Spect Properties inorganic & Organometallic Cmpds, Vol 17 (Spectroscopic Properties of Inorganic and Organometallic Compounds)

Spectroscopic Properties of Inorganic and Organometallic Compounds Volume 17 A Specialist Periodical Report Spectros...

Author: G. Davidson | E. A. V. Ebsworth

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Spectroscopic Properties of Inorganic and Organometallic Compounds Volume 17

A Specialist Periodical Report

Spectroscopic Properties of Inorganic and Organometallic Compounds Volume 17

A Review of the Recent Literature Published up to Late 1983

Senior Reporters G. Davidson, Department of Chemistry, University of Nottingham E. A. V. Ebsworth, F.R.S.E., Department of Chemistry, University of Edinburgh Reporters S. J. Clark, City University, London S. Cradock, University of Edinburgh K. B. Dillon, University of Durham J. D. Donaldson, City University, London S. M. Grimes, City University, London B. E. Mann, University of Sheffield D. W. H. Rankin, University of Edinburgh H. E. Robertson, University of Edinburgh

The Royal Society of Chemistry Burlington House, London W I V OBN

ISBN 0-85186-153-9 ISSN 0584-8555

Copyright 0 1985 The Royal Society of Chemistry

All Rights Reserved No part of this book may be reproduced or transmitted in any form or by any means-graphic, electronic, including photocopying, recording, taping, or information storage and retrieval systems-without written permission from The Royal Society of Chemistry Typeset by Bath Typesetting Ltd., Bath, and printed by J. W. Arrowsmith, Bristol, England

Foreword

This volume follows the form of its recent predecessors; there are no new sections, and the general coverage remains the same. Despite the steady increase in the amount of published work, the reviewers have done wonders in controlling the size of their contributions, and as ever I am extremely grateful to them for their prompt and careful work. The next volume will be produced from cameraready copy; I hope that this will lead to a reduced price and to quicker publication. November 1984

E. A. V. EBSWORTH

Contents

Chapter 1

Nuclear Magnetic Resonance Spectroscopy By B. E. Mann

1 Introduction

1

2 Stereochemistry Complexes of Groups IA and IIA Complexes of Groups IIIA and IVA, the Lanthanides, and Actinides Complexes of V, Nb, and Ta Complexes of Cr, Mo, and W Complexes of Mn, Tc, and Re Complexes of Fe, Ru, and 0 s Complexes of Co, Rh, and Ir Complexes of Ni, Pd, and Pt Complexes of Cu, Ag, and Au Complexes of Zn, Cd, and Hg

2 2

3 Dynamic Systems Fluxional Molecules Lithium Uranium Titanium and Zirconium Vanadium Niobium and Tantalum Chromium, Molybdenum, and Tungsten Manganese and Rhenium Iron, Ruthenium, and Osmium Cobalt, Rhodium, and Iridium Nickel, Palladium, and Platinum Copper Silver Gold Boron

4 6

7 17 20 29 38 49 50

53 53 53 53 53 54 54 54 56 57 59

60 63 63 63 63

Silicon, Germanium, and Tin Phosphorus Antimony Sulphur Selenium Equilibria Solvation Studies of Ions Group IA Scandium and the lanthanides Uranium Chromium Manganese Iron, cobalt, and nickel Copper Zinc Boron Aluminium Thallium Nitrogen Oxygen Fluorine Ionic Equilibria Group IA Group IIA The lanthanides Titanium Vanadium, niobium, and tantalum Chromium Tungsten Manganese Iron Cobalt Rhodium Nickel, palladium, and platinum Copper Silver Gold Zinc Mercury Boron, aluminium, gallium, and indium Thallium Carbon Lead Nitrogen Phosphorus Arsenic Bismuth

63 64 65 65 65 65 65 65 66 67 67 67 67 68 68 68 68 68 68 68 68 68 68 71 72 73 73 73 73 73 73 74 74 75 75 76 76 77

