, 13,382. S. L. Ruby, J . Non-Cryst. Solids, 1972, 8-10, 78. J. J. Hojgaard, Phys. Kondens. Murer., 1972, 13, 273. W. Kundig, A. B. Denison, and P. Ruegsegger, Phys. Letters ( A ) , 1972, 42, 199. J. M. D. Coey, I. DCzsi, P. M . Thomas, and P. J . Ouseph, Phys. Letters ( A ) , 1972,41, 125.

5 18

Sprclroscopic Propertics of' Inorgwric cirtd Organometailic clompormci.7

trigonal symmetry axis of the distorted Fe(H,O), octahedron. The powder spectrum is symmetric, indicating that there is no significant Goldanskii-Karyagin effect."O Fe(HC0,),,2H20 has been studied at room temperature, at ten different temperatures between 4.2 and 1.85 K, and at 0.027 K.I7l In the 4.2 K spectrum [see Figure 4(a)] the two sharp quadrupole doublets arise from

Figure 3 The efective hyperfine field in Fe(C10,),,6H20 [Reproduced by permission from Phys. Letters ( A ) , 1972, 41, 1251

two each of two inequivalent Fez+ ions. The inner doublet is assigned to Fe2+ ions in A-sites surrounded by six oxygen atoms from different carboxy-groups, and the outer doublet to Fez ions at B-sites, surrounded by two oxygen atoms from different carboxy-groups and four oxygen atoms of water molecules. From the temperature dependence of the quadrupole splitting the A- and B-site ions are thought to have a spin-orbit doublet ground state and a singlet ground state, respectively. At 1.6 K [Figure 4(b)] and 0.027 K the inner pair of lines become magnetically broadened, whereas the outer lines are essentially unchanged and suffer only a slight broadening as a result of overlap with magnetic components from the A-site resonance. Approximate hyperfine parameters for the B-site ion, estimated by subtracting the outer doublet from this spectrum +

"O

171

V. K. Garg and K. Chandra, Phys. Statiis Solidi ( B ) , 1972, 50, K49. M. Shinohara, A. Ito, M . Suenaga, and K. Ono, J . Phys. SOC.Japan, 1972, 33, 77.

Miissbauer Spectroscopy 519 and comparing the residual pattern [Figure 4(c)] with computer-simulated spectra, were as follows: H,ff = 8,8 kG, Qe2qQ = 1 .OO mm s-l, 7 = I , 8 = 80*, and = 0", where 6 and 4 specify the directions of the internal magnetic field relative to that of the principal axis of the electric-field

+

+

2.5

4.2 K

. . .

' .. -.

.

*

. *

v

- 2 - 1

8

0

(b) 1.6 K

1

2

.

3

4

Velocity I (rnm s-l I

Figure 4 Mossbauer absorption spectra of powdered Fe( H C 0 2 ) 2 , 2 H 2 0obtained at (a) 4.2 K and (b) 1.6 K . The spectrum in (a) is decomposed into four lines labelled as a, b, c, and d and the inner two lines are attributed to A sites and the outer two to B sites. Spectrum (c) is obtained by subtracting the absorption lines a and d in spectrum (a) from spectrum (b). The curve is the best fit, with Hint = 88 kG,&e2qQ= + 1.0 mm s-l, q = + 1 .O, 8 = 80",and $ = 0" (Reproduced by permission from J. Phys. SOC.Japan, 1972, 33, 77)

gradient.171 Solid-solution formation in the iron(l1) formate-magnesium formate system, which is difficult to detect by X-ray diffraction, has been proved with the aid of Mossbauer spectroscopy. The A-site is preferentially occupied by Fe2+ ions at low iron concentration^."^ 172

K.Nagorny and J. F. March, 2. Phys. Chern., 1972, 78, 311.

520


The probability of thermal electron transfer between the iron(r1) and iron(1rr) ions in the mixed valence compounds Fe11Fe111,(MeC02),0,5H,0 (A), [Fe"Fe"',( MeCO,),O]C1,5H20, and [Fe"Fel",( MeCO,),O]py,., has been shown to increase with temperature. This is illustrated in Figure 5

500 280

I

260

c

9'

L I

-4

I 200

I

230;

100 1

I

,

-3 - 2

-I

0

1

1

I

, I

300

400

,

,

.

2

3

4

Velocity /(mm

0

100

200

300

400

S-'I

Figure 5 Miissbauer spectra of Fe"Fe1"z(MeC0,),0,5H,0 (Reproduced by permission from J. Inorg. Nuclear Chent., 1972, 34, 2803)

for compound A. At room temperature the relaxation time is shorter than the lifetime of the excited Mossbauer level so that the two oxidation states are no longer distinguishable. The increased shielding of the s electrons by the 3d electrons with increasing temperature opposes the second-order Doppler shift and causes the slope of the isomer shift us. temperature curve for the iron(rI1) resonance to be Iron(1r) species formed in the U.V. photolyses of Fe2(Cz04)3,5H20, K3Fe(C,0,),,3H,O, and (NH4)3Fe(C204)3,3H20 have been studied."* D. Lupu, D. Barb, G. Filoti, M. Morariu, and D. Tarina, J . Inorg. Nuclear Chem.,

1972,34, 2803. G. N. Belozerskii, V. V. Boldyrev, T. K . Lutskina, A. A. Medvinskii, A. N. Murin, Yu.T. Pavlyukhin, and V. V. Sviridov, Kinetika i Katalitz, 1972, 13, 73.

52 1

Mossbniier Spec troscopj

Anisotropy of the probability of the Mossbauer effect has been observed in single crystals of pyrite (FeS,) but not in vivianite [Fe3(P0&,8H,0] and is independent of temperature between 90 and 600 K, both for polycrystalline and single-crystal samples. The temperature dependence of the recoil-free fraction is weaker for pyrite than for vivianite, indicating a larger role of optical branches in the vibrations of iron atoms in pyrite and therefore a larger influence of the local surroundings, which in turn have symmetry lower than c ~ b i c . ” ~ Fc 2*

1 2

-2-1

0

1

2 3

Velocity

-10 -5

I.,.

0

1

I

I . ,

5

. I

10

(mm s-1)

Figure 6 Spectra of K,,,,FeF, at 295 and 4.2 K (Reproduced by permission from J . Solid State Chern., 1972, 5, 402)

The hexagonal, tetragonal, and pyrochlore-type non-stoicheiometric iron fluorides M,FeF, (M = K, Rb, Cs, or NH,) have been studied over the temperature range 4.2-295 K . I n all cases the iron(I1) and iron(rI1) ions remain in discrete oxidation states, indicating the absence of charge hopping at least on the microsecond timescale. The spectra of the hexagonal and tetragonal phases, an example of which is shown in Figure 6 , exhibit broadened lines, consistent with the disordering of Fe2+ and Fe3+ in the structure. The magnetic ordering temperatures could be determined to an accuracy of k 1 K and were found to be in the range 116-135 K . By contrast, the pyrochlore-type phases give much sharper spectra, as illustrated in Figure 7, characteristic of structural ordering between the iron(rr) and iron(rI1) ions, and have magnetic ordering temperatures between I 7 and 21 K.17s A re-examination of the temperature dependence of the Mossbauer parameters of [NMe,],[FeCI,] has revealed the presence of a phase transition at 239 K . This is illustrated in Figure 8, which also shows that 175

liU

I. P. Suzdalev, I. A. Vinogravod, and V. K . Imshennik, Soviet Phys. Solid Stare, 1972, 14, 1136. N. N. Grcenwood, F. Menil, and A . Tressaud, J . Solid Store Chem., 1972, 5 , 402.

522

Spcctroscopic Pr.opcr.tic~~ of 1tiorgcltiic

tiritl

0r.gnrtomctcillic ('omporincls

the teniperature dependence of the quadrupole splitting deviates markedly from theoretical prediction based on a tetragonal distortion. Possible causes for this discrepency were discussed, including in particular the effects of vibronic admixture of the I x2 - y 2 ) and I 32' - r2 1 e ~ e I s . I ~ ~

>

-L

r

Fe 3'

f

Figure 7 Spectra of Rb,,,,FeF,, Cs,.,,FeF,, and (NH,),.,,FeF, at 4.2 K (Reproduced by permission from J . Solid State Chetn., 1972, 5, 402)

Spectra have been obtained for a number of six-co-ordinate iron(1i) complexes of FeCI, and FeBr, with amides, ureas, aniline, and benzothiazole, having stoicheiometries FeX,L, FeX,L,, FeXJ,,, FeX,L,, and FeX,L,. Complexes of the first three types are polymeric with bridging halogens and have room-temperature quadrupole splittings i n the range 2.5-3.0 mm s-I, suggesting that the d,, orbital is stabilized as a result of the distortion from pure octahedral symmetry. The FeX,L,-type complexes are monomeric ; the formamide derivative has an unusually small quadrupole splitting with a large temperature dependence which points to a nearly regular octahedral structure with only small distortional splittings in the t a g levels.178 A number of related tetrahedral complexes of the type 17'

T. C . Gibb, N. N. Greenwood, and M. D. Saslry, J.C.S. Drrlton, 1972, 1947. T. Birchall and M. F. Morris, Cnrrnd. J . Chern., 1972, 50, 201.

liB

523 FeX,L, (X = C1 or Br; L = benzothiazole, thioacetamide, thiourea, N-methylthiourea, or NN-dimethylthiourea) have also been studied. They have large ( > 3.0 mm s- l) quadrupole splittings with only small temperature dependences, indicative of considerable distortion from purely tetrahedral gcotnetry.17B I t has been shown by X-ray diffraction that Fe(py),CI,, Miissbairer Spectroscopy

3 .O

2.0

2 0 1.02

Is' 3

2

5.

vl

398

. h

3

394

3 v,

2 I

v

I

1 100

200 Temperature

0.90

300

/K

Figure 8 The tentperature dependence of tlie quadsupole splitting and chemical isomer shift relative to iron metal in "Me, ],[FeCI,]. At temperatures below 239 K the solid line represents the theoretical prediction for a tetragoiiul distortion of 132 cm-I, while abotie 239 K the distortion is 84 cm-l

Co(py),CI,, and Ni(py),C12 are in fact isomorphous, so that Fe(py),CI, must be considered to have a trans-octahedral structure and not a cisoctahedral structure as suggested recently (see last year's Report) on the basis of a theoretical and experimental Mossbauer study.laO The Mossbauer spectrum of the iron(1r) 0-bonded [Fe(bipy),( MeC,H,OSO),] at 295 K has a quadrupole splitting of 2.65 mm s-*, whereas the S-bonded [Fe(bipy)2(MeC,H,S0,)],2H20 has the much lower value of 0.31 mm s-l; in each case the chemical isomer shift is 0.31 mm s-' relative to iron. These values are characteristic of 5T2and 'Al iron(I1) ground T. Birchall and M . F. Morris, CmtoJ. J . Chent., 1972, 50, 211. D. Forster and D. J . Dahm, Inorg. Chem., 1979, 11, 918.

lUo

5 24

Spec t r osr opic Properties of I n orgcin ic ciml 0rgnno me tcr llic C 'ompoir ncjs

states and are consistent with the magnetic moments at 292 K of EL,.^, 5.27 and 0.95 R M , respectively. The temperature dependence of thc quadrupole splitting for the 0-bonded isomer can be rationalized in terrns such of an axial ligand field which splits the 'T2 term (sT2-+sBp + that 6 = -1450 70cm-l.la1 [Fe(napy),](CIO,),, Tetrakis-( 1,8-naphthyridine)iron(11) perchlorate, which contains Fe2+ surrounded by eight nitrogen atoms arranged at the vertices of a distorted dodecahedron (approximately D2d symmetry), has a quadrupole splitting of 4.26 mms--l at 295 K (4.54 mni s at 4.2 K), thought to be the largest reported at the time for any iron(ii) compound. The isomer shift (6 = 1.06 mm s-l) is completely normal, howevcr, for iron(r1). Measurements with an external field of 40 kG showed that VZ7i \ positive. The overall splitting was greater than expected for an applied field of 40 kG, indicating that an additional field is generated at the iron nucleus.1a2 Exposure of this material to air is thought to produce [Fe(napy),(H20~](C104)2,xH,0 in which the eight co-ordination is retained ; this product has a slightly larger isomer shift but a much reduced quadrupole splitting of 3.27 mm s-l.la3 Another extremely large quadrupole splitting (4.65 mm s-' at 300 K and 4.36 mm s-' at 4.2 K) has been reported for bis(thiosemicarbazide)iron(ii) sulphate. The sign of VZzis again positive and indicates a I d,, } ground state, as expected for a tetragonal crystal field with a compression along the z-axis. Since the nitrogen donor atoms are expected to exert the strongest crystal field, the axis of quantization must be NFeN.lR4It should be pointed out that the Russian workers Ablov and Gerbeleu had already reported the large quadrupole splitting for this compound in 1971 (see last year's Report). High-spin Iron(r1r) Compoirnds. Magnetic ordering has been detected in FeC1,,6H20 below a critical temperature of T, = 1.46 k 0.01 K. The magnetic hyperfine field is 396 2 2 k G at 1.16 K, and is oriented at an angle of 73" to the major axis of the electric-field gradient.ls5 There is a continuing interest in the application of Mossbauer spectroscopy to the study of frozen solutions of iron salts, and certain aspects of this work are discussed on p. 516. Extensive studies of paramagnetic iron(1n) salt solutions have shown that the nature of the chemical bonding between iron and its ligand sphere influences the magnitude of the internal magnetic field pertaining to the ml = k 3 -+ i-4 transition of the Kramers' doublet S, = f &, and also influences the relaxation time. The method provides information about the number of solvated and complex species In*

E. Konig, E. Lindner, I . P. Lorenz, and G. Ritter, Inorg. Chim. Acta, 1972, 6 , 123. E. Konig, G . Ritter, E. Lindner, and I. P. Lorenz, Chem. Phys. Letters, 1972, 13, 70.

Is3

E. Dittmar, C. J. Alexander, and M. L. Good, J . Co-ordination Chern., 1972, 2 , 69.

lH4

M. J . M . Campbell, Chern. Phys. Letters, 1972, 15, 5 3 . T. X. Carroll and M. Kaplan, Phys. Letters ( A ) , 1972, 41, 145.

MGssbauer Spectroscopy

525

of iron present as well as on the relative amounts of these components.186-188 Independent measurements have been carried out on frozen aqueous solutions of iron(111) p e r c h l ~ r a t e ,and ~ ~ ~the effects of weak magnetic fields on the paramagnetic hyperfine structure in the Mossbauer spectrum of this material have been studied.loO It was established some time ago that, on rewarming an aqueous solution of FeCl, which had been cooled rapidly to 77 K, the resonance disappeared abruptly at a temperature of 180-200 K but reappeared some time later if the solution was kept at the same temperature. A possible explanation of this behaviour is that the glass formed during the initial cooling transforms at 180--200 K to a supercooled liquid, which then slowly crystallizes. Experiments on frozen aqueous solutions of FeCI, have now established that this explanation is in fact correct. I t was argued that slow crystallization would be accompanied by the formation of an iron-enriched phase, the iron concentration of which could be observed by means of the effect of changes in the spin-spin relaxation on the magnetic hyperfine splitting in the Mossbauer spectrum. An iron-enriched phase would be expected to show fast spin-spin relaxation and therefore no magnetic hyperfine splitting. Accordingly, magnetic lines, which were present in the 90 K spectrum of rapidly cooled aqueous FeCI, solutions, were no longer present in spectra obtained at 9 0 K after the solution had been allowed to warm up to 200 K . As a further check, the process was repeated with Fe3+exchanged resin and anion-exchange resin swelled in FeCI, solution. As expected, the magnetic hyperfine structure did not disappear in these experiments because aggregation of the Fe3+ ions was precluded by the action of the exchange resin.lS1 Experiments on a single crystal of FeBO, have shown that it is possible to recreate antiferromagnetism in this material above its Neel temperature ( T N = 348.35 K) by the application of an external magnetic field. This effect can be observed up to temperatures of more than 15 K above TN for an applied field of 29.3 kG.lo2 Neutron diffraction and Mossbauer studies have been reported for the planar antiferrornagnet KFeF, in the critical region. There is a discontinuity in the isomer shift, but not in the quadrupole splitting, at the Neel point. In the temperature range 0.96 < T/TN < 0.998 the internal magnetic field follows the power law Hint(T) = H(O)D(l - T/TN)B,where H ( 0 ) = H(4.2K) = 540 k 4 k G , T ' = 141.51 _+ 0.05 K, D = 1.12 k

188

A. VCrtes and F. Parak, J.C.S. Dalton, 1972, 2062. A. Vertes and F. Parak, Acta Chim. Acad. Sci. Hung., 1972, 74, 293. A. S. Plachinda, M. Ranogajec-Komor, and A. Vertes, J . Radioanalyr. Chem., 1972, 10, 89.

T. Ohya and K. Ono, J . Chem. Phys., 1972,57, 3240. A. M. Afanas'ev, V. D. Gorobchenko, I. DCzsi, I. I. Lukashevich, and N. I. Filippov, Zhur. eksp. i teor. Fiz., 1972, 62, 673. A. S. Plachinda and E. F. Makarov, Chem. Phys. Letters, 1972, 15, 627. S. S. Yakimov, V. I. Ozhogin, V. Ya. Gamlitskii, V. M. Cherepanov, and S. D. Pudkov, Phys. Letters ( A ) , 1972, 39, 421.

lnD 'go

191 192

526

Spectroscopic Properties of Itiorganic and Organometallic Compounds

0.03, and = 0.209 rt 0.008.The main axis of the electric-field gradient tensor is canted at an angle 8 = I t -t 2" with respect to the hyperfine field direction.le3 Mossbauer and magnetic susceptibility data for the new planar fluoride CsFeF, show that long-range order in three dimensions exists only at temperatures below T, = 160 k 2 K. Good fits to the 4.2 K spectrumwereobtainedwithHjnt = 540 & 3 kG, Je2qQ(l jq2)i = - 1.54 k 0.05 mm s- ', and 7 = 0.3 k 0.3. The polar angle of Hirltin

+

i'::r)[-]Tvy ' ' 1 7 I 1

I

I

I

7

'

.-

.0_

-

-

.920,

.+

0

a,

r

I

.88-

r

;

l

I

I

I

1

I

I

I

1

-

the electric-field gradient principal axis system is 0 = 5 k 40.1g4,lg6 Similar anisotropy in the recoil-free fraction to that described for FeCO, on p. 517 has also been observed for the magnetic layer structure RbFeF,. As can be seen in Figure 9, the ratio of the areas of lines 1 and 2 is much greater than the expected value 8. The observed value of 2.28 5 0.05 yields a value off,,/f, = 6.5 in this case. The spectrum in Figure 9 can be fitted with the following parameters: H ( 0 ) = 457 k 2 kG, t e 2 q Q = 1.71 k 0.02 mm s-l, and 0 = 16.7 k 0.4°.168 Spectra have been obtained for polycrystalline (NH,),FeF, in the temperature range 78-348 K and indicate that the tetragonal to cubic phase transition occurs at 263 K, with a hysteresis of 0.5 K.lg8 Cs,FeCI, has been shown to exist in the solid state in two forms with different isomer shifts and quadrupole splittings; one is or;ange and the other is yellow and met as t able.lg7 Magnetically perturbed Mossbauer spectra have been used to establish that five-co-ordinate monomeric products are formed when the Schiff base le3 loo

lo5

lS0

G. Heger and R. Geller, Phys. Sratus Solidi ( B ) , 1972, 53, 227. M. Eibschutz, H . J. Guggenheim, L. Holmes, and J . L. Bernstein, Solid Srare Conrm., 1972, 11, 457. M.Eibschutz. G . R. Davidson, H. J. Guggenheirn, and D. E. Cox, Atrier. Inst. Phys. Con8 Proc., 1972, No. 5 (Pt. I), 670. S. Morup and N. Thrane, Solid State Comtn., 1972, 11, 1319. E. Frank and D. St. P. Bunbury, J . Inorg. Nuclear Chem., 1972, 34, 5 3 5 .