77 77 78 78 78 78 78 79 79

Fluorine Chlorine Equilibria among Uncharged Species Magnesium Lutetium Uranium Titanium Zirconium Thorium Chromium Molybdenum Tungsten Manganese Iron Cobalt Rhodium Nickel Palladium Platinum Copper Zinc Cadmium Mercury

Boron Silicon Tin Phosphorus Course of Reactions Calcium Titanium Zirconium Molybdenum Tungsten Manganese and Rhenium Iron Ruthenium Cobalt Rhodium Iridium Nickel Palladium Platinum Gold Cadmium Boron Aluminium Carbon

79 79 79

79 79

79 79 79 79 79 79 80 80 80 80 80 80 81 81 81 81 81 81 81 81 81 82 82 82 82 82 82 83 83 83 84 84 84

84 85 85 85 85 85 85 86 86

Silicon Tin Phosphorus 4 Paramagnetic Complexes The Transition Metals Vanadium Molybdenum and Tungsten Manganese and Rhenium Iron, Ruthenium, and Osmium Cobalt Nickel Copper Compounds of the Lanthanides and Actinides Lanthanides Actinides

86 86 86 87 88 88 88 88 88 90

90 91 91 91 92

5 Solid-state N.M.R. Spectroscopy Motion in Solids Structure of Solids Molecules Sorbed onto Solids Water Sorbed onto Solids Atoms and Other Molecules Sorbed onto Solids

93 94 99 115 115 116

6 Group IIIB Compounds

118 119 120 123

Boron Hydrides and Carbaboranes Other Compounds of Boron Complexes of Other Group IIIB Elements 7 Group IVB Elements

124

8 Compounds of Group VB Elements

133

9 Compounds of Groups M and VII and Xenon

147

10 Appendix

Chapter 2

149

Nuclear Quadrupole Resonance Spectroscopy By K. B. Dillon 1 Introduction

155

2 Main-group Elements Deuterium Group I (Sodium-23 and Rubidium-85 and -87)

155 155 156

Group I11 (Boron-10 and -11, Aluminium-27, Gallium69 and -71, and Indium-115) Group V (Nitrogen-14, Arsenic-75, Antimony-121 and -123, and Bismuth-209) Group VI (Oxygen-17) Group VII (Chlorine-35 and -37, Bromine-79 and -81, and Iodine-127) 3 Transition Metals and Lanthanides Copper-63 and -65 Praseodymium-141 Tantalum-18 1 Rhenium-185 and -187

Chapter 3

Chapter 4

156 158 162 163 171 171 172 172 172

Rotational Spectroscopy By S. Cradock 1 Introduction

173

2 van der Waals and Hydrogen-bonded Complexes

173

3 Diatomic Species

175

4 Triatomic Molecules and Ions

178

5 Tetra-atomic Molecules

180

6 Penta-atomic Molecules

181

7 Molecules with Six or More Atoms

182

Characteristic Vibrations of Compounds of Main-group Elements By S. Cradock 1 Group1

184

2 GroupII

184

3 GroupIII Boron Aluminium Gallium and Indium Thallium

185 185 186 187 188

4 GroupIV Carbon Si1icon Germanium Tin Lead

189 189 189 192 192 194

5 Group V Nitrogen Phosphorus Arsenic Antimony Bismuth

195 195 196 198 199 200

6 GroupVI Oxygen Sulphur, Selenium, and Tellurium Ring and Chain Species Sulphur-Nitrogen Compounds Other Sulphur and Selenium Compounds Tellurium

200 200

7 Group VII

204

8 Group VIII

205

Chapter 5

201 201 202 203

Vibrational Spectra of Transition-element Compounds By G. Davidson

1 Introduction

206

2 Detailed Studies

206

3 Resonance Raman Spectra

208

4 Scandium, Yttrium, and the Lanthanoids

210

5 Titanium, Zirconium, and Hafnium

211

6 Vanadium, Niobium, and Tantalum

213

7 Chromium, Molybdenum, and Tungsten

215

8 Manganese, Technetium, and Rhenium

219

9 Iron, Ruthenium, and Osmium

220

10 Cobalt, Rhodium, and Iridium

223

11 Nickel, Palladium, and Platinum

226

12 Copper, Silver, and Gold

228

13 Zinc, Cadmium, and Mercury

230

14 The Actinoids

232

Chapter 6

Vibrational Spectra of Some Co-ordinated Ligands By G. Davidson 1 Carbon and Tin Donors

234

2 Carbonyl, Thiocarbonyl, and Selenocarbonyl Complexes

243

3 Boron-containingDonors

25 1

4 Nitrogen Donors Molecular Nitrogen, Azido, and Related Complexes Amines and Related Ligands Ligands Containing C=N- Groups Cyanides, Isocyanides, and Related Ligands Nitrosyls and Thionitrosyls

252 252 255 256 258 261

5

Phosphorus Donors

6 Oxygen Donors

Molecular Oxygen, Peroxo, Aquo, and Related Complexes Acetylacetonates and Related Complexes Carbonato and Carboxylato Complexes Keto, Alkoxy, Ether, and Related Complexes Ligands Containing 0-N or 0-P Bonds ,Ligands Containing 0-S or 0-Se Bonds Ligands Containing 0-C1 Bonds

263

265 265 26’7 269 271 272 274 275

7 Sulphur and Selenium Donors

276

8 Potentially Ambident Ligands Cyanates, Thiocyanates, Selenocyanates, and Their Is0 Analogues Ligands Containing N and 0 Donor Atoms Ligands Containing N and S Donor Atoms Ligands Containing S or Se and 0 Donor Atoms

278 278 280 283 284

Chapter 7

Mossbauer Spectroscopy By J. 0 . Donaldson, S. J. Clark, and S. M. Grimes

1 Introduction Books and Reviews

286 286

2 Theoretical

288

3 Instrumentation and Methodology

292

4 Iron

296 296 296 297 300 301 301 302 305 305 308 308 3 10 314 314 315 3 17 318 319 320 321 321 322 323 323 324

General Topics General and Metallic Iron Frozen Solutions and Matrix Isolation Emission Studies Compounds of Iron High-spin Iron@) Compounds High-Spin Iron@) Compounds Intercalation Compounds Containing Iron Low-spin and Covalent Compounds Mixed-valence and Unusual Electronic States Spin-crossover Systems and Unusual Spin States Biological Systems and Related Compounds Oxide and Chalcogenide Systems Containing Iron Simple Oxides and Hydroxides Spinels and Related Oxides Other Oxides Inorganic Oxide Glasses Containing Iron Minerals Chalcogenides Applications of 67FeMossbauer Spectroscopy Corrosion Studies and Steel Iron-containing Catalysts Coal and Related Topics Ores, Slags, Soils, and Sediments Other Applications 5 Ti-119

General Topics Tin@) Compounds Inorganic Tin(W) Compounds Organotin(1V) Compounds 6 Other Elements

Main-group Elements Germanium Antimony

325 325 329 333 336 343 343 343 343

Tellurium Iodine Caesium Transition-metal Elements Nickel Zinc Tantalum Osmium Iridium Gold Lanthanide and Actinide Elements Samarium Europium Gadolinium Dysprosium Erbium Thulium Ytterbium Neptunium Americium

346 348 352 352 352 352 353 354 354 354 359 359 359 363 363 365 365 366 367 368

7 Back-scatter and Conversion-electron MasSbauer SpectrOSCOPY

Iron Films Steels Implantation Studies Chemical Reactions Other Elements Chapter 8

368 370 370 372 374 376 378

Gas-phase Molecular Structures Determined by Electron Diffraction By D. W. H. Rankin and H. E. Robertson 1 Introduction