527

Mossbailer Spectroscopy

diiiier [Fe(salen)CI], is crystallized rapidly from nitromethane and pyridine. The dinicr has a negative principal component of the electric-field gradient tensor ( V,,), a non-zero asymmetry parameter, and an internal magnetic field equal to the applied field. By contrast, the products obtained by rapid crystallization show positive Vzz,an asymmetry parameter of zero which indicates axial symmetry, and large internal fields, in accord with their formulation as monomers. Furthermore, their perturbed spectra are broad, which confirms the presence of a high degree of magnetic anisotropy in these The Mossbauer spectra of the compounds TPPFeX (TPP = 01/Iy6tetraphenylporphin; X = CI, Br, I, or NCS) show a broad, asynimetric peak at 298 K and 78 K, which becomes a resolved doublet at 4.2 K . The high-temperature behaviour is interpreted in terms of slow relaxation within the i-g, k 8, and k @Kramers' doublets, which arise from the "Sk ground state of the Fe3+ ion and are equally populated. At 4.2 K the low-lying 5 substate becomes preferentially occupied and because there is a slight splitting of the 3 and - levels, owing to magnetic dipoles in the crystal lattice, relaxation between these levels is so rapid compared with the Mossbauer lifetime of lO-'s that there is no magnetic broadening and a symmetric, sharp Mossbauer doublet results. The probable ordering of the zero-field splitting parameter, D , deduced from the spectra was [TPPFeCl] < [TPPFeNCS] < [TPPFeBr] < [TPPFeI]. At 298 and 78 K the less intense, broadened peak, which corresponds to the + $ +;1 nuclear transition if the magnetic axis is parallel to the crystal-field axis, occurs at positive velocity, indicating that V,, is positive. At 6 K there is a reversal in the asymmetry for the thiocyanate and bromide, which probably reflects a reorientation of the magnetic axis to a direction perpendicular to the axis of the electric-field gradient, rather than a change in sign of Vzz.19Q By contrast, the spectra of eight new p-oxo-bis[ry/!ly6-tetrakis(aryl, pyridyl, or thienyl)porphinatoiron(~~~)] complexes all show well-resolved, reasonably symmetric quadrupole doublets at the three temperatures 298, 78, and 4.2 K. Furthermore, there is little dependence of the quadrupole splitting on the meso substituents, in contrast to the haeniin cases. The absence of magnetic broadening is due to strong spin-spin coupling between the two S = 8 iron(m) ions ria the oxygen bridge, which leads to rapid relaxation.20o The spectra of the compounds a/Iy6-tetrakis(pchlorophenyl)porphinatoiron(~~~)chloride and iodide, a&8-tetrakis(pmethoxyphenyl)porphinatoiron(Iu) chloride, bromide, iodide, azide, thiocyanate, acetate, and trifluoroacetate, and olby6-tetrakis(pentafluorophenyl)porphinatoiron(m) chloride and bromidc show a broad asymmetric peak with a shoulder on the high-energy side at 298 and 78 K ; at 4.2 K

+

+

--f

W. M. Reiff, Inorg. Chim. A d a , 1972, 6 , 267. C . Maricondi, D. K . Straub, and L. M. Epstein, J . Amer. Chem. Soc., 1972, 94, 4157 M . A. Torrens, D. K. Straub, and L. M . Epstein, J . Amer. Chem. Soc., 1972, 94 4 160.

Ion

lag

528

Spectroscopic Properties of Inorganic arid Organometallic Compounds

this asymmetric broadening reverses for several of the haemins, particularly the p-methoxyphenyl derivatives.201 Spectra have been obtained at 295 and 77 K for enH,[(FeHedta),O],6 H 2 0 , Na4[{Fe(edta)),0],12H,0, NaFe(edta),3H20, and Fe(Hedta),l SH,O and compared with established dataon twoother pairsof 0x0-bridged iron(ii1) dimers and corresponding high-spin monomers [(Fe(terpy)],O](NO,),,H,O, Fe(terpy)CI,, [Fe(salen)120,2py, and Fe(salen)CI,(MeNO,),. However, no definite conclusions were drawn regarding the spin-state of t h e iron(rr1) ions in these molecules. The isomer shifts are all similar ( C U . 0.78 nim s-' at 77 K) and although the quadrupole splittings show differences they do not follow a set pattern.", A Mossbauer study of the distorted octahedral iron complexes of glycine. leucine, lysine, tryptophan, and methionine at 82 and 298 K has shown that the high-spin Fe3+ ion is bound to the carboxylic and amino-acid groups and not to the side-chains of the a m i n o - a c i d ~ . ~ ~ ~ The intramolecular antiferromagnet [Fe{NN'-ethylenebis(salicylaldimato)}CI],, which contains two coupled Fe3+ ions bridged by oxygen, has been studied in the temperature range 4.2-22 K and in applied magnetic fields of 0-80 kG. At 4.2 K o n l y the ground state, with effective spin S = 0, is populated appreciably. An analysis of the magnetic hyperfine field and its temperature dependence yields an exchange constant J = - 6.7 cni-l and a hyperfine field of - 192 kG per unit spin at each iron nucleus.2o4 Comparison of the chemical isomer shifts for FeX,(ox) and FeX(ox), (X = C1 or Br; oxH = quinolin-8-01) with those of related species has suggested that the compounds contain five- and six-co-ordinate iron, respectively, and are therefore probably dimeric. The two most likely structures for dimeric FeX(ox), and FeX,(ox) involve either halogen bridges [(l) and (2)] or oxygen bridges [(3) and (4)]. Further evidence in

X

r N

19, I

X-Fc ,Fe-X 1'0 I NJ X 201 202 203

20p

M. A. TorrCns, D. K. Straub, and L. M. Epstein,J. Amer. Chem. Soc., 1972,94,4162. H. J. Schugar, G. R. Rossrnan, C. G. Barraclough, and H. B. Gray, J . Amer. Chew. sot.,i972,94, 2683. R. Raudsepp and I. Arro, Eesti N . S . V . Tead. Akad. Toim.,Fuus., M n t . , 1972, 21, 187. R . Lechan, C. R. Abeledo, and R. B. Frankel, Amer. Itist. Phys. Cot$ Proc., 1972, No. 5 (Pt. I), 659.

529

M i i s s b n r ~ ~Spectr.o.viwpj* t-

favour of these suggestions comes from the sign of V,,, which is positive for FeX,(ox) and negative for FeX(ox), ; the five-co-ordinate complexes FeCl(acac), and Fe(salen),O are known to have a positive V,,, whereas the six-co-ordinate [Fe(salen)Cl] has a negative Vzz. The complexes show relaxation effects due to the population of states other than the nonniagnetic S = 0 ground state at temperatures above 4.2 K, and a

c

0

. v) -

E

F c

-6

-3

0

1

3

3

6

Velocity /(mm s - ' )

Figure 10 Experimental and calculated Miissbuuer spectra of the coriipoirncl

[Fe3(MeC02)6(H20)31C1,6H20

(Reproduced by permission from J. Phys. So(*.Japan, 1972, 33, 1312)

Goldanskii-Karyagin effect may be present in the spectra of FeCl(ox)2.2"s The magnetism of the trinuclear complex salt [Fe,(MeCO,),(H,O),]C1,6H20, and the isomorphous chromium salt with 57Fe3+substituting for Cr3+ ions up to 2%, has been studied. In the absence of an external field, both materials show only quadrupole-split spectra (Figure 10). When an external field of 50 kG is applied at 1.5 K the spectrum of the iron salt consists of three sets of magnetically split patterns with effective fields of 210, 175, and 80 kG,but the (CrZ5'Fe) clusters in the substituted material show only a single pattern with an effective field of 235 kG. These results were discussed in terms of the antiferromagnetic intracluster interactions, which cause the Fe3+and Cr3+ions to have small positive or negative spin D. Cunningham, M . J. Frazer, A. H. Qureshi, F. B. Taylor, and B. W. Dale, J.C.S. Drrltori, 1972, 1090. 18

530

Spectroscopic Propcrties of' f)ior;Scinicatid Orgartometallic Cornpounds

components along the large polarizing field. I n an iron cluster the three interactions are not equivalent and in a (Cr,Fe) cluster the Fe31--Cr:i' interactions are stronger than the CrR+--Cr3 1 one.206 A number of other compounds containing high-spin iron(r1i) which have been studied are discussed elsewhere, see refs. 117, 173, and 176. Spin-crossover Systems, Unusual Electronic States, and Biological Conzpounds. Results on the 5K2,-1Al, spin-equilibrium in iron(rr) complexes have been reviewed.38 Depending on the experimental conditions, the abstraction of one molecule of 2,2'-bipyridyl from [Fe(bipy),]X,, X = NCS or NCSe, produces [Fe(bipy),X,] or [Fe,(bipy)&]. [Fe(bipy),(NCS),] exists i n three polymorphs and is well known for its transition between the ST, and ' A l ground states. It has now been shown that the compounds [Fe3(bipy),X6] contain iron(I1) ions in 'A, and 6T2 ground states simultaneously in a 2 : 1 ratio which is temperature independent. The structural formulation of these species as [Fes*'(bipy)2X2]z[Fea'(bipy)2X2],bipy [Fe'I' and Fesf denote spin-paired and spin-free iron(rr)] is consistent not only with the Mossbauer data but also with magnetic measurements and i.r. and electronic spectroscopy. The temperature dependence of the quadrupole splitting in the 5Tzspectrum is rationalized in terms of an axial ligandfield splitting of 8 = -630 cm-' for the NCS compound and - 600 cinfor the NCSe A 5T2-1A1 spin equilibrium has been observed for thc complexes [Fe(py),phen(NCS),] and [Fe(phen),(NCS),],20Eand for the novel series of complexes [Fe(mephen),]X, [mephen = 2-methyl-I ,lo-phenanthrolinoiron(r1); X = CIOp,209 BF4,,00 BPh4,210or I 210]. At 295 K the chlorate salt exhibits a quadrupole splitting of 1.03 nim s- and an isomer shift of +0.95 mm s-l, which are characteristic of a 5T2ground state. At 244 K , line-broadening is observed as a result of slow electronic relaxation between the 5E2and l A l states. At even lower temperature, e.g. 196 K, a second doublet appears with parameters (a = 0.57, 8 := + 0 . 3 8 mm s - I ) , typical of the lA1 state. At 4.2 K, 72.7% of the resonance is due to the ' A l state. The other salts show essentially similar behaviour. From the temperature dependence of the quadrupole splitting for the T2 state, the axial ligand-field splittings for the four salts were found to be 6 = -640, -580, -440, and -440 cm-l, respectively. With the aid of magnetic susceptibility data, the 5K2-1A1 energy separation E was shown to vary with temperature and to have the values 300 and 99Ocni-l at 294 and 98 K , 208

M. Takano, J . Phys. SOC.Juparr, 1972, 33, 1312.

208

33, 327. P. Spacu, M. Teodorescu, G. Filotti, and P. Telnic, Z . anorg. Chent., 1972, 392, 88. E. Konig, G . Ritter, H. Spiering, S. Kremcr, K . Madeja, and A. Rosenkranz, J . Chem.

'" E. Konig, G. Ritter, K. Madeja, and W. H . Bohmer, J . Phys. and Cherri. Solids,1972, ?O@

Phys., 1972, 56, 3139. 210

E. Konig, G . Ritter, B. Braunecker, K . Madeja, €1. A. Goodwin, and F. E. Smith, Ber. Birrisetigesellshuft phys. Cherrr., 1972, 7 6 , 400.

Miissbnriet. Spectrosropj53 1 respectively. Froin measurcnicnts wilh an applied magnetic ficld of 50 kG, the sign of V-, was shown to be positive for the 'Al component. l'hc signal for the 'T.. component was smeared ovcr a wide vclocity range and did not interfere with the ' A , component. None of the complexes [Fe(mephen),lX, (X = CN, CI, Br, NCS, N3, or malonato)211exhibits a spin equilibrium; the cyanide is exclusively in the low-spin l A l state, whereas the others adopt the high-spin 5TT,configuration. Measurements of the magnetic susceptibility and Mossbauer spectrum of [Fe(phen),ox],5H,O have now been extended down to 1.2 and 4.2 K, respectively, and are consistent with a 3AT,ground state, characterized by a zero-field splitting of D = 4.6 cm into an upper Ms = I f 1 } and a lower 10 ) level. The high value of g = 2.80 indicates significant mixing-in of quintet levels of higher energies, and this is apparently the source of the considerable increase in the high-temperature moment of about 3.96 BM. A complex Mossbauer pattern is obtained on application of an applied magnetic field of 20 and 40 kG, indicating that in at least a fraction of the iron atoms an internal magnetic field is generated.,12 Spectra have been obtained for six different iron(m) dithiocarbamates of general formula Fe(S2CNR,)3 between 100 and 300 K . In each case only a single quadrupole doublet was observed at all temperatures, and the temperature dependence of the quadrupole splitting of this doublet was considered to be inconsistent with the presence of a 2T2g-6A1,, equilibrium.213 I n a closely related study a linear dependence was found between the isomer shift and magnetic moment for a series of 19 compounds of the same general type. To explain this dependence it was suggested that the 6Alr, and states are both populated to varying degrees from compound to compound and that there is fast relaxation between these two states such that the resulting spectra reflect a weighted average of the two electronic configurations.213A study on the chelate bis-(NN-diethyldithiocarbamat0)iron(ii1) chloride is discussed on p. 539 and some iron(rv) dithiocarbamates are mentioned later in this section. Full details have now appeared of the sA1-2T2spin equilibrium in four tris(monothio-/3-diketonato)iron(iii) complexes (5a-d), preliminary studies of which were communicated in 1970. In favourable cases, superimposed spectra are observed in which both spin states can be recognized. Because the total degeneracies of the 6Al and ?-TT, states are the same, a 1 : 1 mixture is expected to be present at sufficiently high temperatures; however, the thermal equilibrium was found to be far from ideal in that the theoretical maximum ratio of isomers is exceeded in some cases. It was suggested that the failure to detect individual spin states in the dithiocarbamates discussed

"" ?I3 213

414

E. Konig, G. Ritter, K . Madeja, and A. Rosenkranz, J . Inorg. Nuclear Chern., 1972, 34, 2877. E. Konig and B. Kanellakopulos, Chetn. Phys. Letters, 1972, 12, 485. P. B. Merrithew and P. G . Rasmussen, Itiorg. Clwtn., 1972, 1 1 , 325. R. R . Eley, N. V. Duffy, and D. L. Uhrich, J . Inorg. Nuckear Chetn., 1972, 34, 3681.

5 32

Spec t roscop ic Properties q f

( 5 ) ~ 7 : R'

'

Iiio rgnii ic o i r ti

=

b;

R1 =

d:

Rl

c; K 1 =

=

R2

0rgniio t i w t allic Cotiipouii cI.7

Ph hl e Me, R 2 = Ph Ph, R 2 = Me RZ

-

=

earlier may arise simply from an unfavourable similarity in the quadrupole splittings of the two states, rather than from relaxation effects.215 The 6A1-27'2spin equilibrium has been confirmed in Na[Fe(thsa),],3H20 and NH,[Fe(sesa),] (H,thsa = thiosemicarbazone of salicylaldehyde; H,sesa = selenosemicarbazone of salicylaldehyde), whereas the compounds Li [Fe(thsa),],2H20, NH, [Fe(sespu),], NH,[Fe(t hpu),], N H4[Fe(phthsa),],O.SH,O, and Li[Fe(thpu),],3H20 (H,sespu = selenosemicarbazone of pyruvic acid; H,thpu = thiosemicarbazone of pyruvic acid,

Figure 11 A siriiplifiecl diagram of' the local encironnrent for the iron ion showing the x- and y-axes as chosen to bisect the Fe-As axes. With these axes, the tzn basis states are I x2 - y 2 ), I x z >,and I y z (Reproduced by permission from J . Cheni. Phys., 1972, 57, 3709)

>

H,phthsa = phenylthiosemicarbazone of salicylaldehyde) are exclusively low spin, and the compounds [FeCl(thdac)] and [FeBr(thdac)],H,O [H,thdac = H,NC(SjNHN(CH2C0,H),] are both high spin.21o The new complexes [Fe(R,dtc),]BF, (R = Me, Et, Pr', or cyclohexyl), [Fe(pyr)(dtc),]BF,, and Fe(Pridtc),BF, (dtc = dithiocarbamate) have all ?la

M. Cox, J. Darken, B. W. Fitzsimmons, A . W. Smith, L. F. Larkworthy, and K. A . Rogers, J.C.S. Dalton, 1972, 1192. V. V. Zelentsov, A . Ablov, K. I. Turta, R. A . Stukan, N. V. Gerbeleu, E. V. ivanov, A. P. Bogdanov, N. A . Barba, and V. G . Bodyu, Zhur. neorg. Khim.,1972, 17, 1929.

Miisshnuer Spectroscopy 533 been found to have isomer shifts which are smaller than expected for either iron(r1) or iron(1rr) and are therefore thought to contain iron(rv). The nature of the last complex mentioned is uncertain; the BF, may be present as the ion F3B02- derived from F3BOH2.217 The iron(1v) complex [Fe(diars),X,](BF,), (X = C1 or Br) has been studied in detail in the presence of magnetic fields up to 53 kG and at temperatures ranging from 4.2 to 348 K. The results were interpreted in terms of spin Hamiltonian parameters with an effective spin S = 1 and were consistent with a 3A2 ground state, corresponding to a strong compression, or strengthening of the ligand field, along the CI-Fe-Cl axis. A simplified diagram of the local environment for the iron ion is shown in Figure 11. The strong axial distortion can be understood in terms of the bonding scheme shown in Figure 12. A value for the covalency parameter of N 2 0.90 was estimated from the quadrupole splitting and magnetic hyperfine interaction, indicating that there is very little n-back-bonding to the empty d-orbitals of the diarsine ligands. Because of this the in-plane dT2+ orbital remains essentially non-bonding. However, the high formal charge on the metal is reduced by forward o-donation from the filled n-orbitals on the chlorine ligands, with a concomitant increase in the energy of the d,, and d,, orbitals relative to dd2+,*. As indicated in Figure 12, the ligand-field splitting was found to be A 2800 cm- l . Spin-orbit coupling in this complex leads to a zero-field splitting of D = 23 cm-l, with a oneelectron spin-orbit coupling parameter of ( = 467 cm- 1.218 Paramagnetic hyperfine structure has been observed in the 4.2 K Mossbauer spectra of FeOa2- diluted in concentrated NaOH solutions in the presence of applied magnetic fields ranging from 0 to 2 kG. The spectra, which are shown in Figure 13, can be interpreted as the superposition of components from each of the three members of a spin triplet. Because of the dilution and low temperatures, the relaxation time among the electronic states is long enough for the "Fe nucleus to couple to the magnetic moment which is induced in each state by the applied magnetic field. It should be remembered that in the present case the electronic states themselves have no moments in the absence of an external field. This is in contrast to the half-integral spin systems which have Kramers' degeneracy, where each member of a Kramers' doublet does have a non-zero magnetic moment which can couple to the nuclear magnetic moment if the relaxation rate is slow enough. The data yield an isotropic hyperfine interaction A = - 1.17 mm s-l in the nuclear excited state, g = 2.0 (isotropic) and zero electric-field gradient, all of which are consistent with an eg2configuration for the Fe"' ion. The saturation value of the hyperfine field is somewhat smaller than expected (1 75 kG).21Q

-

-

217 218

L'*'

E. A . Pasek and D. K . Straub, Inorg. C'hettr., 1972, 11, 259. E. A. Paez, D. I,. Weaver, and W. T. Oosterhuis, J . Clwm. Phys., 1972, 57. 3709. W. T. Oosterhuis and F. de S. Barros, J . Chrrti. Pli,~>s., 1972, 57, 4304.