381

2 Compounds of Main-group I Elements

383

3 Compounds of Main-group 111 Elements

384

4 Compounds of Main-group IV Elements

384

5 Compounds of Main-group V Elements

387

6 Compounds of Main-group VI Elements

390

7 Compounds of Main-group MI Elements

393

8 Transition-metal Compounds

393

Conversion Factors

1 kJ mo1-1 2.3901 1.0364 8.3593 2.5061

1 kcal mol-l

x 10-l kcal mol-l x eV atom-' x 10 cm-l x lo6 MHz

4.1840 kJ mol-I 4.3364 x lov2eV atom-l 3.4976 x lo2 cm-l 1.0486 x lo7 MHz

1 cm-1

1.1963 2.8592 1.2399 2.9979

x x x x lo4

1 MHz

kJmol-l kcal mo1-l eV atom-l MHz

3.9903 9.5370 4.1357 3.3356

x lo-' kJmol-' x kcal mol-l x eV atom-l x 10-5cm-1

1 eV atom-'

9.6485 2.3060 8.0655 2.4180

x x x x

10 kJ mol-l 10 kcal mol-1 lO3crn-l lo8 MHz

Mossbauer Spectra: E,(57Fe) = 14.413 keV 1 mm s-J

4.639 1.109 4.808 3.878 1.162

x kJ mol-1 x kcal mol-l x eV atom-l x cm-' x 10 MHz

For other Mossbauer nuclides, multiply the above conversion factors by E,(keV)/ 14.4 13

1 Nuclear Magnetic Resonance Spectroscopy BY B. E. MANN

1 Introduction

Following the criteria established in earlier volumes, only books and reviews directly relevant to this chapter are included, and the reader who requires a complete list is referred to the Specialist Periodical Reports ‘Nuclear Magnetic Resonance’,l where a complete list of books and reviews is given. Reviews which are of direct relevance to a section of this Report are included in the beginning of that section rather than here. Papers where only lH n.m.r. spectroscopy is used are only included when the lH n.m.r. spectra make a non-routine contribution, but complete coverage of relevant papers is still attempted where nuclei other than the proton are involved. Several reviews have appeared, including ‘Physical methods and techniques. Part (ii). N.m.r. spectroscopy’,2 ‘High resolution multinuclear magnetic resonance: instrumentation requirements and detection procedure^',^ ‘Transition metal n.m.r. spectro~copy’,~ ‘Nuclear magnetic resonance studies in cluster ~hemistry’,~ ‘Magnetic resonance of oxidised metalloporphyrins’,6 ‘Methods to analyze metal-protein binding. Multinuclear n.m.r. studies of metal lop rote in^',^ ‘Nuclear magnetic resonance of calcium-binding proteins’, ‘N.m.r. and e.p.r. investigations of bimetal lo enzyme^',^ and ‘N.m.r. and e.p.r. studies of chromium and cobalt nucleotides and their interactions with enzymes’.lO A number of papers have been published which are too broadly based to fit into a later section and are included here. The nuclear magnetic shielding function for H2 has been extracted from spin-rotation and isotope-shift data.ll lJ(13C,13C) l

‘Nuclear Magnetic Resonance’, ed. R. J. Abraham (Specialist Periodical Reports), The Royal Society of Chemistry, London, 1983, Vol. 12; 1984, Vol. 13. R. F. M. White, Annu. Rep. Prog. Chem., Sect. B 1982, 1981, 78, 15. C. Brevard, NATO ASI Ser., Ser. C, 1983, 103, 1 (Chem. Abstr., 1983, 99, 132 383). R. G. Kidd, NATO ASI Ser., Ser. C, 1983, 103, 445 (Chem. Abstr., 1983, 99, 132 402). B. T. Heaton, Philos. Trans. R . SOC.London, Ser. A , 1982, 308, 95. H. M. Goff, M. A. Phillippi, A. D. Boersma, and A. P. Hansen, Adv. Chem. Ser., 1982, 201, 357 (Chem. Abstr., 1983, 98, 67 206). Y. Arata and T. Sawatari. Tanpakushitsu Kakusan Koso, Bessatsu, 1983,74 (Chem. Abstr., 1983, 99, 172 101).

@

Y. Shibata and T. Miyazawa, Tanpakushitsu Kakusan Koso, 1982,27,2226 (Chem. Abstr., 1983, 98, 29 719). J. J. Villafranca and F. M. Raushel, Adv. Inorg. Biochem., 1982, 4, 289 (Chem. Absfr., 1983, 98, 175 332).

lo

J. J. Villafranca, Methods Enzymol., 1982, 87, 180 (Chem. Abstr., 1983, 98, 13 374). W. T. Raynes and N. Panteli, Mol. Phys., 1983, 48, 439.

1

2

Spectroscopic Properties of Inorganic and Organometallic Compounds

and lJ(M,13C) have been reported for 27 organometallic derivatives of alkanes, alkenes, benzene, and alkynes (M = B, Sn, Pb, Hg, or Bi).12 The spin-lattice relaxation times of 170at 54.25 MHz have been found to range from 8 to 50 ms for several metallocarbonyls, and a stereochemical dependence has been found.13 Spin-lattice relaxation times of 35S, 51V, 53Cr,and 55Mnin tetrahedral oxoanions have been determined in aqueous s01ution.l~The temperature dependence of TI of [MO,]"- (M = C1, Br, Mn, Cr, V, Mo, Tc, Re, or Ru) has been determined, and for [MnO,]-, [V0413-, RuO,, and [TcO,]- a minimum was found.15 15N n.m.r. spectra of transition-metal nitrosyl complexes have been reported, and for MNO angles near 120" the nitrogen atom is strongly deshielded relative to linear MNO c o m p l e x e ~ . ~Deshieldings ~J~ of 350-700 p.p.m. have been observed in the 15Nn.m.r. spectra of strongly bent nitrosyl groups.l* A model of the interaction of metal ions with the phosphate group, based on 31Pn.m.r. studies, has been described.lg The interaction of metals with N,N,N',N'-tetrabutyl-3,6-dioxaoctanedithioamidehas been investigated using 13C, l13Cd, lQ5Pt, and lQQHg n.m.r. spectroscopy.20A sensitive 13Cn.m.r. shift thermometer using Dy3+ in acetate buffer has been described.21 The effect of cation on [MF6l2(M = Si, Ge, or Sn) Tl has been examined by 19Fn.m.r. spectroscopy.22

2 Stereochemistry This section is subdivided into ten parts which contain n.m.r. information about Groups IA and IIA and transition-metal complexes presented by Groups according to the Periodic Table. Within each Group, classification is by ligand type.

Complexes of Groups IA and 1IA.-Two reviews have appeared: 'N.m.r. of the alkali and 'N.m.r. of the alkaline earth The degree of aggregation in solution of organolithium derivatives has been correlated with the multiplicities of the signals due to 1J(13C,6Li).25 The structures of monosilylated pentadienyl-lithium and 1,5-disilylated pentadienyl-lithium, la B.

Wrackmeyer, Spectrosc.: Znt. J., 1982, 1, 201. S. Aime, R. Gobetto, D. Osella, L. Milone, G. E. Hawkes, and E. W. Randall, J. Chem. SOC.,Chem. Commun., 1983, 794. l P E. Haid, D. Kohnlein, G. Kossler, 0. Lutz, and W. Schick, J. Magn. Reson., 1983, 55, 145. l5 V. P. Tarasov, V. I. Privalov, and Yu. A. Buslaev, Dokl. Akad. Nauk SSSR, 1983, 269, 640 (Chem. Abstr., 1983, 98, 226 750). l6 D. H. Evans, D. M. P. Mingos, J. Mason, and A. Richards, J. Organomet. Chem., 1983, 249, 293. l7 L. K. Bell, J. Mason, D. M. P. Mingos, and D. G. Tew, Znorg. Chem., 1983, 22, 3497. l3