534


The fluoride, chloride, azide, imidazole, cyanate, a n d methane-thiol derivatives of iron(1xi) haemoglobin have been studied in the temperature range 4-195 K . I n favourable cases measurements a t the higher teniperatures distinguish unambiguously between the high- and low-spin forms of

',,

'

1,

,',' .I,

d a

7d d d d

I

'

! I/ I

1

i'

':/ .'

,

'd2sp3

FeJ

A tc m tc Orbitals

M o 'e c uI e r Crbi tals

Llgsnd

Atornlc Orbit a Is

Figure 12 A A 4 0 diagram for the complex [Fe(diars),X,](BF,), representing the one-electron energies of the orbitals involced. There is only a small delocalization of the unpaired electrons according to the Mossbauer data. A is found to be 2760 cm-l, and V is less than 700 cm-' (Reproduced by permission from J . Chem. Phys., 1972, 57, 3709)

the compounds. Changes in isomer shift from compound t o compound and from spin-state t o spin-state are relatively small, but variations in the qiiadrupole splitting are more appreciable and depend greatly on the nature of the axial ligand. Measurement in a n applied field a t 4.2 K provides a far more direct method of spin-state determination.22o An interaction between the elcctronic magnetic moment of the iron atom and the nuclear 22n

M. R. C . Winter, C . E. Johnson, G. Lang, and Acta, 1972, 263, 5 1 5 .

R. J . P. Williams, Biochinr. Biophys.

535 magnetic moments of the ligands has been clearly observed in the paramagnetic hyperfine structure of the zero-field Mossbauer spectrum of acid metmyoglobin, pH 6 . Calculated spectra give good agreement with experiment if the nuclear moments are approximated by a n effective field of Miissbnuer Spectroscopy

.

___

. \

[ '... -

..

.

.-... .

, .-., .. .. . . ..

',::

03G

-

1

....

I

..,..-.... .. ' '

..

, I -

.

.

.. . . . . .. . . . . . . '

.. .

'

1.55

_ _ A * -

-3 - 2 - 1

0

I

2 3

Velocity /(mm s-'

- 3 -2 -I

0

I

2

I

Figure 13 Mussbauer spectra of FeOd2- diluted in concentrated NaOH at 4.2 K in a variable magnetic field applied parallel to the ganinra beam. The vertical bars at the left indicate 0.5% of the background and the bars at the top indicate the line positions of an Fe impurity which could not be eliminated. The solid ciuves at the right are calculated from the parameters D = 0.1 1 cm-l, E = 0.02 cm-l, A = - 1.17 mm s-l, P = 0,g = 2.00, and the oalue of the applied field is indicated for each case (Reproduced by permission from J . Chem. Phys., 1972, 57, 4304)

10 Gauss.221 An emission experiment with a n oxygenated haeme complex is mentioned on p. 515. Iron chelated by deferoxamine has been studied by Mossbauer spectroscopy.222 J21 222

W. T. Oosterhuis and P. J. Viccaro, Biochirii. Riuphys. Acfa, 1972, 264, 11. J. L. Bock and G. Lsng, Biochim. Biophys. Ai,tti, 1972, 264, 245.

536

Spectroscopic Pr0pertic.s of' Itioi-gc~nicand Organonietallic Compounds

The iron atoms in the reduced paramagnetic form of putidaredoxin, a 2Fe-S protein from Pseudomonas putida, have been shown to give spectra typical of high-spin Fe3' ( S = 4) and Fez+ ( S = 2), respectively. From applied field measurements it was shown conclusively that the spins are coupled antiferromagnetically to give a total spin S = &. The magnetic hyperfine tensor of Fe3+ is small and highly anisotropic, which implies strong covalency and relatively low symmetry in the arrangement of the ligands. The oxidized diamagnetic form of the protein is thought to contain two Fe3+ ions of spin S = #, coupled to give a total spin of zero.22:$ The hyperfine field at the high-spin Fe3+ ion in the oxidized form of rubredoxin isolated from Chloropseridunionas ethylica has been found to be 370 rL- 3 kG. In the reduced form the hyperfine field tensor is anisotropic with a component perpendicular to the symmetry axis of the iron atom of about -200 kG. The ground state of the Fezit ion is a dzzorbital. There is a large non-cubic ligand-field splitting A / k = 900 K and a small 4.4cm-') of the Fez+ levels. The contribution spin-orbit coupling ( D of the core polarization to the hyperfine field in the Fe3+and Fez+ ions is - 370 and - 300 kG, respectively.224 The nitrogenase of Klebsielltr pnerrmoniae has been studied and the results compared with published data on nitrogenase components from Clostridiiim pasteitrianrrm and Azotohacter vinelandii.226 The ferredoxin from the blue-green alga Micvocystis flos-nqirae has also been studied.226 Spectra have been reported for a number of iron-sulphur compounds which might be considered as potential models for the non-haeme iron protein systems termed ferredoxins. For example, the reaction of the ligand (CF,),C,S, (L) with Fe(CO), in the presence of H,S produces a black crystalline tri-iron compound Fe3L4SBH2,which in disulphidecontaining solution is converted, reversibly, into a di-iron species. The iron atoms appear to be equivalent in both solid and solution, with octahedral co-ordination in both states. However, the parameters differ significantly from those of the proteins, indicating that the value of the compound as a model is limited.227 The behaviour of the isomer shift for the series of compounds [Fe4S4L4In--[AsPh4],+ [L = S2Cz(CF3),] is similar to that exhibited by the HPI chromatium. I n both systems a small increase in isomer shift accompanies the reduction, consistent with a slight decrease in the s-electron density at the iron nuclei, which remain equivalent.22* Related results on some dinuclear bridged sulphido-derivatives of iron are discussed in the following section (see p. 540).

-

22J

224

2z6 226

2L'i

22s

E. Munck, P. G . Debrunner, J . C. Tsibris, and I. C. Gunsalus, Bioc~herriistr~., 1972, 1 1 , 855. K . K. Rao, M. C. W. Evans, R. Cammack, D. 0. Hall, C. L. Thompson, P. J. Jackson, and C. E. Johnson, Biochem. J . , 1972, 129, 1063. R. R. Eady, B. E. Smith, K. A. Cook, and J. R. Postgate, Biochem. J . , 1972, 128,655. K. K. Rao, R . V. Smith, R. Cammack, M . C. W. Evans, D. 0. Hall, and C . E. Johnson, Biochem. J . , 1972, 129, 1159. K . A . Rubinson and Ci. Palmer, J . A w r r . C'fiern. Soc., 1972. 94, 8375. I. Bernal, B. R . Davis. M . 1.Good, and S. C'handra, J . Court/. CIieni., 1972, 2, 61,

Mossbauer Spectroscopy

537

Low-spin and Covalent Complexes. The quadrupole splitting of Li,,Fe(CN),,4H20 decreases from 0.80 to 0.25 mm s-l after hydration, presumably

because of a redistribution of the Li+ cations around the ferricyanide ion. The spectrum of a frozen aqueous solution of Na,Fe(CN),,H,O shows only a broad singlet, whereas the solid gives a quadrupole splitting of 0.96 mni s-l. The zero quadrupole splitting is attributed to a cancellation of the electric-field gradient arising from the low-spin iron(rrr) ions by that arising from the The effect on the Mossbauer parameters of varying the cation in a series of iron cyano complex anions had been Spectra have been obtained for a number of Prussian Blues produced from the thermal decomposition of H,Fe(CN), and H3Fe(CN)s.231 Three iron species have been detected in the decomposition products of benzene and anisole solutions of [Bu,PCH,Ph] [Fe1'(CN),]-.232 I t has been shown that hydrated sodium and lithium ferricyanides are reduced by electron irradiation to the corresponding ferrocyanide, but the anhydrous complexes are unaffected. The reduction is therefore attributed to hydrogen radicals produced from the radiolysis of water. Silver ferricyanide shows different behaviour and it is thought that a species of the type Ag,Fe'"(CN),(NC), with an iron-isocyanide bond, is Proton irradiation effects in potassium iron cyanides have also been studied. K4[Fe(CN),],3H,0 gives metallic iron, which is in the superparamagnetic state for low beam currents (0.05--0.30 PA) and in the ferromagnetic state for higher beam currents (0.6 PA). It is suggested that a reaction of the type +

K,[Fe(CN),]

-

Fe

+ 4KCN + (CN),

may occur. The disintegration of K,[Fe(CN),] is more complex. Fe,C is detected in the Mossbauer spectrum of the products and is believed to be formed in the initial conversion of K,[Fe(CN),] into K,[Fe(CN),], which then decomposes as already described.,,, Data have been given for addition compounds of [Fe(CN),N0I2- with CS(NH2),, MeCSNH,, PhCOMe, S2-, and SO,,- and for derivatives in which the nitrosyl group of this anion is substituted by Me,SO, morpholine, PhCH2NH2, HOCH,CH,NH2, p- and m-H2NCeH40Me, pyrollidine, p-(H2N)&H4, 2,4-( H,N),C,H,OMe, J+(P~NH)C~H,OH,and pyridine The predicted correlation between the ,'Fe quadrupole splitting and the 'T, splitting in the electronic spectra for low-spin iron(i1) compounds 22u s'O

231

232 233 234

P. H . Domingues and J . Danon, Cheni. Phys. Letters, 1972, 13, 365. L. Korecz, P. Mag, S. Papp, B. Mohai, and K. Burger, Magyar h'km. FoIy(jiru1, 1972, 78, 479. J. C. Fanning, C. D . Elrod, B. S. Franke, and J . D. Melnik, J . Inorg. N d e o r Chem., 1972, 34, 139. S. Papp and A. VCrtes, Rndiochetn. Rndiocitiolyt. Letters, 1972, 9, 231. E. Baggio Saitovitch, D . Raj, and J. Danon, Chem. Phys. Letters, 1972, 17, 74. K . Kisynska, M . Kopcewicz, and A . Kotlicki, PhJzs. .Stf/trrs Solid' ( B ) , 1972, 49, 85. U. Weihofen. Z . Nnturforsch.. 1972, 27a. 5 6 5 .

538

Spectroscopic Properties of Inorgartic- and Orgariometallic Compounds

has now been observed for the series of compounds cis- and trans[FeX,(ArNC),] (X = CI or SnCl,; ArNC = p-methoxyphenyl isocyanide), cis-[Fe(SnCl3),(ArNC),], and [Fe(ArNC),SnC1,]C104. The llRSn spectra for the compounds containing the SnCI, ligand are discussed on p. 574.2J6 The sign of V,, has been shown to be negative (A = - I . 14 mni s- I ) in trans-[FeH(L)(depe),I+BPh,(L = p-MeOC,H,NC; depe = 1,2-bisdiethylphosphinoethane) and on the basis ,]O,. For small values of x a magnetic structure of the Nee1 type exists; for x > 0.5 this structure disorders, and for x = 1.75 a partially ordered angular spin structure of the Yafet-Kittel type This system has previously been studied in great detail by Wertheim and co-workers (see Vol. 5 , p. 537). Mossbauer effect studies on cubic and tetragonal Mn,.,Fe,.,O, have failed to detect the presence of Fe2+ions. This rules out the possibility of an equilibrium of the type Mn2+ Fe3+ + Mn3+ + Fez+, and indicates that the cubic to tetragonal phase transition is not associated with a significant change in the concentration of Fe2+ions in octahedral sites.28H The manganites M2+Mnl.BFeo.104 (M = Cd, Mg, Zn, or Co) have also been studied both above and below the temperature of the cubic-tetragonal dist~rtion.~*~ The spectra of the nickel ferrites Fe,-,Ni.O, ( x = 0, 0.2, 0.4,0.6, or 0.8) have been analysed in detail. For x = 0 (Fe,O,) there is a magnetic hyperfine pattern from Fe3+ ions in tetrahedral sites and a second pattern from the octahedral Fe3+and Fez ions which are rendered indistinguishable by rapid electron hopping. As x increases, the Ni2+ions are progressively substituted for Fe2’ ions in the octahedral sites and the spectra distinguish between four types of iron ions in the octahedral sites: (i) for 0 < x < 1 a fraction of the Fe3+ ions are not involved in electron hopping and give a pattern which is superimposed on that due to the tetrahedral Fe3+ ions; (ii) for 0 < x < 0.4 there is a pattern from an equal number of Fe2+and Fe3+ ions which are rendered indistinguishable by electron exchange; (iii) for 0.2 < x < 0.8 there is a group of Fe3+ and Fe2+ ions in the proportion 1 : 2 which are also coupled by electronic exchange; (iv) for x > 0.6 some of the octahedral Fe3+ ions are not involved in electron exchange and are distinguishable from the first type by a relatively higher isomer shift and internal field. For x = 1 (Fe,NiO,) only two hyperfine patterns are observed, the one with the lower isomer shift and Heffbeing assigned to tetrahedral Fe3+ ions, and the other to octahedral Fe3+ ions. It is proposed that, at low values of x , the itinerant electrons from the Fe2 ions are delocalized in the sublattice leading to metallic conductivity, whereas at high values of x they are in localized groups of exchangecoupled iron ions.2Bo Angular ordering of the Fe3+ spins has been detected in the ferrites NiFe,.-,AI.O,. For x = 0.2 and 0.5, two six-line patterns of equal intensity are observed, indicating that the Fe3+ ions are evenly distributed over the

+

+

287

z90

A . S. Bukin, A . K . Gapeev, R. N. Kuz’min, and A . A. Novakova, Kristallogrojiyci, 1972, 17, 799. M . K . Hucl, F. Van der Woude. and G . A. Sawatzky, Phys. Letters, 1972, 42A,99. G . Filoti, A. Gelberg, V . Gomolea, and M . Rosenberg, Internat. J . Mugn., 1972, 2, 65. J. W. Linnett and M. M . Rahman, J . Phys. orrd Chern. Solids, 1972, 33, 1465.

Miissbauer Spectroscopy 549 tetrahedral and octahedral sites and that all of the Ni2+and A13+ions are in octahedral sites. For x > 1 several distinct hyperfine components are present, three from Fe3+ in tetrahedral sites and one from Fe3+ in octahedral sites, and these are attributed to an angular ordering of the spins, rather than to the existence of a range of different environments. In nickel ferrite itself the axis of easy magnetization is directed along the [I 111 axis at an angle of 55" to the direction of VZz;the development of angular ordering is accompanied by a deviation of the angle 6 from 55" and the appearance of a quadrupole splitting because the expression (3 cos26 - 1) now becomes non-zero. For large concentrations of A13+ ( x > 1) a paramagnetic component also appears in the spectrum with a relative intensity which decreases as the temperature is Fe2+ has been shown to exist in both the tetrahedral and octahedral sites in the ferrites Ni,_,_,Fe~i-Zn,Fe~+04,z92 Possible explanations for the discrepancy between the measured magnetic moments of NiCr,-,Fe,O, and the values calculated on the basis of the Nee1 model have been d i ~ c u s s e d . ~The ~ ~ isomer - ~ ~ ~ shift of the Fe3+ ions in tetrahedral sites in N ~ C I - ~ . ~ F ~ ,increases ,.~O, at the magnetic ordering temperature, indicating a decrease in the spin density in the region of the iron nuclei.296 The processes which occur in nickel-cobalt ferrites during thermomagnetic treatment have been investigated. 297 -299 Relaxation effects have been observed in the spectra of Co,Zn,-,Fe204 (h: = 0.3, 0.5, or 0.75) in the temperature range 80-700 K . The theoretical spectra calculated on the basis of the stochastic model (in which the hyperfine interaction is replaced by an interaction between the nuclear spin and a randomly varying time-dependent external magnetic field) show good agreement with the experimental data in all cases. For each composition the relaxation time decreases very slowly with increase in temperature, but in the region of the Nee1 temperature it decreases rapidly and leads to the total collapse of the magnetic hyperfine splitting. The initial introduction 2''1

znz

V. F. Belov, M. N . Shipko. T. A . Khimich, V. V. Korovushkin, and L. N. Korablin, Soiliet Phys. Solid Stute, 1972, 13, 1692. V. A. Potakova, N. D. Zverev, and V. P. Romanov, Plij.s. Stutus Solidi ( A ) , 1972, 12, 623.

203

"04

SHB

2u(1

?u7 2u8

V. 1. Nikolaev, S. S. Yakimov, F. I . Popov, and V. N. Zarubin, Soviet Phys. Solid State, 1972, 14, 521. P. P. Kirichok, V. F. Bclov, V. A. Trukhtanov, G . S. Pdval'nykh, M . N. Shipko, V. V. Voitkiv, and V. V. Korovushkin, Ukrain. fiz. Zhur., 1972, 17, 459. P. P. Kirikchok, G. S. Podval'nykh, and V. F. BeIov, I z w s r . Akacl. Nauk S.S.S.R., Ser. Jiz., 1972, 36, 397. V. A. Gordienko, V. V. Zubenko, V. I. Nikolaev, and S. S. Yakimov, Soviet Phys. Solid State, 1972, 14, 530. P. P. Kirichok, G . S. Podval'nykh, N. V. Kobrya, and 0. R. Borovskaya, Izzoest. Akod. Nauk S . S . S . R . , Ser. Fiz., 1972, 36, 402. P. P. Kirichok, G . S. Podval'nykh, N. V. Kobrya, 0. R. Borovskaya, and L. M . Letyuk, Izuest. Vyssh. Ucheb. Zaved., Fiz.,1972, 15, 133. P. P. Kirichok, G . S. Podval'nykh, N. V. Kobrya, 0. R . Borovskaya, and L. M . Letyuk, Zhur. f i z . k'hiil/., 1072. 46, 1550.