L. K. Bell, D. M. P. Mingos, D. G. Tew, L. F. Larkworthy, S. Sandell, D. C. Povey, and J. Mason, J. Chem. SOC., Chem. Commun., 1983, 125. IQ J. Pokorny, Biologia (Bratislava), 1983, 38, 289 (Chem. Abstr., 1983, 98, 156 744). 8o P. Hofstetter, E. Pretsch, and W. Simon, Helv. Chim. Acta, 1983,66,2103. 21 P. J. Smolenaers, M. T. Kelso, and J. K. Beattie, J. Magn. Reson., 1983, 52, 118. 22 Yu. N. Moskvich, A. M. Polyakov, G. I. Dotsenko, and M. L. Afanas'ev, Zh. Neorg. Khim., 1982, 27, 1972 (Chem. Abstr., 1983, 98, 45 626). 23 P. Laszlo, NATO ASZ Ser., Ser. C, 1983, 103, 261 (Chem. Abstr., 1983, 99, 132 394). 24 0. Lutz, NATO ASZ Ser., Ser. C, 1983, 103, 297 (Chem. Abstr., 1983, 99, 132 395). 26 D. Seebach, R. Haessig, and J. Gabriel, Helv. Chim. Acta, 1983, 66, 308. l8

Nuclear Magnetic Resonance Spectroscopy

3

-potassium, and -caesium are in the W form as confirmed by the lH and 13C n.m.r. spectra.26The effect of HMPA on the 13Cchemical shift of the a-carbon atom of benzyl-lithium in T H F parallels its effects on the one-electron electrochemical oxidation p~tential.,~The low-temperature 13Cn.m.r. spectrum of 1-Li-3,3-dimethyIbut-l -yne in THF has shown a non-fluxional cubic tetramer with lJ(13C,8Li) = 6 Hz.,* The 13C, 170,7Li, and 23Nan.m.r. shielding tensors have been computed for M+-CO (M = Li or Na).297Li n.m.r. measurements, including Tl and T,, have been carried out in halotolerant bacterium B,l.ao Lithioesters obtained from Pr',NLi with cycloalkanecarboxylates at low temperature have been examined by 13Cn.m.r. 7Li n.m.r. spectroscopy supports a tight ion pair for LiBr(Me,NCH,CH,NMeCH,CH,NMe).32 23Na n.m.r. signals have been observed from frog skin.33 The 23Nan.m.r. spectrum of Na+[Ph,PCHPPh,R]- and the 31P broadening suggest a tight ion pair.34 Cholesteric and nematic lyotropic mesophases from disodium N-lauroylaspartate have been investigated using ,H and 23Nan.m.r. s p e ~ t r o s c o p yThe . ~ ~ nuclear g factor of 3sK+ and the diamagnetic shielding-constant difference between 30K and 39K+have been determined.36 Intracellular K+ concentration has been determined by 39Kn.m.r. spectros~opy.~~ N.m.r. data have also been reported for (cyclo-C,H,Li),( LiBr),(Et,O), (13C),38Li [C(SiMe,Ph),] - T H F (7Li),39M(CH,PPh2CHPPh2), Ag(PPh2)&PPh2CHPPh, (M = Li, Na, or K ; 13C, 23Na, 31P),40 and Li2P16 8THF (31P).41 Di-co-ordination of beryllium in Be(NR,), results in a high-frequency shift of the gBen.m.r. signal and a large linewidth relative to tri-co-ordinate beryllium. 13C and 14Nn.m.r. spectra were also recorded.42 The ring-current model has been applied to determine the geometry of the aggregated species of porphpins

a6

*O

H. Yasuda, T. Nishi, K. Lee, and A. Nakamura, Organometallics, 1983, 2, 21. R. Breslow and J. Schwarz, J. Am. Chem. SOC.,1983, 105, 6795. G. Fraenkel and P. Pramanik, J. Chem. SOC.,Chem. Commun., 1983, 1527. T. Weller, W. Meiler, H. Pfeifer, H. Lischka, and R. Hoeller, Chem. Phys. Lett., 1983, M, 599.