550

Spec?roscopicProperties of Inorganic and Orgonometallic Compounds

of Zn2' ions into thc system (x = 0.7) increases the relaxation time at low T ( T < T N ) ,but further increase in the Zn?+ concentration from x = 0.5 to x = 0.3 has little effect, because of the role of Zn2' ions in increasing the magnetic disorder in the ferrite.300 The quadrupole coupling constants associated with the tetrahedral and octahedral sites in the rare-earth iron garnets R3Fe5012(R = Lu, Yb, Dy, Sm, or Gd) have been estimated and compared with experimental values. The good agreement indicates that covalency effects are not important as regards the quadrupole coupling in these oxides. The apparent contradiction of this conclusion with the interpretation of the isomer-shift data was rationalized in terms of cancellation effects of the distant contributions from the various s-orbitals to the electric-field gradient.301 A single crystal of yttrium iron garnet magnetized in the [ l l l ] direction with a field of 55 kG has been used in a determination of the quadrupole coupling at the octahedral Fe3+ site. The result, +e2q& = -0.46 nim s-l, disagreed with that estimated recently on the basis of an LCAO h a 0 calculation. It was suggested that neglect of the electrostatically produced dipoles on the oxide ions might be the cause of the disagreement and a procedure for constructing MO's which takes such dipoles into account was The change in the direction of easy magnetization in oriented slices of yttrium iron garnet single crystals, which occurs at about 500 "C,has been shown to be due to non-axial magnetic anisotropy induced by tensile stresses generated in the plane of the sample by polishing. The effect was absent in samples which had been annealed at 850 "C for 4 h. In this case the direction of magnetization (along the [111] axis) is determined by the intrinsic magnetic anisotropy energy.3o3 The Mossbauer spectra of diamagnetically substituted yttrium iron garnet have been considered in detail. In favourable circumstances it is possible to use the Mossbauer effect to measure not only the cation distribution among different sites, but also to determine whether the cation distribution in a given sublattice is random. This was found to be the case in {Y>,(Fel-~S~,,.)3[Fe]:~0,3 with .Y = 0.10 and 0.25 (the different brackets refer respectively to dodecahedral, octahedral, and tetrahedral sites). In3+ and Rh3+ were also found to prefer the octahedral sites, whereas A13 and Ga3+ prefer the tetrahedral sites. At higher temperatures, central peaks appear in the spectra of the mixed oxides, as illustrated in Figure 16 for { Y}3(Fe)a[Feo.,5Gao.25]3012. These peaks grow in intensity at the expense of the magnetically split spectrum which finally disappears at T,. An applied magnetic field was found to increase the proportion of hyperfine splitting in the spectrum. The mixed spectra could not be explained by a range of ordering temperatures in different parts of the crystal, or by 300 302

303

S. C. Bhargava and P. K . Iyengar, Phys. S/ci/rts Solidi ( B ) , 1972, 53, 359. R . R. Sharma, Phys. Rev. ( B ) , 1972, 6, 4310. R. M. Housley and R. W. Grant, Phys. Rec. Letters, 1972, 29, 203. G . N. Belozerskii, Yu. P. Khimich, and Yu. M. Yakovlev, S m i e t Phys. Solid .S/n/c, 1972, 14, 993.

Mossbauer Spectroscopy 55 1 independent relaxation of the ionic spins. Instead, the central peaks were thought to arise from iron in clusters of short-range order. The size of the clusters was estimated to be 10” lo” ions just below the temperature at which the last trace of magnetic hyperfine splitting disappears. A study of the geometry of the random lattice, with nearest-neighbour interactions, showed no tendewy for localized regions of this magnitude to form and it was suggested that thcy are evanescent.3u4 I

I

.. ..... . . ... .. . .

I

,

1

:

I

I

7 - 1 - - -

. ..-. . ,:--.

Figure 16 Illiksbnuer spectr~?of IY)3(Fe),[Fe,.7,Ga,,,,],0,2 lures

.....

uf

..

.

diflkrent tempera-

[Reproduced by permission from Pliys. Rep. ( B ) , 1972, 6 , 32401

The Fe3+ ions in Ca,Zr,TiFe,O,, have been shown to occupy tetrahcdral positions, whereas i n Ca,Zr,.,Ti,.,Fe,O,, they are partially replaced by The Fe3+ ions in Ca,Fe, sTi4+ions and shifted into octahedral M,Ge,O,, and Cd3Fe2-.M.Ge3012 (M = Al”+, Ga3+, Cr3’, Sc:”, or Cation distributions in the garnets In3+) all occupy octahedral Gd,Fe,-,Al,O,,, Gd,Fe,O,,, and Er3Fe,01, have also been 30G 306

307

J. M . D. Coey, Pfrys. Reti. ( B ) , 1972, 6, 3240. R. Hrichova and J . Lipka, Toll. Czech. Chcm. Cor,irn., 1972, 37, 3352. I. S. Lyubutin, L. M . Belyaev, R. Crizhtkhova, and I . Lipka, Kristnflogrnfiya, 1972, 17, 146. V. N. Belogurov, B. M. Lcbcd, V. I. Moscl, and P. E. Scnkov, Phys. S r n m Sofidi ( A ) , 1972, 11, K93.

552

Spectroscopic Properties of Itiorgcrtiic urtd Organontetullic Compounds

The Mossbauer effect in antiferromagnetic substances with garnet structures has been considered elsewhere.308

Other Oxide Sysferns. The solid solutions CaAl,,-zFe,O,, ( x d 4.8) have been shown to give three resolvable quadrupole doublets from Fe3+ ions in tetrahedral, trigonal-bipyramidal, and octahedral sites. Analysis of the

423 K

0 X

c . v)

c

t

3

0

u

[AULU

-8

-6

-4

-2

0

2

4

6

0

Velocity I (mm s - 1 )

Figure 17 Miissbarier spectra of Sr,Fe,O,,. The relative intensities are A:B:C= 3:1:2 (Reproduced by permission from J . Phys. mid Cliem. Solids, 1972, 33, 1169)

relative areas indicates a marked preference for iron to occupy the tetrahedral sites. Magnetic ordering is observed for x = 4.8 and 6.309 The new strontium ferrate Sr,Fe,O,, gives a complex spectrum at room temperature (see Figure 17), which can be interpreted in terms of three overlapping six-line magnetic hyperfine patterns from iron atoms in non-equivalent environments, with relative intensities in the ratio 3 : 1 : 2. The material is not attracted to a magnet at room temperature and is A. P. Dodokin, I. S. Lyubutin, B. V. Mill, and V. P. Peshkov, Zhur. eksp. teor. Fiz., 1972,63, 1002. F. P. Glasser. F. W. D. Woodliams, R. E. Meads, and W. G . Parker, J. Solid S m f c Chem., 1972, 5 , 255.

Mossbauer Spectroscopy

553

therefore antiferroniagnetic. The isomer shifts are characteristic of Fe3+. Above the Nee1 temperature (145 k 5 "C)the spectrum consists of two absorption bands from three overlapping quadrupole doublets. The quadrupole splitting (ca. 1.3 nim s-l) is approximately double that observed below TN and is consistent with the magnetization being directed along an axis perpendicular to the major axis of the electric-field gradient.310 Spectra have been obtained for the solid-solution series Sr, rLarFeO,., , J / 2 . The intensity of the characteristic six-line absorption pattern of the tetrahedral iron site in the brownmillerite-type phase (0 < x < 0.2) decreases as the La content increases. This is attributed to a change in the co-ordination state of Fe3+from tetrahedral to octahedral as a result of the increased oxygen content. The spectrum for the composition x = 0.15 contains a new six-line pattern with parameters intermediate between those for the tetrahedral and octahedral sites and is thought to arise from the presence of Fe3+ ions in a five-co-ordinate trigonal-bipyramidal oxygen environment. The brownmillerite phase disappears completely at x = 0.3 and is replaced by a cubic perovskite structure: however, absorption peaks corresponding to a m a l l proportion of tetrahedrally co-ordinated Fe3+ ions still remain. At x 2 0.5 only six-co-ordinate Fe3+ions can be detected. The values of the isomer shift, quadrupole splitting, and internal magnetic field for the sample with x = 0.15 at room temperature are, respectively, +0.380 mm s-l, +0.109 mm s-l, and 515 kG for the octahedral site, + 0.136 riim s l , - 0.150 m m s-l, and 41 I kG for the tetrahedral site, and + 0.326 mni s +0.326 mm s-l, and 488 kG for the proposed trigonalbipyramidal The influence of the thermal history on the Miissbauer spectra of samples of the type SrO6-,Fe,O3,xAI2O3 has been The ordered perovskite Ba,FeReO, has been shown to give a single line with an isomer shift of + 0.65 k 0.03 mni s above the Curie temperature. At 77 K a six-line pattern is obtained, indicating that the material is magnetically ordered with an internal field of 456 k 4 kG. At room temperature the intermediate behaviour of partial magnetic order is observed. Although the lack of any quadrupole splitting suggests that the iron is tervalent, the isomer shift and hyperfine field are intermediate between the values expected for high-spin Fe3+ and Fez k. Furthermore, this material exhibits metallic conductivity and a high Curie temperature, which may indicate that the Fe3+-Re5+combination is degenerate with the Fe2+-Rea+ combination. Ordinary superexchange rules, which assume a-type interactions to be stronger than n-type interactions, predict that this material should be ferromagnetic. Instead, it is found to be ferrimagnetic, which suggests that n-type interactions may in fact be F. Kanamaru, M. Shimada, and M . Koizumi, J . Phys. atid Chetti. Solids, 1972, 33, 1169. H . Yamamura and R . Kiriyama, Brill. Chetn. Snc. Jupcrn, 1972, 45, 2702. JIL V. Fluorescu, I. Bunget, D. Barb, M. Morariu. and D. Tarina, Re(>. Roumnitie Phys., 1972, 17, 261. 4. W. Sleight and J . I-. Weilier. J . Ph? s . trtrd C / r e / j i . Solid\, 1972, 33, 679.

310

554

Spectroscopic Properties of’Irrorganic mid Organometaliic Compounds

Data have been given for nine ferrites in the series BaFelz-z,rZn,Ti,O,B. For x = 0, four Fe3+ six-line patterns are observed, whereas for x > 0 there are five patterns from non-equivalent iron environments314 Effects similar to those described earlier for { Y}3(Fe)z[Feo.75Gao.z5]301z have also been observed for the disordered solid solution Ba(Feo.,,Al,.&O,.

350

-

90

-

-10

a

0

Velocity/(inm s ’)

For explanation of arroned Figure 18 Mossbauer spectra of Bat Fe,.,,Al, &)04. peaks, see original paper (Reproduced by permission from J . P11ys. arid Cltem. Solids, 1972, 33, 1631)

Above 2 0 K the spectra consist entirely of a quadrupole doublet, but below this temperature magnetic lines also appear and their intensity grows as the temperature is lowered further, as can be seen in Figure 18. These results indicate that the solid solutions contain antiferromagnetic clusters of various sizes, the smaller ones being above their blocking 314

J. P. Mahoney, A . Tiiuber, and R. 0. Savage, Atner. I m t . Phjqs. Cot$ Pro(.., 1972, No. 5 (Pt. 2), 816.

Miissbauer Spectroscopy 555 iemperatures and having rapidly fluctuating nett moments, and the larger mes being stable and producing well-defined magnetic splitting. The variation with temperature of the ratio of the intensity of the sextet to that of the doublet is shown in Figure 19 and is seen to be discontinuous,

Temperature I K

Figure 19 Temperature variation of the ratio of the intensity of the sextet to that of the doublet, 18/Id (Reproduced by permission from J . Pliys. and Chem. Solids, 1972,33, 1631)

which suggests successive blocking according to the Ntel theory. The theory of random clusters in disordered solid solutions, due to de Gennes et a/., was used to determine the blocking temperatures, and the anisotropy constant K values were deduced on the basis of the Neel theory of superparamagneti~m.~~~ Mixed oxides prepared by heating the hydroxides coprecipitated from solutions of Fe3 and A13+have been The system (1 - x)Fe,O,xAl,03 (x = 0, 0.56, 1.98, 5.27, or 10.17 wt.O/,) has been studied in detail in the temperature range 10-1000 K. There is a rapid and non-linear decrease in the Morin temperature TM of the a-Fe20, lattice. The phase transition is not sharp and becomes more and more diffuse as the magnetic dilution increases. The Fe3+ spins are canted at an angle of about 30* away from the c-axis at low temperatures for the 0.56 wt.% diluted sample, and the canting angle appears to remain constant with increased dilution. The ratio TM/TN(TN = Neel temperature) and the anisotropy energy, K , deduced from the temperature and concentration dependence of the hyperfine field, decrease with increased dilution, which supports the existing anisotropy theory. Three magnetic phases are thought to be present in the 5.27 wt."/, diluted sample.268 The Morin transition temperature decreases from 260 to 153 K when Sn4+(0.34 at.%) is doped into a-Fe203. +

''Ie

R. Chevalier and C. Do-Dinh, J . Phys. and Chern. Solids, 1972, 33, 1631. L. Korecz, I. Kurucz, G. Menczel, E. Papp-Molnar, E. Pungor, and K . Burger, Mugynr Kdm. Folyoirat, 1972, 78, 508.

556

Spec t r oscopic Properties of

/iior.iJciii ic

cr k i d 0rganome t a l k Compounds

Spectra taken at room temperature in a magnetic field indicate that the hyperfine field at the llgSn nucleus is oriented in the (111) plane of the rhombohedral lattice of ~ u - F e , o , . ~ ~ ~ The effect of the impurity ions Fez+, Cr3+, Pr3+, and Gd3+ on the spill relaxation time of the Feat- ions in the AI,O,-Fe,O, system has been Spectra have been obtained for the system YFe,-,AI,O, (X = 0, 0.1, 0.2, or 0.3). Non-equivalent Fe3 positions are produced as a result of the statistical distribution of A P ions. The increased orthorhombic distortion of the crystal lattice is mainly due to distortion of those octahedra in which there is located an Fe3’ ion having two or three A P + ions in its nearest-cation shell.31H The temperature dependence of the hyperfine field in the system (1 - x)Cr,O,-xFe,O, (X d 4.95 wt.%) in the temperature range 80 300 K supports the cone spiral structure originally proposed on the basis of neutron diffraction work. There is a linear decrease in the cone halfangle, 8, with increasing temperature and also to some extent with increasing x . The variation of the quadrupole splitting with temperature and x follows qualitatively the temperature and composition dependence of the trigonality, c/o, of the rhombohedral lattice. It was suggested that the anomalous spectra observed earlier in the 0.965Cr20,-0.035Fe,0, system were probably due to superparamagnetic A study of ferrimagnetic cobalt-doped y-Fe,O, has failed to detect the presence of either Fe2+or Fe4+,and indicates that cobalt replaces iron on B sites and fills B-site vacancies.32o Hyperfine interactions at the Fez’-sites in ilmenite, FeTiO,, have been determined by Mossbauer spectroscopy. The spectrum of a synthetic polycrystalline sample at 5 K is shown in Figure 20. The small internal magnetic field (Hilit = -43 k 3 kG) and the large quadrupole coupling (&ezqQ = 1.44 0.01 mm s-l) shifts the I -8 ) I - 4 ) transition to ) transition and leads to relative higher energy than the I + & ) -+ 1 intensities 2 : 1 : 1 : 2 : 3 : 3 in order of ascending energy. The negative sign of Hilitwas determined by application of an external magnetic field of 5 5 kG parallel to the c-axis of a single-crystal mineral sample of ilmenite at 87 K. Under these conditions the magnetization is far from saturated and only a small reduction in the internal field (Hint = 41 k 3 kG) was observed. This was sufficient, however, to establish the negative sign. The orbital, dipolar, and core polarization contributions to the internal field in both FeTiO, and FeCO, were recalculated to be Herb = +420 and +579, Htlip= + 5 9 and + 8 5 , Hk- = - 522 and -479 kG, respectively. The +

+a

:I1” :i20

--f

J. K . Srivnstava and K . G . Prasad, Pft.rs. Letters, 972, 40A,37. V. F. Belov, 7’. A . Khimich, M . N . Shipko, and M. I. Dakhis, Soi.iet Phys. Solid State, 1972, 14. 437. J. K . Srivustava and K . G . Prasad. f’hj<s. S t ( i t i i . s Solitli ( R ) , 1972. 54, 7 5 5 . D. Khrilafiilla and A . H . Morrish, J . Appl. Phj*.s.,1972, 43, 624.

Miissbairrr. Spec?roscop?y 557 theoretical interpretation of the internal fields in terms of these contributions was shown to depend critically upon the lattice contribution to Bes@, which is still unknown.3s1 The room temperature spectrum of FeVO, has been shown to contain six resonance lines (see Figure 21), which are assigned to three non-

1

-4

Figure 20 at 5 K

I

I

-2

I

I

0 Velocity /(mm s-'1

I

I

2

I

1

4-

Miisshauer spectrunr of slwthetic polj'crysralline ilnienire (FeTiO,)

[Reproduced by permission from Phys. Rev. ( B ) , 1972, 5, 17001

equivalent Fe3+ ions. The outer doublet arises from Fe3+ in a distorted trigonal-bipyramidal environment and the inner doublets to Fe:] in distorted octahedral Eleven different compositions in the system LiCr,-,Fe,O,, which has the ordered rocksalt structure, have been studied from 4.2 K to 300 K . All compositions order antiferromagnetically at low temperatures. There is a sharp discontinuity in the composition dependence of all the Mossbauer parameters at the cubic-to-rhombohedra1 phase transition at x = 0.7.323 Fe,TeO,, which crystallizes in a trirutile structure and is magnetoelectric, has been shown to contain Fe3+ ions. I t is magnetically ordered at 77 K but not at 300 K.324 s21

322

~4

R. W. Grant, R. M. Houslcy, and S. Geller, Phys. Rec. ( B ) , 1972, 5, 1700. B. Robertson and E. Kostiner, J . Solid State Chem., 1972, 4, 29. A. Tauber, W. M . Moller, and E. Banks, J . Solid State Chem., 1972, 4, 138. S. Bukshpan, E. Fischer, and R . M. Hornreich, Solid State Comnr., 1972, 10, 657.

558

Spectroscopic Properties of Itlorgattic curd Orggnnometattic Conipoirttds

A Mossbauer study of the oxides Fe,Mo,OB and FeZnMo,O, has confirmed the local trigonal symmetry of the tetrahedral and octahedral sites and has shown that the octahedral Fe2+ ions have a strong axial magnetic anisotropy. FeZnMo,O, is ferromagnetic below 20 K , whereas

I

0.0

I

0.5

1

I .o

I

1.5

1

Velocity /(mm s-1)

Figure 21 Miissbauer spectrum of FeVO, at room temperature. Velocity scale is relative to sodium nitroprusside. Solid line is the least-squares f i t , dashed lines are the individual peaks, arid circles indicate the normalized data. See text for peak assignment (Reproduced by permission from J . Solid State Chem., 1972, 4, 29)

Fe,Mo,O, is antiferromagnetic with TN = 6 0 K . In both cases the magnetic moments lie along the trigonal axis of the Spectra have also been reported for six catalysts prepared from MOO, and Fe,O,.ll Minerals. For the third year in succession, this section is dominated by a discussion of Mossbauer studies on lunar samples. Most of the work described here was published very recently in the Proceedings of the Third Lunar Science Conference which met in Houston, Texas, in January 1972 to discuss results on samples from five lunar landings-Apollo 1 1 , 12, 14, and 15 and Luna 16. The iron-bearing minerals in the four Apollo 14 fines (14003,20, 14162,48, 14163,50, and 14259,17) have been examined. The results parallel earlier data on the Apollo 1 1 and 12 samples but show significant differences in mineral content. A typical soil spectrum at 78 K is shown at the top of Figure 22 and can be interpreted in terms of three overlapping doublets from Fe2+in (ij olivine and A41 sites of pyroxenes, (iij M2 sites s26

A. Czeskleba, P. Imbert, and F. Varret, Amer. Inst. Phys. COT$Pro(.., 1972, NO. 5 (Pt. 2), 81 1.

559


of pyroxenes, and (iii) ilmenite, with quadrupole splittings which decrease i n that order, together with an ill-defined absorption from glassy material. Spectra at higher velocities exhibit a weak magnetic pattern, with broad lines, attributable to iron-nickel alloys (see below). The proportion of the iron as ilmenite is much lower than that of Apollo 11 fines (23%) but is similar to that found for Apollo 12 (5-8:(). There is no evidence for

00 18

36 94

too 90

96 94

100 98

1

196

78 K I

I

I _

560

Spectroscopic Properties of Itlorganic ntid Organometnllic Cot?ipont~S

the presence of Fe3 or troilite (FeS), aIthough the latter has been reported in previous Apollo The fines returned by the automatic station Luna 16 give essentially similar spectra to those discussed above. The results indicate that these samples differ from those returned by Apollo 11 in having a lower ilnienite and greater olivine content. The olivine content is also greater than that in Apollo 12 samples. The hyperfine field of the small magnetic component

velocity / ( m m s-')

Figure 23 MGssbauer spectra at 78 K atid 4.2 K of a highly magnetic separate from soil 14259,17 (Reproduced by permission from Proceedings of the Third Lunar Science Conference, Vol. 1 , Ceochint. Cosmnchim. Acto, Supplement 3 , MIT Press, 1972, p. 2479)

present is identical with that in pure iron, indicating that the sample contains no nickel impurity (see later). This result was contrasted with data for two iron meteorites, which were known to contain respectively 6 and 16% nickel and which give hyperfine fields 1.03 and 1.026 times greater than that in pure iron.327 The remaining spectra in Figure 22 correspond to various density fractions from sample 14259,17. The heaviest fraction shows the narrowest lines and, although the degree of separation is disappointing, there is substantial enhancement in the olivine resonance. The poorly resolved resonance from the lightest fraction is associated with a high glass content T. C. Gibb, R. Greatrex, N. N. Greenwood, and M. H. Battey, Proc. 3rd Lunar n ~, . Supplement 3, MIT Press, Science Conference, Vol. I , Geochirii. C o . ~ t r ~ o ~ hAi m 1972, p. 2479. T. V. Malysheva, Proc. 3rd Lunar Science Conference, Vol. 1 , Geochirn. Cosmochim. Acfn. Supplement 3 , M I T Press, 1972, p . 105.

Miissbnuer. Spectr.oscopj*

56 I

and is also noteworthy in containing a discernible residual quantity of metallic iron. The greater part of the latter is therefore associated with the glassy phases. Fractionation with a hand magnet was more successful and yielded 7 mg of a highly magnetic fraction (from an initial sample weighing 4.5 g), the spectrum of which is shown in Figure 23. The sample contains a comparatively small silicate residue and the majority of the iron is ferromagnetic with a magnetic hyperfine field of 333 f 1 k G at 295 K, 345 k 1 kG at 77 K , and 346 f 1 at 4.2 K. These values compare with fields of 330, 337, and 338 kG for pure iron. The majority of metals which alloy with iron reduce the hyperfine field, the exceptions being cobalt and nickel. The data are consistent with an average nickel content of 3 at.% and this figure was confirmed by X-ray fluorescence and electron microprobe analysis.326 The spectrum of the soil 14259,69 has also been analy~ed.~~~ Spectra of partial magnetic separates from Apollo 1 1 fines 10084, taken at various temperatures and applied magnetic fields, have yielded a value for the magnetic hyperfine field at the iron nucleus at 5 K of H h t = 340.6 k 1.0 kG, compared with a redetermined value of 339.7 k G for pure iron metal. This determination places an upper limit of 1.5% on any nickel admixture into the iron grains, which is taken as strong evidence that the metal originates from a reduction process rather than by direct meteoritic addition. The iron was believed to be present in the superparamagnetic, as well as in the ferromagnetic, state and it was estimated that approximately 20% of the iron grains were between 13.4 and 8.5 nm in diameter and that there were considerably fewer grains in the size range 8.5-2.0 nm. An upper limit of 0.04% was placed on the amount of magnetite or similar Fe31-containing magnetic spinel present in the 10084,85 fines and this was estimated to be about an order of magnitude lower than that required to account for the characteristic ferromagnetic resonance observed in the fines.328 Spectra for the rock chips 14301,15, 14303,36, 14310,66, 1431 1,32, 14318,35, and 14321,179 326 and the rock samples 10048, 12053, 14047,47, 14053,48, 14063,47, 14301,65, and 14303,35 328 have been analysed in detail. The spectra have significantly narrower resonance lines than those of the soils, attributable to the much lower glass content, and show greater differences from sample to sample. Rock 14310,66 appears to have a site occupancy of (~ g o . , o ~ e o . ~ o ) ~ , , [ ~ g o . 0 2 ~ e o the . ~ 6high ~ a degree ~ . ~ 2 ]of~ 2 ~ i 2 ~ 6 , cation order being consistent with equilibration at a temperature of about 900 K.326Rock 14053 is exceptional in having a very high content of nearly pure metallic iron (see Figure 24) and it is claimed that in the spectrum at s2a

329

F. C. Shchwerer, G. P. Huffman, R. M . Fisher, and T. Nagata, Proc. 3rd Lunar . Supplement 3, MIT Press, Science Conference, Vol. 1 , Geochim. C o sn i o c h i ~ ~Actn, 1972, p. 3173. R. M. Housley, R. W. Grant, and M. Abdel-Cawad, Proc. 3rd Lunar Science Conference, Vol. 1, Geochim. Cosmochim. Acla, Supplement 3, MIT Press, 1972, p. 1065. 19

562

Spectroscopic Propertics of Inorganic and Organometallic Compounds

86 K there is evidence of an additional magnetic component, with a hyperfine field of about 400 kG,due possibly to a spinel. Rock 14063 has an

exceptionally high olivine content, whereas 14047 contains a large amount of glass and gives a broad magnetic component suggestive of a high nickel content. In 14303 most of the iron in the pyroxene phase occupies the M 2 sites. For samples 10048 and 12053 it was shown that increases which

4

- A pD . I14400 5 3 - 1 9 - 2 T = 295K

I

-.3

-c

I

-4

1

c

0

++-+--+ '

Velocity [ ( m m s-5

Figure 24 Mussbauer spectra of 14053. The arrows denote the positions of the outermost peaks for the weak magnetic phase discussed in the text

(Reproduced by permission from Proceedings of the Third Lunar Science Conference, Vol. 1, Geochint. Cosriiochitn. Acta, Supplenient 3 , M IT Press, 1972, p. 3173) occur in the electrical conductivity on heating the sample are paralleled by changes in the Mossbauer spectrum, corresponding to a redistribution of about 2% of the A42 iron into the A 4 1 sites and, for 10048 only, to a dramatic increase of about 30% in the ilmenite resonance. For samples 12053 and 14303 interesting relaxation phenomena were observcd at 2 K.328 Cation distributions derived from Miissbauer spectra and exsolution relationships from single-crystal X-ray studies have been compared for three pyroxene fractions from Apollo 12 rock 12021, and it is claimed that the Mossbauer nieasurements indicate an anomalous excess of cations in M 2 sites. It is suggested that the anomaly is a result of a bias in the Mossbauer measurements owing, firstly, to the presence of large amounts of calcium and other minor impurities, which produce differing local environments for the iron atoms in M I sites and split the A41 absorption so that

Miissbarrer. Spectroscopy 563 part of it lies beneath the R.12 doublet and, secondly, to non-supcrposition of the M I doublets for the exsolved pigeonite and augite in each fraction.33o It was pointed out that this effect would be more pronounced in augite than in pigeonite, because samples of the latter contain much less calcium and smaller amounts of exsolved augite lamellae. Furthermore, the cation distributions in augite and pigeonite phases, as determined by Mossbauer spectroscopy, are statistical averages because they both show a wide range in chemical composition as well as extensive exsolution. Despite these difficulties, the technique is still considered to be extremely useful for determining the relative cooling histories of lunar rocks. The pigeonites from rocks 12021, 12053, 12038, and 143 10 all show a high degree of cation order, consistent with a final equilibration at temperatures of about 970 K . The presence of secondary generation exsolution lamellae in these samples indicates that the rocks were reheated to these temperatures some time after crystallization from the melt at a much higher temperature ( - 1470 K). Rock 14053 shows the highest degree of cation disorder and probably equilibrated at a temperature of about 1100 K . However, second-generation exsolution lamellae are absent so the duration of reheating must have been very short. The augites from rocks 12021, 12053, and 14053 all show high degrees of cation order which correspond to equilibration temperatures similar to those deduced for the pigeonites from the same The distribution of Mg2+and Fe2+ions over the M I and A42 positions in pyroxene separated from the basaltic rocks 14053 and 14310 has been studied in order to analyse their subsolidus cooling history. The results suggest that the pigeonite from 14053,47 equilibrated at approximately 1100 K and must have been quenched extremely rapidly by impact at Fra Mauro as a fragment of a larger body from the lmbrian ejecta. By contrast, the orthopyroxene from 14310,116 probably equilibrated at about 870 K at a depth of several metres in a coherent body of appreciable size.332 This result is in excellent agreement with that discussed earlier for rock 14310,66.326 The centre of gravity of the total resonance area of 57Fein plagioclases from rocks 14053, 14310, and 15415 and from sonie terrestrial anorthosites and basalts has been tentatively interpreted in terms of the Fe3$/Fehtal ratio. The values for the lunar samples range from 0.04 to 0.12 and those for the terrestrial materials frotn 0.18 to 0.57. The values can be correlated with the oxygen partial pressure conditions which prevailed during ~rystallization.~~~ 330

azl

E. Dowty, M. Ross, and F. Cuttitta, Proc. 3rd Lunar Science Conference, Vol. 1 , Geochim. Cosmochim. Acro, Supplement 3 , MIT Press, 1972, p. 481. S. Ghose, G. Ng, and L. S. Walter, Proc. 3rd Lunar Science Conference, VoI. 1 , Geochim. Cosmochim. Acta, Supplement 3 , MIT Press, 1972, p. 507. K. Schurmann and S. S. Hafner, Proc. 3rd Lunar Science Conference, Vol. 1, Geochinr. Cosmochim. Actn, Supplement 3 , MIT Press, 1972, p. 493. K. Schurman and S. S. Hafner, Proc. 3rd Lunar Science Conference, Vol. 1, Geochim. Cosrnochim. Acta, Supplement 3 , MIT Press, 1972, p. 615

564

Spectroscopic Properties of Imwgotiic. cind Organometnllic C'omporrnds

The temperature dependence of' the hlg, I e distribution in a lunar olivine has been Previous applications of Mossbauer spectroscopy in mineralogy have been reviewed 25 but, compared with last year, relatively few papers dealing with new work on terrestrial minerals have appeared. Hyperfine interactions of Fe2+in ilmenite, FeTiO,, are discussed in the previous The technique has been used to determine the temperatures of formation of samples of olivine. The degree of ordering was the same in olivine samples heated at 1000 "C for 2 days or at 1100 "C for 5 days but disordering occurred in samples heated at 1150 "C for 5 h. It was therefore concluded that the olivine was formed originally at a temperature of 1100-1150 " C . Thermometric studies indicated that the sample had equilibrated at 1 100-1 130 0C.335 The Fe2+and Fe3+ ions in tourmalines have both been shown to occupy six-co-ordinate sites, with substantial amounts of iron in the smaller octahedra generally assumed to be filled with A13+ ions. In titaniferous garnets the Fe3+ions not only occupy the octahedral sites, but also substitute for silicon in the very small tetrahedral sites in amounts proportional to the titanium content of the garnets. Discrepancies between the F e z + content of garnets as determined by Mossbauer spectroscopy and by chemical analysis are attributed to the presence of Ti3+ in the garnets. The geochemical significance of these results lies in the observation that many minerals are in fact chemically resistant or contain significant amounts of titanium, with the result that errors in chemically determined Fe2+/Fe3+ratios and unusual cation site-occupancies may be prevalent in certain rock-forming The phosphate minerals triplite, zwieselite, triploidite, and wolfei te have been shown to contain non-equivalent Fe2+ ions. Line-broadening which is present in the spectra is thought to indicate microscopic disorder due to half occupied F sites in the fluoride minerals and to sets of closely related metal sites in the hydroxy minerals.337 Other minerals studied include biotite,33B w ~ l l a s t o n i t e , iron-man~~~ ganese nodules from the Pacific Ocean,34o* 341 and arfvedsonite and aegirineaugite from the Joan Lake agpaitic complex, Labrador.342 Mossbauer spectroscopy has also been used in the backscattering mode to monitor pyritic oxidation. It is possible to distinguish between unreacted and y3p

336 330

337 338

:WI

s40

341

s4a

D. Virgo and S. S. Hafner, Earth and Plnrierry Sci. Lerters, 1972, 14, 305. T. V. Malysheva, B. P. Romanchev, and V. D. Shvagerov, Geokhirniytr, 1972, 496. R. G. Burns, Canad. J . Spectroscopy, 1972, 17, 51. E. S. Kostiner, Amer. Mineral., 1972, 57, 1109. E. V. Pol'shin, I. V. Matyash, V. E. Tepikin. and V. P. Ivanitskii, KristallogruJyn, 1972, 17, 328. 1. Shinno, Kyushu Daigaku Kyoyobu Chignku Kenkyu Hokoku, 1972, 17, 51. A. Z . Hrynkiewicz, A . J. Pustowka, B. D. Sawicka, and J. A. Sawicki, Phys. Stntrrs Solidi ( A ) . 1972, 9, K 159. A. Z. Hrynkiewicz, A. J. Pustowka, B. D. Sawicka, and J. A. Sawicki, Phys. Starus Solidi ( A ) , 1972, 10, 281. S. K . Singh and M . Bonardi, Lifhns. 1972, 5, 217.

Miissbairet- Spectroscopy 565 oxidized pyrite minerals from spectra of the mineral surface obtained through 2 mm of water.343

Clialcogenides. Tetragonal FeS has been studied to resolve discrepancies in the literature. The observed spectrum contains only an unresolved quadrupole doublet with an isomer shift of 0.62 mm s-l. It was suggested that magnetic components seen by other workers probably arose from impurities of other sulphides. The results were discussed in terms of a tentative bonding scheme for the compound; the iron is considered to be lowspin.344 Solid solutions in the wurtzite (ZnS) -troilite (FeS) system have been The anisotropy of the Mossbauer effect in pyrites (FeS,) 175 and pyritic oxidation studies 343 have already been referred to. The thiospinel Fe[Cr,]S, has been studied in detail over the temperature range 2-500 K and in zero and externally applied magnetic fields. The magnetically split spectra were fitted with a zero value of the asymmetry parameter over the temperature range 7-170 K, but for T < 4.2 K a non-zero value was required. Experiments in applied magnetic fields at 7 and 81 K showed that the quadrupole interaction, which appears below the magnetic ordering temperature, is not produced by a crystallographic distortion. Asymmetric line-broadening, observed in some of the spectra, was attributed to the presence of relaxation effects in the compound. These observations, coupled with the temperature dependence of the isomer shift which shows deviations from the Debye model behaviour, were explained in terms of a model for the compound. It was suggested that the sixth d-electron is localized at both very high and very low temperatures, whereas at intermediate temperatures it occupies a very narrow band formed by electron transfer between octahedral and tetrahedral sites. Below about 179 K most aspects of the spectra can be explained in terms of localized behaviour and a dynamic Jahn--Tellereffect which at very low temperatures resolves itself into a static distortion of the tetrahedral More detailed experiments at low temperature have substantiated this suggestion that the electric-field gradient arises from the Jahn-Teller stabilization of the 5E,(Fe2+) ground state. The stabilization energy, A/k 28 K (0 < T d 8 K), is at least an order of magnitude smaller The quadrupole splitting in than in the corresponding oxide Cdo.BBFe,,.02Cr,S,below the Curie temperature (96 K) is thought to be magnetically induced. The observed temperature dependences of the quadrupole and magnetic hyperfine splittings were rationalized in terms of the combined action of a crystal field, an exchange field, and a spin-orbit interact ion.348 N

343

3u4 345

34R y47 :Irn

R . A. Baker, Woter Res., 1972, 6, 9. A. Kjekshus, Actn Cherrr. Scand., 1972, 26, 1105. V. V. Kurash, T. V. Mdysheva, V. D. Shvagerev, V. I . Goldanskii, and A . Ya. Volkova, G e o h h i m i ~ ~1972, a, 5, 568. M. R. Spender and A . H . Morrish, Cwrod. J . Phj*s., 1972, 50, 1125. M. R. Spender and A . H . Morrish, Solid Stafr Conrtu.. 1972, 11, 1417. A. M. van Diepen and R . P. van Stapele. Phys. Rec. ( B ) , 1972, 5, 2462.

566

Spn-troscwpic Properties of' Iiiorgrriiic and Orgnnornetallic Comporrnds

The magnetic ordering in cubanite, Cu,FeSnS,, has been studied by Mossbauer spectroscopy. The spectrum at 4.2 K is shown in Figure 25 and reveals that the internal magnetic field, HilIt = 205 kG,is perpendicular to the tetragonal electric-field gradient axis and that Be2@ = -2.7 inm s-*. The negative sign of the quadrupole interaction was corroborated by

322 318

f

li 3021

-6

I

-4

1

-2

I

0

I

2

I

4

I

6

1

8

Velocity /(mm s")

Figure 25 Mossbauer spectrum of C U , ~ ' F ~ Sat~ S4.2 ~ K. The f i l l line is a cornpuler fit to the case of Hi,,t 1 z and negative e2qQ/2 (Reproduced by permission from J . Phys. and Chem. Solids, 1972, 33, 1873)

the spectrum obtained at room temperature in an applied magnetic field of 28 kG and indicates that the orbital ground state for the tetrahedral Fe2+ ion is 132' - r2 ). This is separated from the first excited state I x 2 - y 2 by 1700 K. The negative sign disagrees with a point-charge calculation, which neglects important dipolar terms, but calculations of the single-ion anisotropy based on the observed negative sign correctly predict the relative orientation of the magnetic- and electric-field gradient axes. The llQSn spectrum of cubanite is discussed on p. 590.349 The sulphides Cu,Fe,S,, Cu18Fe16Ss2,and CugFesS16have also been studied.35o Preliminary measurements have been reported on the ternary selenides listed in Table 2. These six selenides are of the type M , 0 X 4 with ordered vacancies. Half of the iron atoms are located in (001) vacancy planes and other iron and M atoms are statistically distributed in full planes. The compounds are all ferrimagnetic and show a metallic type conductivity. In the paramagnetic region the Mijssbauer spectra exhibit resonances which correspond to neither ionic Fe2+nor Fe3+, and in the magnetically

>

U. Ganiel, E. Hermon, and S. Shtrikman, J . Phys. nnd Chem. Solids, 1972, 33, 1873. M . G . Townsend, J . L. Horwood, S. R. Hail. and J. L. Cabri, Amer. Inst. PJtjvs. Car$ Proc., 1972, NO. 5 (Pt. 2), 887.

Miissbaues Spectroscopy 567 ordered region the magnetic hyperfine fields recorded for the two iron sites (see Table 2) are much less than those normally found in ionic oxides. These results indicate that extensive electron delocalization occurs in these compounds and that an ionic model is i n a p p r ~ p r i a t e . ~ ~ ~

Table 2

coI? 1po1111(I TiFe,Se, CrFe,Se, Fe3Se, CoFe,Se, NiFe,Sc,

Ititernat f i e t d ~( H

221, 248, 230, 115, 70,

t 5)/kG

130 141

110

75 35

Spectra have been obtained for the iron tellurides FeTe, ( x = 0.95, 1.50, or 1.97) at room temperature and have been fitted with two doublets from two non-equivalent iron atoms. The isomer shifts for each iron atom are similar and are compatiblc with 3 8 4 . ~ h4 y~b ~r i d i z a t i ~ n . ~ ~ ~ 5 Tin-119 A number of papers containing information relevant to this section are mentioned 9G H R y

General Topics.-- The magnetic moment of the 89 keV excited state of ll'Sn in a cubic Co-Fe matrix has been detected by Mcssbauer measurements at 30--75 niK to be - 1.40 ? 0.08 px.353The quadrupole moment of this 1; - state has also been determined with sources of 11RSn(OI-1)2 at temperatures between 14 mK and 4.2 K. The experiment is based on the fact that nuclear orientation in the 12'state at low temperatures leads to an alignment in the state which results in an asymmetry in the intensities of the two quadrupole lines. The value obtained was Q , , , , = - 0.13 k 0.04 b.354 A value has also been calculated for the quadrupole moment of the 23.9 keV $ + state of llDSn by comparing "'Sn and lzlSb quadrupole splittings for isoelectronic and isostructural compounds (see Figure 26). All of the antimony compounds and two of the tin compounds, [Me,SnCI,]- and [Ph,SnCI,]-, are known to have negative e2qQ values and it is assumed that the other R,SnX, compounds have negative values also. From the slope of the graph the quadrupole moment was calculated to be -0.062 k 0.02 x m2. The quadrupole splitting of the SnC1,- i m was deduced to be negative."'

z+

3G1 352

5b3

:154 355

B. Lambert-Andron, G . Berodias, and D. Babot, J . P h j s . orid Chem. Solids, 1972, 33, 87. V. Fano and I. Ortalli, Phys. Status Solidi ( A ) , 1972, 10, K121. D. F. Gumprecht, T. E. Katila, L. C. Moberg, and P. 0. Lipas, Phys. Lcrrers ( A ) , 1972, 40, 297. G . N. Beloserski, 1). M . Gumprecht, and P. Stciner, Ph-vs. Letters, 1972, 42B, 349. G . M . Bancroft, K . D. Butler, and E. T. Libbey, J . C . S . Dalton, 1972, 2633.

568

Spec.troscopic. Properties of‘ Iiiorgmic.

aid

Orgunometullic Coniporrrrdr

Spectra have been obtained for l19Sn atoms isolated in rare-gas matrices at 4.2 K and are dominated by a single line with an isomer shift of + 3.21 f 0.01 mm s-’ relative to BaSnO, at 300 K (see Figure 27). The shift is independent of rare-gas matrix and tin atomic concentration. The resonance is ascribed to an isolated tin monomer with the atomic

0

2

4

-r‘po (sn) I ( m m r-1)

6

Figure 26 e’ qQ Jbr SbV coiupoimh plotted ugaitist e‘yQ j o r isuelectronic Sn’’ compounds

configuration 4d105s25p2.A comparison of the isomer shift data for tin compounds with those for the isolated monomer (see Figure 28) suggests that the electron densities at the tin nuclei in tin compounds are higher than the electron densities in the corresponding free-ion configurations by a factor of 1.25, because of solid-state effects. Detailed analysis of the isomer for the 23.9 keV y-transishift data yields a value of A R / R = 7.3 x tion. At higher concentrations a weak quadrupole-doublet resonance, assigned to tin dimers, appears in the spectrum (see Figure 27). The observed quadrupole splitting of 3.5 k 0.25 mm s-l agrees closely with previous estimates of the quadrupole splitting for a single p z electron in stannous compounds and it is therefore assumed that the tin dimer contains both 5p electrons in either the p s or p v level (i.e. IqdiIllerI = 2 I qpz(3)I = I qpzI). The data yield a value of I Q I = 0.065 k 0.005 b for the quadrupole moment of the I = 2 excited state of 119Sn.s5sStudies of llsSn isolated in solid nitrogen are discussed a b 0 ~ e . l ~ ’ H. Micklitz and P. H . Barrett, Phj3s. Rea. ( B ) , 1972, 5 , 1704.

569 Preliminary spectra have also been given (see Figure 29) for matrixisolated SnO molecules. The large quadrupole splitting of ca. 4.10 mm s-' yields a lower limit of cn. 3.0 mm s-l for the quadrupole splitting due to one p z electron. The more concentrated matrices give spectra with additional doublets, corresponding to simple polymers [e.g. Figure 29(c) and Miissbarrrr Spmtroscop.v

100.0-

99.9-

c .In .-

5!E

99.8-

+-

Q,

2

.-

99.7-

CY

99.6 -

I

0

1

]

2

_

4

-

6

I

Velocity / ( mm s-'1

Figure 27 Miissbauer spectrum of l%n in mi argon matrix at 4.2 K. Ar/Fe = 60; 205 pg cm-2 tin (84% enriched llRSn). The solid curue is a computer f i t to the monomer and dimer resonances [Reproduced by permission from Phys. Rev. ( B ) , 1972, 5, 17041

(d)]. Similar peaks are also observed in the spectra of matrix b after annealing at 34.5 K.357 Accurate values of 1.328 k 0.003 x lo-'* cm2 for the maximum resonance cross-section of lls*%n, 0o, and of 0.63 k 0.02, 0.45 k 0.02, and 0.050 k 0.005 for thef-factors of BaSnO,, SnO,, and white tin have been determined by use of a high-resolution silicon-lithium drifted detect or.89 Mossbauer emission spectra of 119Sb-labelled antimony, Sb,Te,, and Sb,S3 have been obtained (see Figure 30) and indicate the appearance of Sno, Sn", and Sn" + Sn'" states, respectively, in the three solids. The final state of lleSn therefore depends on the properties of the matrices rather than on the direct effects of the electron-capture decay and the subsequent Auger process. The difference in the distribution of the lleSn in the a';

A . Bos, A .

730.

I. HOMC.B . W. Dale, and L . W . Bcckcr, J.C.S. Chrni.

Coriiiii.,

1972,

5 70

Sp L. L’ I r o s w p ic. Proper f ies of’ It!orgli tiic

(it1d

0r g m oin P t ii f f ic Cotrip(I 11t ids

two chalcogenides of antiniony(u1) suggests the importance of the electronegativity of the ligand in determining the valence state of the tin. Sb,S, has a relatively low electrical conductivity, in contrast to the other two materials, and because of the low mobility of the electrons in the solid the appearance of more than one valence state of tin is not ~nexpected.”~ The emission spectra of frozen solutions of SnCI, in HCI, Me,CO, and

-120

- 100 s n - monomer

-80

a-

60

-

=?

N

0

b

4d1’5s5p3

4d1*

-

-40

1

0

I

I

2 Isomer shift I (mm

4

4

- 20

-

Sn-monomer I S the literature

-

K2

3.

-0

6

S”)

Figure 28 Correlation between the electron density I #(O) l2 at the nucleus and the isomer shift for ll@Sn. The open circle is the measured shift for the tin tmnomer; the filled circles are taken from the literature [Reproduced by permission from Phys. Rev. ( B ) , 1972, 5, 17041

MeOH, previously exposed to air, have been measured at 80 K. The systems with HCl and Me,CO were shown to contain only tin(iv), whereas MeOH stabilized tin in the bivalent In addition to the cubic-to-tetragonal ferroelectric phase transition at 393 K, BaTiO, also exhibits a tetragonal-to-orthorhombic transition at 278 K and an orthorhombic-to-rhombohedra1transition at 183 K . The two lower transitions have now been investigated with the aid of ll’Sn 36s

359

F. Ambe, H. Shoji, S. Ambe, M . Takcda, and N. Saito, Chem. Phys. Letters, 1972, 14, 522. S. I . Bondarcvskii and V. A . Tarasov, R~diokhiti~iya, 1972, 14, 162.

Miissbauer Spectroscopy 57 I Mossbauer spectroscopy. The spectra obtained with sources of llsSn diffused into BaTiO, show only the presence of tin(1v) in the lattice. The normalized resonance area and the percentage absorption both show minima at the two transition temperatures, consistent with Cochran‘s 1001-

a

L

3

8

Velocity (mm

s-‘)

Figure 29 l%Sn hliissbauer spectra obtained at 4.2 K front matrices having SnO : Ar ca. 1 : 10 000 (a) and SnO : N, ca. 1 : 3000 (b) 1 : 400 (c),and 1 : 100 (d). Sn content 20-400 pg cm-2 (90% l19Sn). The arrow indicates the position of u fin inipurity peak dericed from the thermocouple solder

suggestion that these two phase transitions are caused by lattice instabilities.”O Spectra have been obtained for llSSn impurity atoms in Mn03‘j1 and transferred hyperfine fields have been observed at l19Sn nuclei in the magnetically ordered perovskites Yo.9Cao.lFeo.9Sno.103,362~ 363 Lao.9Cao.lCr,.,Sn,.,O,, and Lao.,Ceo.3Mno.sSno.103.363 At 85 K the field is large (170 kG) in the ferrite, but small (30 kG) in the chromite. These results were explained on the basis of a MO method Mqhich indicates that direct transfer of spin density to the 5s orbitals of tin is only possible via the e(, orbitals of the paramagnetic constituent and that these are unoccupied in Cr3+(&). The spectrum of the ferromagnetic manganite indicates a 3R0

Bo2 30s

V. G. Bhide and V. V. Durge, Solid State Cornni., 1972, 10, 401. P. B. Fabrichnyi, E. V. Larnykin, A. M . Babeshkin, and A. N . Nesmeyanov, Sotiet Phys. Solid State, 1972, 13, 2874. I. S. Lyubutin and Yu. S. Vishnyakov, Kristallografiya, 1972, 17, 960. V. A. Bokov, G. V. I’opov, N. N. Parfenova, and G . G . Yushina, Soviet Phys. Solid Store, 1972, 14, 83.

512

Spectrostvpic Properties of’Inorgarlic and Orgurronietrrllic Compoirric1.s

large spread of hyperfine fields, ranging from 130 t o 200 kG,on account of the distribution of non-equivalent cation-envir~nrnents.~~~ Transferred fields have also been observed in the ferrite garnets ( Y 3-,Ca,)[Fe,-,Sn,](Fe,)O,, ( x = 0.1-0.9) and the existence of a non-collinear spin configuration established for the Fe3’ moments in the d - ~ u b l a t t i c e . The ~~~

-1 0

-5

1

0

1

5

I 10

Velocity i ( m m 5 - l )

Figure 30 l19Sn Mossbauer emission spectra of ”‘Sn-labelled antiniony nietal, Sb,Te,, and Sb,S3 at liquid nitrogen iernperature versus BaSnO, at room temperature (Reproduced by permission from Chem. Phys. Letters, 1972, 14, 522)

effect of tin impurity atoms o n the Morin transition temperature in haematite is described on p. 5 5 5 . Spectra have been obtained for llgSn impurity atoms in gallium in porous glass,3s5and the effects of the glass-crystal transition on the local surroundings of I1’Sn impurity atoms in As,Te, and in As,Se,.As,Te, have been 864

sa6

I . S. Lyubutin and A. P. Dodokin, Pis’ttiu Zhur eksp. i teor. Fiz., 1972, 15, 339. V. N. Bogomolov, N. A. Klushin, and P. P. Seregin, Souiet Phys. Solid Store, 1972, 14, 1729. P. P. Seregin arid L. N. Vasil’ev, Sorict P / i j * ~Solid . SfntP, 1972, 14, 1325.

Mossbriim Speciroseopj573 Mossbauer spectra have been presented for palladium-based sols, generated by reduction with Sn". From Figure 31 it can be seen that the spectra of the "'Sn atoms in the sol show directly the metal sol core and the inner part of the stabilizing double layer as distinct phases. In Figure 31(a) the Snq line is constrained to the position determined in a

Velocity I (mm s-1)

Miissbauer spectra of frozen Sn-Pd sols. For explanation see text (Reproduced by permission from Chent. Phys. Letters, 1972, 16, 128) Figure 31

separate experiment using pure Sn4+ dissolved in 4M-HCl. Figure 31(b) shows the spectrum of a centrifugally separated sol in which the Sn4+ line is absent and the components of interest are clearly differentiated. Figure 31(c) shows the spectrum of a sample prepared in a similar fashion but having larger particles and therefore a smaller total surface area. These are believed to be the first resonance experiments of any kind to 368 provide information of this 3nn

R. L. Cohen and K . W. West, Chtm. Phys. Letters, 1972, 16, 128. R. L. Cohen and K . W. West. J . Electrocheni. Soc., 1972, 119, 433.

5 14

Spec*(roscopicProperties of Itiorgotiic

citirl

Orgorronietnllic~( b m p o r t r d r

Tin(ri) Compounds.--Estimates of the lattice contributiun to tlw elcctricfield gradient have been made for the five tin(ii) materials SnO, SnSO,, NaSn,F,, CsSnCI,, and SnCI,. The sign of the lattice contribution is positive in all cases except SnCI,, a typical calculated value being 10l3e.s.u. Considering that one p z electron produces a field gradient of about - 3 x 1Ols e.s.u. it is clear that, even when allowance is made for shielding effects, the lattice contribution must be negligible in comparison with the valence contribution. Indeed, the signs of V,, are known to be negative for SnO, SnSO,, and Experimental data on frozen solutions containing Sn2+ indicate that cooling rates normally obtainable are insufficient to prevent the precipitation of crystalline hydrated salts unless a glass former, such as glycerol or methanol, is added to the system. I t was shown that water is not displaced from the tin co-ordination sphere unless the additive concentration is very high.370 Attempts to prepare a covalently bound tin(i1) nitrate, by the reduction of tin(iv) tetranitrate with anhydrous nitric oxide, have produced only a white solid of formula SnN,O,, which gives a tin(iv) Mossbauer resonance (6 = 0.29 mm s-l, h = 0.96 mm s-l). However, addition of a freshly prepared solution of 100% nitric acid in methyl cyanide to a suspension of di(methylcyc1opentadienyl)tin in the same solvent has been shown to give a non-separable mixture of tin([]) dinitrate and a methyl cyclopentadiene polymer. The dinitrate has one of the largest shifts so far observed for a tin(i1) compound ( 6 = 4.10 mm s l). The i.r. spectrum suggests that it has two types of covalent nitrate l i g a n d ~ . ~ ' ~ Data have been given for a total of 33 complexes of the types MSnX,, MX,MSnX,, and MSn,X, ( M = Na, K, Rb, Cs, or N H 4 ; X = Cl or Br) isolated from the aqueous and molten MX-SnX, systems. The results are discussed in terms of the likely environments for tin(ii) and of the use of tin bonding orbitals in complex formation.372 The complex [Co(dpe),CI]SnCl, [dpe == bis-(l,2-diphenylphosphino)ethane] has been shown to crystallize in two forms, each containing an isolated trichlorotin(1i) group. The 2 + oxidation state was confirmed by the large isomer shift (6 = 3.10 mm s- relative to BaSnO,). This is the first such arrangement found in a transition-metal compound. Normally the SnX,- group is linked covalently to the metal and gives an isomer shift in the tin(iv) region.,', This is found to be the case in the compounds cis- and tmns-Fe(SnC1,),(ArNC),, cis-FeCI(SnCl,)(ArNC),, and [Fe36s 370 3i1

J. D. Donaldson, D . C. Puxley, and M. J. Tricker, Inorg. Nuclear Chern. Letters, 1972, 8, 845. R. L. Cohen and K. W. West, Chem. Phys. Letters, 1972, 13, 482. P. G . Harrison, M. I. Khalil, and N. Logan, Inorg. Nuclear Chern. Letters, 1972, 8, 551.

372 37:i

S . R. A. Bird, J. D. Donaldson, and J. Silver, J . C . S . Dalton, 1972, 1950. J. Stalick, D. W. Meek, B. Y . K . H o , and J. .I.Zuckerman, J.C.S. Chem. Cornrir., 1972, 630.


575

(ArNC),SnCI,]CIO,, which have isomer shifts of cn. 2 min s-l relative to RaSnO,. These results show that the formal oxidation state of tin in SnCI, complexes has significance only when the oxidation state of the other atoms and ligands is well defined, However, the valency of tin in all SnCI, complexes is four.236 The presence of an asymmetric doublet in the Mossbauer spectrum of Sn,BrF, has now been explained by a crystal-structure determination of this compound by X-ray diffraction. Instead of two very distinct tin sites which would be required by a formulation of the type SnF,.SnFBrSnF,, three very similar tin environments were found in the infinite tin(r1) fluoride cationic network, each tin having a pyramidal three-co-ordinated environment .375 The first oxidative-addition reactions of stannous halides with carboncarbon multiply bonded systems to form organotin(ii) derivatives have been reported. The i.r. and Mossbauer data for products of the reactions between stannous halides and dimethylacetylene dicarboxylate in dry TH F are consistent with the cis dimeric structure (12), in which the co-ordination number of each tin atom is raised to six by intermolecular co-ordination via the c a r b o x y - g r o u p ~ . ~ ~ ~ Data have been given for 15 novel tin(ii) derivatives obtained by photolysis of dicyclopentadienyltin(i1). The 2 + oxidation state was confirmed by the isomer shifts of these compounds which included carboxylates, alkoxides, aryl oxides, oximes, hydroxylamines, metalloxanes, azoles, thiolates, and pseudo halide^.^^^ Tin(i1) oxalate and phthalate have been studied and are thought to have polymeric structures with bridging carboxylate groups as shown in ( I 3).377 The oxidation of tin(ir) chalcogenides has been R R

Tin(iv) Compounds.---The relationship between Il9Sn Mossbauer shifts and atomic parameters, such as Mulliken valence-state electronegativities, has continued to arouse controversy. It appears that equally good correlations are found with both Pauling and Mulliken v a I ~ l e s .380 ~~~* 374 371

376 377

378

379

380

J . D . Donaldson and D . C. Puxley, J . C . S . Chetn. Comrn., 1972, 289. P. G. Harrison, Inorg. Nuclear Chern. Letters, 1972, 8 , 555. P. G. Harrison, J.C.S. Chern. Comrn., 1972, 544. N. W. G. Debye, D . E. Fenton, and J. J. Zuckermann, J . Inorg. Nuclear Chetn., 1972, 34, 352. P. P. Seregin, S. I. Bondarevskii, V. T. Shipatov, and V. A. Tarasov, Izvest. Akud. Nauk S.S.S.R., neorg. Materialy, 1972, 8, 571. J. C. Watts and J. E. Huheey, Chem. Phys. Letters, 1972, 14, 89. R. V. Parish, Chern. Phys. Letters, 1972, 14, 91.

576

Spertroscopic Properties of' Itior/:(ttiic utid Ot-gntionietallic Cot?ipoiuidv

The tin 3 4 electron binding energies for octahedral tin conipiexes o f formula [(MeCH,),N],[SnX, - n Y n ](X = Y = halogen), determined froin X-ray photoelectron spectroscopy (ESCA), have been found to correlate linearly with average ligand electronegativities, Mossbauer isomer shifts, and estimated atomic charges on the tin atom.38* The replacement of ethyl groups by halogen atoms in the series Et4-,X,Sn (X = halogen) has been shown to increase the isomer shift relative to the tetraethyltin precursor. These results were explained in terms of the relative electronegativities of the ligands, coupled with the rehybridization theory that the s-character of a central atom tends to concentrate in orbitals directed towards electropositive substituents. It was suggested that compounds of the type RSnX, should show smaller quadrupole splittings than the R,SnX species.382 A general MO model for the correlation of Mossbauer quadrupole splitting with stereochemistry has been developed and applied in detail to organotin(rv) compounds, The model, which treats the electric-field gradient at the tin nucleus as a sum of partial field-gradient tensors, was used to discuss the implications of changes in structural type and of distortions from idealized co-ordination geometry. The partial fieldgradient associated with a given ligand was shown to be different for tetrahedral, trigonal-bipyramidal-apical,trigonal-bipyramidal-equatorial, and octahedral co-ordination positions, e.g. the octahedral value is about 70% of the tetrahedral value. Absolute numerical values for partial field gradient parameters cannot be obtained from experiment and only relative values were discussed. A list of working values for a variety of ligands in tetrahedral or octahedral structures is given in Table 3. The quantity

Table 3

Working values for partialfield-gradient parameters in organotin(1v) compounds Octahedral structures Tetrahedral structures Ligand Value (mm s-l) Ligand Value (mm s- I ) Alkyl - 1.03 Alkyl - 1.37 Ph - 0.95 Ph - 1.26 1 -0.14 I -0.17 NCS MeCO, c6 F5

c6c15

CF3 u-CF~C~H, p-FC6H4

C d CO), M n(CO), WCO),

CpFdCO), HCO, snl yus

+0.21

NC S

- 0.70 - 0.83 - 0.63

MPY) DMSO PY(3 PY 1(edt)

-0.15

- 1.04 - 1.12

- 0.76

- 0.79 - 0.80 - 0.91

4 (phen)

CH,CH

4 (dipyam ) h(PiC)

+ 0.07 - 0.04

- 0.08

+ 0.01 - 0.08

-0.10 - 0.56 - 0.96 -0.17

+ 0.06

-0.18

W. E. Swartz, P. H. Watts, E. R . Lippincott, J. C. Watts, and J. E. Huheey, Inorg. Chent., 1972, 11, 2632. N. Watanabe and E. Niki, Bull. Cftem. Soc. Japan, 1972, 45, I .

Miissbauer. Spectroscopy

577

tabulated is I Q I ([L] - [XI), where X = F, C1, or Br, and the sign of Q is negative for the excited state of 110Sn.3RsQuadrupole splittings for fifty compounds calculated by use of these values agree with observed splittings to within 0.4 mm s-l or better.3Hs The signs of the quadrupole coupling constants have been shown to be positive for cis-SnCI4,2MeCN, tr.ans-SnC1,,2PEt3, and rrans-SnCI4,2AsEt3, consistent with the order of bond polarity Sn-N (sp-hybridized) > Sn-CI > Sn-P, Sn-As. The asymmetry parameter, 7,is of the order of 0.5 for each compound and suggests a distorted octahedral environment for the central tin atom.384 Spectra have been recorded for 25 complexes of the type SnX,L,, where X = C1, Br, or 1; L = R 3 P 0 (R = Et, Bu, or Ph), Ph3As0, Me,SO, Ph3As, R3P (R = Bu, Ph, or C8H,,), or PhMe,P, or La = o-PhZPC6H4, o-Me2N(C6Hp)PPh,, and [o-Me,N(C6H,)],PPh. In agreement with predictions of the point-charge model it was found that compounds which are known to have trans-structures give quadrupole splittings of approximately 1 nim s-l, whereas those with cis-structures give no resolvable splitting. A cis-configuration is suggested for SnCI4,2PPh3 on the basis of the Mossbauer spectrum, but the i.r. spectrum favours a t r a n s - s t r ~ c t u r e . ~ ~ ~ The 1 : 1 adducts of SnCI, with azines (14) and the 2 : 1 adducts with hydrazones (15) all give zero quadrupole splitting and have similar isomer shifts to each H,N-N=CHPh

Data have been given for quick-frozen solutions of SnCl, and SnI, in anhydrous (Me,N),PO, DM F, EtOAc, Me,CO, MeCN, PhNO,, (BuO),PO, Me,SO, EtOH, and CC14.3871 388 The spectrum of solid SnC1,,2DMF is identical with that of a frozen solution of SnCI, in D M F at 77 K.389 Mossbauer and vibrational spectra for the new compounds MeSnF,, MeSnCI,F, Me,SnCIF, and SnF2(S03F),indicate that they are all polymeric :i”3

:in4

3R6

387 3HH 3HU

M. G. Clark, A. G . Maddock, and R. H . Platt, J.C.S. Dalton, 1972, 281. D. Cunningham, M. J. Frazer, and J. D. Donaldson, J.C.S. Dalton, 1972, 647. P. G . Harrison, B. C. Lane, and J. J. Zuckerman, Inorg. Chem., 1972, 11, 5 3 7 . C. H. Stapfer, R. W. D’Andrea, and R. H. Herber, Inorg. Chem., 1972, 11 204. A. Vtrtes, K. Burger, and S. Nagy, Magyar. Kdm. Folydirat, 1972, 78, 476 A. VCrtes and K. Burger, J . Inorg. Nuclear Chenr., 1972, 34, 3665. W. G . Movius, J . Inorg. Nuclear Chem., 1972, 34, 3571.

578

Spectroscopic Properties of Iiiorgcrnic. uiui Orgatiometnllic Compounds

I F CI\ I

cI

/

I

"I"--M c

i~ I 0... I .:o Sn

F hie, I ,Sn-CI Me I F

,1'0

0

/

F

\

and have the repeating units shown in structures (l6)--(19). There is evidence that SnC12F2does not have a tetrahedrally co-ordinated configuration with CZVsymmetry, as suggested earlier, but the true structure of this compound is still in doubt. The signs of the electric-field gradients in these and some related compounds were deduced. For the fluorosulphate compounds Me,Sn(SO,F),, Me,Sn(SO,CF,),, Me,SnSO,F, and Me2SnCI2SO3F, and the fluorides Me,SnF,, MeSnF,, and SnF,, a plot of A as a function of the sum of the Hammett u values of the axial ligands is linear if V,, is taken to be negative. For CI,Sn(SO,F), the negative sign can also be deduced from partial quadrupole splitting considerations. By contrast, MeSnC1,F and Me,SnCIF appear to have a positive V,,, as found recently for Me,SnF.3s0 The relationship between quadrupole splitting and structure has been analysed for 37 triphenyltin compounds. The work complements two recent studies which were discussed in last year's Report. The three

structures (20)-- (22) which are possible for compounds of this type have quadrupole splittings given by the following point-charge expressions: -3[R]

A20

A,,

cc

-2[Rj

A22 a (3[RI2

+ 4[X] + 2[X]

-

6 [ R l . [XI

+ 4[XI2)*

L. E. Levchuk, J. R . Sams, and F. Aubke, Inorg. Chem., 1972, 11, 43.

Miissbnuer Specfroscopy 579 I t is concluded that triphenyltin nitrate has a structure with bridging nitrate groups and evidence is presented that the oxinate group is clielating in triphenyltin ~ x i n a t e . ~ ~ ~ The bis(triorganotin) oxides, (R,Sn),O, and the triorganotin hydroxides, R,SnOH (R = Me, Et, Pr, Bu, Oct, or Ph), have been characterized by i.r. and Mossbauer spectroscopy. The former exhibit quadrupole splittings of 1.18- 1.63 mm s - l and are therefore probably tetrahedral monomers, whereas the latter have splittings of 2.78- 2.99 mm s-I and are therefore probably co-ordinatively associated into linear polymers containing fiveco-ordinate tin, as in (23).3Q2

R H

H

I

/

I

R I i

/

-0-Sn-0-Sn-0-Sn-

R/

i

R

R/’ R

I

R /

R/’ K

The tributyltin alkoxides Bu,Sn(OR) (R = Me or Ph) have been shown to give similar quadrupole splittings and probably have a structure similar to (23) in the solid at 77 K . The compact methyl and planar phenyl groups, like hydrogen, are able to occupy the spaces between the planar R,Sn moieties. By contrast, the larger organic substituents, R = Et, Pr”, But, and CPh3, disrupt this 0-Sn co-ordination. The acyclic dialkoxides Bu,Sn(OR), (R = Me or Et) have quadrupole splittings of 2.32 and 2.00 mms-l, respectively, and are thought to be polymeric with the tin atom occupying a cis-R2SnX4 configuration (24). The quadrupole splittings for three dibutyltin 1,2-gIycoxides are slightly larger (2.72-2.85 mm Bu, Bu‘

1 ,OR

Sn

... KO,

RO‘

’OR ...

Sn’ :

Bu

‘Bu

__ R

0-Sn \

K

s-l) and are consistent with the presence of the five-co-ordinate dimer (25) in the solid state. The quadrupole splittings for four dialkyltin catechoxides are the largest so far observed for any organotin alkoxide (3.353.60 mm s-l) and are consistent with a linear polymeric structure (26) in which the tin atoms are six-co-ordinate and occupy a distorted transoctahedral R,SnX4 801

392

~3

R. C. Poller and J. N. R. Ruddick, J . Organornetulfic Chem., 1972, 39, 121. J. M . Brown, A. C. Chapman, R. Harper, D. J. Mowthorpe, A. G. Davies, and P. J. Smith, J.C.S. Dalton, 1972, 338. P. J. Smith, R. F. M . White, and L. Smith, J . Organometallic Chern., 1972, 40, 341.

K

R (76) R

-==

hlc. l i t .

t3tl.

Oct

Data have been given for eleven organostannylazoles RiSnR2 (R1 = Me, Et, or Ph; R 2 = pyrazole, imidazole, Me-2-imidazole, benzimidazole, or benzotriazole). In all cases the ratio, p, of the quadrupole splitting to the isomer shift is greater than 2 : 1 and the compounds are therefore considered to have associated structures with five-co-ordinate tin in the solid Preliminary data have been recorded for the organotin hydroxylamine derivatives Me3Sn-0- NEt,, Me,Sn- 0- NPhCOPh, PrtSn-0- NPhCOPh, Ph3Sn-0-NPhCOPh, Me3Sn-0-NHCOPh, and [NEt,H]+[Ph,Sn-O-NCOPh]-.3e5 A large number of both mono- and bis-addition compounds of dimethyland diphenyl-tin dichloride with oxygen donor molecules of the general type R,EO (E = C, N, P, or S) have been studied. The 1 : 2 adducts all have large quadrupole splittings (ca. 4.0 mm s-l), consistent with trans-R, configurations, but there are no systematic changes in the quadrupole splitting as the ligand is changed, because of the domination of the electricfield gradient by the R groups. The 1 : 2 complexes all have smaller isomer shifts than that of the parent species R2SnCI,, as a result of the increased donation into the vacant 5d orbitals of tin. The 1 : 1 adducts have quadrupole splittings which lie between those for Ph2SnC1, and the corresponding 1 : 2 a d d ~ c t s . ~ ~ ~ The methyltin(1v) fluorosulphonates Me,Sn(SO,X), (X = F, CF,, CI, Me, Et, or C,H,Me), the methyltin(1v) chlorofluorosulphonates MeCISn(S03X), (X = F or CF3), Me,CISnSO,F, and MeCl,SnSO,F have all been shown to contain only one type of tin environment and to be polymeric ( i . e . they give a room-temperature Mossbauer effect). The quadrupole 5.50 mm s-l) for Me,Sn(SO,F), and Me2Sn(S0,CF3), are splittings (A larger than any values reported previously. To account for these large values it was suggested that the bonding is highly ionic with essentially linear Me2Sn cations interacting covalently with SO,X anions. The great electronegativity of the S 0 3 X groups then leads to a strong withdrawal of p-electron density in the equatorial plane, with concomitant deshielding

-

3w*

R. Gassend, M. Delmas, J.-C. Maire, Y. Richard, and C. More, J . Organotnetollic Chem., 1972,42, C29. P. G . Harrison, J . Orgonometallic Chenr., 1972, 38, CS. B. V. Liengme, R. S. Randall, and J . R . Sams, Cnnnd. J . Chem., 1972, 50, 3212.

Miissbci N P r Spec't r o s o py 58 I of the tin 5s electrons and a resulting positive isomer shift. Simultaneously, a large imbalance develops in the p-orbital charge density on the tin atom, which results in the exceptionally large electric-field gradients. For the compounds X,Sn(SO,F), (X = Me, F, CI, Br, or SO,F), linear correlations were found between the sums of the Pauling electronegativities for the axial ligands and the isomer shifts, and between the sums of the Taft inductive constants (a*) for the axial ligands and the quadrupole splittings. The sign of the electric-field gradient is probably negative for the Me,Sn(SO,X), derivatives and positive for the Me,SnSO,X corn pound^.^^^ In an extension of this work, data were obtained for the compounds R,SnX, (R = Me, Et, Prn, Bun, or n-C8HI7;X = S 0 3 F , S0,CF3, or PO,F,), all of which have quadrupole splittings greater than 4.0mm SKI and are therefore thought to be octahedral with trans-organo groups and bidentate anionic groups bridging through oxygen. Substitution of Et for Me increases the isomer shift but decreases the quadrupole splitting; both parameters then remain almost constant for R = Pr" and Bull within each series. For a given R group, the numerical values of both the isomer shift and the quadrupole splitting decrease in the order X = SOSF, S03CF3, P02F2,F. The trends can be rationalized in terms of the ligand electronegativities and point-charge c o n ~ i d e r a t i o n s . ~ ~ ~ Moss bauer data for the dime t h y Ich 1or0t i n car boxylates Me,CI SnOOCR (R = Me, CH2CI,CHCI2, CCI,, CH,Br, CF3, C2F5,C3F7,or CF,CI) have been compared with data from compounds of known structure and it is concluded that these materials are polymeric with five-co-ordinate tin atoms. It is interesting to note that the compounds do not display a Mossbauer effect at room temperature, despite the fact that this is usually taken to be diagnostic of polymeric tin corn pound^.^^^ llsSn Mossbauer spectroscopy and i.r. techniques have been used to distinguish between open-chain and cyclic structures in some organo-tin and -lead esters for which both structures may occur. Dimethyltin(1v)phthalate (A = 3.63 mm s-l) probably has a highly distorted six-coordinate octahedral structure with trans-methyl groups, but a five-coordinate structure with equatorial methyl groups is not ruled out. The five-co-ordinate structure is favoured for the compounds o-phenylenedioxydialkyltin(1v) (alkyl = Me, Et, Bun, or Oct) and 2,2'-biphenylenedioxydimethyltin(1v) (A < 4 mm s-l). The species formed from dimethyltin(1v) carbonate in a silver chloride matrix is thought to contain equatorial methyl groups and bridging carbonato-groups in a polymeric trigonalbipyramidal structure. Dimethyltin oxalate monohydrate (A = 4.41 mm s-l) is believed to be trans-octahedral, involving bridging carboxylate groups. A sixth position is occupied by a water molecule and one ( 8

m7 nUH

P. A. Yeats, J. R. Samsand F, . Aubke, Inorg. Chern., 1972, 11, 2634. T. H. Tan, J . R. Dulziel, P. A . Yeats, J. R . Sams, R. C . Thompson, a n d F. Aubke, C(irmd.J . C h t T w . , 1972, 50, 1843. C. S. Wang and J. M . Shreeve, J . Olgotioiwltillic C'hetii., 1972, 38, 287.

582

Spectroscopic Properties of Inorgnnic arid Organornetallic Compounds

carboxylate group is bound as a n organic ester (27). All of the tin(1v) compounds have p > 2.1, which is indicative of some intermolecular coordination to the tin atom.377 From the temperature dependence of the area under the resonance curve for Me,Sn(salen), it has been concluded that the molecular unit is

monomeric with the two oxygen and two nitrogen atoms in the equatorial plane about the metal atom belonging to one (salen),- moiety (28). The absence of a Goldanskii-Karyagin asymmetry in the spectrum between 78 and 130 K is thought to reflect the severe distortion of the symmetry of the nearest-neighbour environment around the metal atom from an idealized Oh configuration. The observed quadrupole splitting (A = 3.46 mms-l) is rationalized in terms of a modified point-charge formalism which predicts a value of 13.27 I mm s-l. The quadrupole splitting of Ph,Sn(salen) (A = 2.84 mm s-l) is intermediate between those normally observed for cis-octahedral and for six-co-ordinate trans-octahedral diphenyltin(1v) compounds, and it is thought that the phenyl groups cause considerable steric distortions of the Data have been given for the adducts RPhSnCI,,2Me2S0 (R = Me, Et, Pr, Bu, or PhCH,).401 Mossbauer and i.r. spectra have been obtained for terpyridyl complexes of dimethyl-, di-n-butyl-, and diphenyl-tin di-isothiocyanates and the corresponding [R,Sn(NCS)(terpy)] [BPh4]- compounds, and for the 8-(2-pyridylmethyleneamino)quinoline complexes with di-n-butyl- and diphenyl-tin di-isothiocyanates. 1.r. spectra of the neutral complexes indicate seven-co-ordination for the tin atoms, and the Mossbauer parameters indicate the presence of axial C-Sn-C bonds with greater tin s-character than in trans-octahedral complexes. The largest quadrupole splitting (A = 4.73 mms-l) is given by the terpyridyl complex with di-nbutyltin d i - i ~ o t h i o c y a n a t e . ~ ~ ~ Data have been given for 31 compounds containing Sn-S Sn(tdt), (tdt = toluene-3,4-dithiolato) gives a large effect at room temperature and is probably polymeric with six-co-ordinate tin, whereas three other spirocyclic bis(dithio1ato)tin compounds Sn(pZdt),, Sn(p3dt),, and Sn(tdt), (p2dt = propane-l,2-dithiolato, p3dt = propane-l,3-dithiolato, +

m0 401 do2 403

R. Barbieri and R. H. Herber, J . Organometallic- Chem., 1972, 42, 65. K. L. Jaura and V. K . Verma, Indian J . Chem., 1972, 10, 536. J. C. May and C. Curran, J. Organotnetallic Chpm., 1972, 39, 289. R. C. Poller and J. N. R . Ruddick, J.C.S. Dalton, 1972, 555.

A fiissbuuer Spectroscopy 583 tdt = toluene-3,4-dithiolato), are thought to be weakly associated, with five-co-ordinate tin. Sn(SPh), does not give a room temperature effect and has zero quadrupole splitting, consistent with a simple tetrahedral structure. These tetrathiolatotin compounds all form adducts of the type SnX,Y, (X = S , Y = N or 0) with uni- and bi-dentate donor molecules and, apart from trimethylaniine oxide, the unidentate ligands give transconfigurations with quadrupole splittings of 1.77--1.95 mm s-l, whereas the bidentate ligands give cis-structures with quadrupole splittings of 0.81-1.38 mm s-l. The relationship 3rrans) 2 2A(cis) is therefore valid for compounds of the type SnX,Y, as well as for R,SnX, complexes. For the latter, the sign of V,, is predicted to be positive for the trnnsconfiguration and negative for the cis-configuration, because of the greater donor power of the organo R group compared with X. However, as a result of molecular distortions, this sign reversal has not yet been observed. For the SnX,Y, compounds, the X group is a better donor than Y and the predicted signs of VZzare negative for the trans and positive for the cis geometry. This prediction was confirmed for the cis-bipyridyl and trunsdiethyl sulphoxide adducts of bis(ethane- 1,2-dithioIato)tin by use of a 60 kG applied magnetic field. A number of monothiolatotin compounds were also studied both in the solid and in frozen pyridine solutions. Ph,Sn. S. CSH4N-4,which is five-co-ordinate in the solid, shows no increase in quadrupole splitting (A = 2.6 nim s l ) in the pyridine solution, whereas compounds such as Ph,SnSPh, which is approximately tetrahedral in the solid, shows an increase in quadrupole splitting from 1.41 in the solid to 2.39 mni s-l in the frozen solution where interaction with pyridine occurs.4o3 Single-line Mossbauer spectra have been observed for a number of (3-tria1kylstannyl)propyl aryl sulphides of the type RiSnCH,CH,CH,SR2 (R1 = Me, Et, or Bu; R2 = Fh or p-tolyl), which confirnis that these compounds are formed by the addition of the arenethiol to the allyltrial kyltin compound in preference to cleavage. Typical compounds which would have been formed by cleavagc, c . g . Bu,SnSPh and Bu,SnSC,H,Me-p, give well-resolved quadrupole-doublet ~pectra."~ The spectrum of (BrCH,),SnO is characteristic of R,SnO-type compounds and rules out alternative formulations such as (HOCH,),SnBr,. The infusible white solid bis(phenylthiomethy1)tin oxide, (PhSCH,),SnO, gives a resonance effect at room temperature and is thought to be polymeric. Treatment of the latter with acetic acid does not give the diacetate; instead, the (phenylthiomethy1)stannoxane acetate, [PhSCH2Sn(0)OCOMe],, is obtained. Data were also given for (PhSCH,),Sn, (BuSCH,),Sn, Bu,SnCH,Ph, [PhSCH,Sn(O)OCOMe],, [PhSn(O)OCOCMe,],, (PhSCH,),SnO, and (BrCH2)2Sn0.405 4n4

G . Ayrey, R . D. Brasington, and R. C . Pollcr, J . Orgnnonirtallic Cheni., 1972, 35, 105. R. D. Brasington and R. C. PolIer, J . Orgarioniefollic Chern., 1972, 40,115.

584

Spectroscopic Properties of’ Inorgarlic rrnd Organometallic Cornpowids

The monoalkyltin orthosulphites (29) have all been shown to give similar spectra and are thought to be isostructural. There are small differences in isomer shift and quadrupole splitting, which are attributed to steric and bonding effects of the groups X, and these indicate that the electron-withdrawing power of the OX groups decreases along the series SO,(C,H,)Me > OCOMe > OS03H > OH. The results for these compounds were compared with data for the oxy-bridged polymers (30) both

of which show quadrupole splittings which are significantly smaller than the values for (29). The difference is attributed to a change in stereochemistry due to the fact that the polymers have a less restrictive geometry than that imposed by the four-membered 0-Sn-0 ring in (29), rather than to differences in electron donor-acceptor properties of the 0-bridged moiety compared with the SO,-bridged group, because the isomer shifts for the two sets of compounds are very similar. Data were also given for (31).,06 Possible structures have been suggested for various mono-organotincompounds on the basis of quadrupole splitting data.407 The sesquisulphides (RSnSl.,)p (R = Me, Et, Bu, C8H17n,or Ph) all give similar data,

R I

Bun Bu” I I -Sn- S -SnI I SH SH (31)

suggesting that they are isostructural with the methyl compound which i s known to have structure (32). They appear to be one of the few classes of organotin(1v) compounds which are tetrahedral and unassociated in the solid state. The quadrupole splittings are small (1.2--1.5 mm s-I), as expected for a tetrahedral RSnX, structure. The values observed for the species RSnCl, lie in the range 1.8-2.0 mm s-l, and are inconclusive in differentiating between tetrahedral and associated five-co-ordinate structures. The organostannoic acids [RSn(O)OH], give splittings of 1.29.1.83 mm s-l, which are consistent with structures, of the type (33) and (34), containing tetrahedral tin, but do not exclude the possibility of association. C . H. Stapfer and R. H . Herber, J . Orgntioniefallic Chern., 1972, 35, 1 1 I . A. G . Davies, L. Smith, and P. J . Smith, J . Orgnnomefallic Chem., 1972, 39, 279.

M iissbci rr er Spec t ros copj'

5 85

HO(33)

(34)

The quadrupole splitting ( I . 18 mm s- l ) for PhSn(OR'), is very similar to that of the sesquisulphide (32), indicating that the tin atom is probably tetrahedral also. By contrast, the alkyltin trialkoxides R1Sn(OR2),,(R' = Et, Bu, or n-C,H,,) have values between 1.9 and 2.0 mm s-' and to account Sn for this increase it is suggested that the tin is five-co-ordinate with a N interaction of the type shown in (35).,07 7

K l

l19Sn spectra have been obtained (X = Cl, Br, or I) and for cis- and There is no evidence in the spectra lar bridging of the types shown in

for the compounds cis-[Fe(CO),XSnX,] ~rans-[Fe(CO),(SnX,),] (X = CI or Br). of the latter complexes for intermolecustructures (36) and (37). CI,

Sn

,CI

(OC),F-k

\ Id

CI

,sn

'CI

The electric-field gradient tensor at the tin atom in [(Fe(rr-C,H,)(CO),),SnCI,] has been studied in detail by application of a 50 k G magnetic field at 4.2 K and by use of an oriented matrix of single crystals i n a zero-field experiment at 78 K.,OR The magnetically perturbed spectrum is shown in Figure 32, together with a series of spectra simulated for a positive e2qQ (negative Vzz) and various values of the asymmetry parameter, 7. The result, 7 = 0.65 +_ 0.05, constitutes the first determination of the asymmetry parameter at a tin atom. The molecular geometry at the tin is shown in Figure 33: the FeSnFe plane is perpendicular to the ClSnCl plane and consideration of the general electric-field gradient tensor for this geometry reveals that two of the principal axes, arbitrarily labelled i andj, lie in these 408

T. C . Gibb, R. Greatrex, and N. N. Greenwood, J . C . S . Dalton, 1972, 238.

586

Spectso.scopic Properties of' Itiorgatiic cind Organonietallic Comporinds

planes as shown. Evaluation of the principal values of the EFG i n the light of the known crystal structure then yields the equations: V , , = -0.8714[Fe]

V J j = -2[Fe] Vkk

J

+

+ 0.7858[C1]

1.2142[C1]

= + 2 . 8 7 1 4 [ F ~ ]- 2[C1]

I

- 6 - 1 - 2

I

1 V c I o c i t y / [ m m I-') 0

2

l

6

l

I

Figure 32 The Miissbauer spectrum of [{Fe(rr-C,H,)(CO),},SnC12] uf 4.2 K nvith a magnetic field of 50 kG applied perpendicular to the direction of obseroation. The solid curves are computed spectra for a range of values of the asyninietry parameter 7. The experimentally determined value is q = 0.65 k 0.05

in which [Fe] and [CI] refer to the expectation values of - e < $ I ( 3 cos2B l ) r 3 1 $) for the Sn-Fe and Sn-CI bonds, respectively. Numerical evaluation of these equations in the range 0 < R < 00, where R = [Fe]/[CI], reveals that the direction of V,, depends on the ratio R as shown in Figure 34 and can adopt any of the three axes. The sign of Y,, also alters and shows a complex behaviour. The experimentally determined negative c i n n nf

V

olirningtoc

throe nf tho

ciu

nnccihlp

w i 1 1 1 o c fnr

TEnlITPll - - A

restricts the direction of V,, to either the i or k axis. The results of the single-crystal experiment finalIy remove this ambiguity and indicate that

Miissbaiter Spectroscopy

i

a-

Figure 33 The molecular geometry of the SnFe,CI, unit in [{Fe(n-C,H,)(CO),},SnCI,] and the two possible orientations in the crystal unit cell

V,, is directed along Vkk, at 48" to the bc plane of the crystal. It then follows from Figure 34 that [Fe]/[CI] = 1.2 k 0.1, which shows conclusively that the value of < r - 9 is greater for the Sn-Fe bond than for the Sn-Cl bond and that there is therefore less withdrawal of tin 5p-electron density into the Sn-Fe bonds than into the Sn-Cl bonds.*O*

I

--x2-

I = [Fell (CI1

Figure 34 The dependence of the asymmetry parameter 77 and the arbitrarily normalized value of V,, which is denoted by ' Vzz' on R = [FeJ/[CI]. Note the expanded horizorital scale iit the centre

588

Spcctt.o.sc'opic Ptwpc~rtic~s of' I i i o r g u t i i c trnd 0rg.Ktrnonietnllic Compound,r

There have been several, more general studies of the ll9Sn quadrupole splitting in four-co-ordinate tin compounds containing tin-transition-metal For example, data have been given for the low-symmetry four co-ordinate organotin compounds [ M n(CO),Sn Me,-,CI .] and [Fe(.rr-C, H5)(CO),SnPh, ,Cl,,] (n = C k 3 ) . For n = 1 and 2 the quadrupole splittings are much larger than those for n = 0 and 3 and are beyond the range commonly associated with four-co-ordinate tin. These observations can be rationalized on the basis of the point-charge model, using self-consistent partial quadrupole splitting values, provided account is taken of distortions of the bond angles from the purely tetrahedral value.4o9Similar arguments have been used elsewhere to rationalize the trends in the quadrupole splitting and asymmetry parameter for the series [Mn(CO),SnR,. ,,X,] (R = Me or Ph; X = C1 or Br; n = 0---3).410 In a more comprehensive study, the partial quadrupole splitting values for Ph, R (Me, Et, etc.), and X (F, C1, Br), listed on p. 576, have been used to enable predictions to be made of the magnitudes of the quadrupole splitting and the asymmetry parameter and of the signs of e24Q for forty compounds containing Sn-Fe or Sn-Mn bonds. With only four exceptions the predicted values agree with the observed values to within 0.4 mm s-1 and the predicted signs agree with the known signs and with those determined for Me,CISnMn(CO), ( - ve) and MeCI,SnMn(CO), ( + ve). The predicted values of r ) for these two complexes are 0.41 and 0.89, respectively, compared with the experimental values of 0.35 and 0.46. The poor agreement in the second case may well reflect the fact that 7 is very sensitive to variations in the partial quadrupole-splitting values. The quadrupole splitting is much less sensitive. New partial quadrupole splittings were derived for C6F, ( - 0.76), Mn(CO)S ( - 0.97), and Fe(7r-C5H,)(CO), ( - 1.08). The centre shifts for compounds of the type MSnR,-,X, [M = Mn(CO), or Fe(7r-C5H5)(C0),; R = Me or Ph; X = CI, Br, or C6F5] increase as n increases, Owing to the concentration of s-electron density in the Sn-M bond and the high p character in the Sn-X bonds. The s character in the Sn-L bonds increases in the order and L = CI, Br < C6F, < Ph < Me < Mn(CO), < F ~ ( T - C ~ H ~ ) ( C O )~, this series can be used to rationalize the known distortions about the tin ato in. l 1 The nature of the tin-manganese bond in the series of compounds [{Mn(CO),),SnR,-,I ( n = 1, R = CI, Br, I , Et, or Ph; n = 2, R = CI, Br, or Ph), [Mn(CO),SnR,._,X,] (n = 1 or 2 ; X = CI, Br, or I ; R = Ph), and rrans-[Mn(CO),PPh,SnR,] (R = C1 or Ph) has also been discussed. The importance of the tin-manganese bond in determining the values of the isomer shift and quadrupole parameters was emphasized.412 The 409

410 411

41L

G. M. Bancroft, K . D. Butler, and A . T. Rake. J . Orgnnometnllic Cltetn., 1972, 34, 137. V. B. Licngiiic, J . R. Sams, and J . C. Scott, Brill. Clietn. Soc. Jupntt, 1972, 45, 2956. G . M. Bancroft, K . D. Butler, A . T. Rake, and B. Dale, J . C . S . Dciltotr, 1972, 2025. S. R . A. Bird, J . D. Donaldson, A . F. Le c'. Holding, B. Ratcliff, and S. Ccnini, Irrorg. Cltitti. Acfn, 1972, 6,379.

hliisshnrrcr. Spectrmcopj-

589

quadrupole splitting decreases from 0.61 nit11 s to zero when the carbonyl group t m i w - to the tin atom i n [Mn(CO),SnMe,] is replaced by a ligand of weaker Ir-accepting ability ( e . g . PPh, or AsPh,); this has been attributed to a long-range effect through the n-electrons of the manganese atom and the 5d orbitals of tin. The complete absence of quadrupole splitting in the analogous Ph compounds is attributed to the predominant n-delocalization effect of the phenyl groups attached to the tin atom.413 The isomer shifts for the series [Co(CO),l,-,SnX, (X = Cl, Br, or I, n = 0-4) have been shown to increase non-linearly as the halogens are successively replaced by Co(CO), groups, the change in isomer shift becoming smaller as n decreases. The quadrupole splittings are smaller than those of the corresponding organotin halides and are a maximum for n = 2. The results may be summarized by Bent's rule, which suggests that the s-character is concentrated in the orbitals directed toward the more electropositive substituents, in this case in the Sn-Co bonds, while the p-character is concentrated in the Sn-X bonds. This results in Co-Sn-Co angles which are greater than 109" 28' and X-Sn-X angles which are less than this value.414 From the temperature dependence of the recoil-free fraction and the Goldanskii-Karyagin asymmetry (zero in this case) of the quadrupole splitting in Me2Sn(S2CNEt2)2,it has been concluded that the compound is monomeric with an essentially isotropic amplitude of vibration for the central tin atom in the temperature range 78-150 K . The latter is perhaps surprising in view of the anisobidentate nature of the dithiocarbamate moieties in this complex. I t is also surprising that the tetrakis(dimethy1- and diethyl-dithiocarbamate) complexes give no resolvable quadrupole splitting, despite the fact that they have been shown by X-ray crystallography to contain tin in a distorted octahedral ligand configuration, involving two isobidentate and two unidentate ligands. From isomer shift electronegativity systematics, a group electronegativity of 5.7 (on the MullikenJaffe scale) was deduced for alkyl groups bonded to t i n ( ~ v ) . ~ l ~ Data have been reported for twelve chloro-(NN-dia1kyldithiocarbamato)diorganostannanes RiSnCI(S,CNR;) [R' = Me, Bu, or Ph; R2 = Me, Et, CH,Ph, or (CH2)J. The alkyl derivatives have quadrupole splittings in the range 2.72-3.14 mm s-l and the phenyl derivatives, 2.19-2.34 mm s-l. The isomer shifts show less variation and fall in the narrow range 1.081.45 mm s-l. Comparison of the above A-values with theoretical quadrupole splittings calculated from partial field gradients led to the conclusion that these compounds contain unidentate dithiocarbamato-groups in an essentially tetrahedral stereochemis try. 416 The ll9Sn spectrum of cubanite, Cu,FeSnS,, at 4.2 K is magnetically broadened and indicates a transferred hyperfine field of about 20 kG at the 113

414 416 110

S. Onaka and H . Sano, Bull. Chern. SOC.Jupun, 1972, 45, 1271. S. Ichiba, M . Katada, and H . Negita, Bull. Chenr. SOC.Japan, 1972, 45, 1679. J. L. K . F. de Vries and R. H . Herber, Inorg. Chenr.. 1972, 11, 2458. B. W. Fitzsimnions and A. C. Sawbridge, J . C . S . Dalton, 1972, 1678.

590

Spectroscopic Properties of Inorganic and Organometallic Compoiinds

tin nucleus. The 5iFe spectrum of this compound is discussed on p. 566.:34R Spectra have also been obtained for the compounds SnP, Sn,P,, Sn,P,, SnAs, Sn,As3, Sn,As,, and SnSb,,17 and for alloys of the As-S-Sn, P-S-Sn, and P-Se-Sn Glasses in the As-Se-Ge-Sn system ,lg and sodium-tin silicate glasses 420 have also been studied.

6 Other Elements This section covers elements other than iron and tin. In each of the three sub-sections - main group elements, transition elements, and lanthanide and actinide elements - the isotopes are treated in order of increasing atomic number. It has been shown, by careful analysis of the lineshapes for fourteen different Mossbauer transitions, that dispersion terms are clearly present in absorption spectra of y-rays with E2 or mixed E2/M1 character. The dispersion terms are caused by interference effects between conversion electrons, emitted after resonance absorption, and photoelectrons. It was pointed out that this fact has to be taken into account whenever the positions of such absorption lines need to be measured with great accuracy. The fourteen transitions studied were Q 9 R (90 ~ keV), lssEr (80.6 keV), 170Yb (84.3 keV), 171Yb (66.7 keV), leoHf (93.3 keV), lezW (100.01 keV), la3W(46.5 and 99.1 keV), la4W(111.1 keV), laaW(122.5 keV), lseOs (137.2 keV), lasOs (155.0 keV), lglIr (129.5 keV), and 236U(45.3 keV).,,l

Main Group Elements.-Germanium (73Ge). The Mossbauer effect for the 13.3 keV, @++ Q + , E2 transition in 73Ge has been detected for the first time in single crystals of germanium. The source consisted of ',Ga in a germanium lattice, and was produced by the photonuclear reaction 74Ge(y,p)73Ga. Scattering geometry was employed to detect the 9.89 keV germanium internal conversion X-rays, thereby avoiding the problem of the very high conversion coefficient. Spectra obtained for an Sb-doped n-type crystal of germanium contain both a singlet and a quadrupole multiplet from 73Gein tetrahedral and hexagonal interstitial sites, respectively. The best fits to the data yield values of I QalQp 1 = 0.25 and I q I = 1.3 x 10ls c.g.s. for the quadrupole moment ratio and electric-field gradient, respectively. The latter agrees well with the value of 1.5 x lolo, estimated by substituting the spectroscopically determined quantity < r - 9 = 38.8 x loz4~ r n into - ~ the equation I q I = ($)e

Spectroscopic Properties of Inorganic and Organometallic Compounds: v. 6: A Review of Chemical Literature (Specialist Periodical Reports)

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

Spectroscopic Properties of Inorganic and Organometallic Compounds

Inorganic Chemistry of the Transition Elements: v. 4: A Review of Chemical Literature (Specialist Periodical Reports)

Inorganic Chemistry of the Transition Elements: v. 3: A Review of Chemical Literature (Specialist Periodical Reports)

The Alkaloids: A Review of Chemical Literature: v. 6 (Specialist Periodical Reports)

Spectroscopic Properties of Inorganic and Organometallic Compounds Volume 37

Spect Properties inorganic & Organometallic Cmpds, Vol 17 (Spectroscopic Properties of Inorganic and Organometallic Compounds)

Gas Kinetics and Energy Transfer: v.4: A Review of Chemical Literature (Specialist Periodical Reports)

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Electrochemistry: v.8: A Review of Chemical Literature (Specialist Periodical Reports) (Vol 8)

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Organometallic Chemistry, Volume 36 (Specialist Periodical Reports)

Organometallic Chemistry, Volume 31 (Specialist Periodical Reports)

Spectroscopic Properties of Inorganic and Organometallic Compounds vol.38 A Review of the Literature up to Late 2004

Dielectric and Related Molecular Processes, Vol. 1: A Review of Chemical Literature (Specialist Periodical Reports)

Catalysis: v. 18 (Specialist Periodical Reports)

Organosphophorus Chemistry (Specialist Periodical Reports) (v. 4)

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Chemical Modelling: Vol. 2: Applications and Theory (Specialist Periodical Reports)

Physical Properties of Chemical Compounds

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Inorganic Chemistry of the Transition Elements, Volume 2 (Specialist Periodical Reports) (v. 2)

Inorganic Chemistry of the Main-group Elements: v. 4 (Specialist Periodical Reports)

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Inorganic Compounds with Unusual Properties

Spectroscopic Properties of Inorganic and Organometallic Compounds: v. 6: A Review of Chemical Literature (Specialist Periodical Reports)

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