M. Goldberg, M. Risk, and H. Gilboa, Biochim. Biophys. Acta, 1983, 763, 35 (Chem. Abstr., 1983, 99, 119 087). 81 L. Gorrichon, P. Maroni, Ch. Zedde, and A. Dobrev, J . Organomet. Chem., 1983, 252, 8o

267. S. R. Hall, C. L. Raston, B. W. Skelton, and A. White, Znorg. Chem., 1983, 22, 4070. 88 M. M. Civan, H. Degani, Y. Margalit, and M. Shporer, Am. J . Physiol., 1983, 245, C213 (Chem. Abstr., 1983,99, 190 934). H. Schmidbaur, U. Deschler, and D. Seyferth, Z . Naturforsch., Teil B, 1982, 37, 950 (Chem. Abstr., 1983, 98, 143 594). 86 M. R. Alcantara, M. V. Marques, C. De Melo, V. R. Paoli, and J. A. Vanin, Mol. Cryst. Liq. Cryst., 1983, 90, 335 (Chem. Abstr., 1983, 99, 46 364). E. I. Obiajunwa, S. A. Adebiyi, E. A. Togun, and A. F. Oluwole, J . Phys. B, 1983, 16, 2733 (Chem. Abstr., 1983, 99, 204 909). P. J. Brophy, M. K. Hayer, and F. G. Riddell, Biochem. J., 1983,210,961 (Chem. Abstr., 1983,99, 190 916). H. Schmidbaur, A. Schier, and U. Schubert, Chem. Ber., 1983, 116, 1938. C. Eaborn, P. B. Hitchock, J. D. Smith, and A. C. Sullivan, J, Chem. SOC.,Chem. Commun., 1983, 1390. 40 H. Schmidbaur and U. Deschler, Chem. Ber., 1983,116, 1386. 41 M. Baudler and 0. Exner, Chem. Ber., 1983, 116, 1268. H. Noth and D. Schlosser, Znorg. Chem., 1983, 22, 2700. 81


4

and ~ h l o r o p h y 1 1 The . ~ ~ ~13C ~ ~n.m.r. spectrum of chlorophyll b has been fully assigned.45 The 13Cn.m.r. spectrum of chlorophyll a formed when excized etiolated corn leaves were greened in the presence of [l-13C]glutamateshowed that the 4-methine bridge carbon atoms and the 4-pyrrole a-carbon atoms were considerably enriched.4643Ca and 25Mgn.m.r. spectroscopy has been used to investigate calcium and magnesium binding to regulatory 43Can.m.r. signals have been obtained for Ca2+bound to calmodulin, parvalbumin, and troponin C. Both Tl and T2 were determined to give the quadrupole-coupling constant and correlation time.48lH n.m.r. spectroscopy has been used to compare the structural changes induced in bovine cardiac troponin C on binding of Ca2+ and Cd2+.4glH and 31Pn.m.r. spectra have been used to investigate complexes of ethylenediamine tetrakis(methy1enephosphonic acid) with Ca2+ and the lanthanide~.~~ Calcium binding to proteins has been investigated using 43Can.m.r. spectro~copy.~~ Complexes of Ca2+and lanthanides with carboxymethoxysuccinate have been studied by lH and 13Cn.m.r. spectroscopy.62 N.m.r. data have also been reported for chlorophyll (13C),53 bacteriochlorophyll (13C),64acetate kinase (25Mg,31P),55and M{[OP(OR),],N}, (M = Ca or Ba; 31P)?

Complexes of Groups IIIA and IVA, the Lanthanides, and A~tinides.-~~Scn.m.r. chemical shifts, linewidths, and longitudinal relaxation rates have been measured in aqueous solutions of ScCl, and Sc2(S0& as a function of the appropriate acid con~entration.~~ lH and 13Cn.m.r. spectra have been used to study the structure of some yttrium and lanthanum complexes of EDTAS8N.m.r. data have also been reported for [(C5H4Me)Y(HCNBu')12 (13C),59 M(C,Me,),(dmpm) (M = Eu

R. J. Abraham and K. M. Smith, J . Am. Chem. SOC.,1983, 105, 5734. R. J. Abraham and K. M. Smith, Tetrahedron Lett., 1983, 24, 2681. 45 N. Risch and H. Brockmann, Tetrahedron Lett., 1983, 24, 173. 46 R. J. Porra, 0. Klein, and P. E. Wright, Eur. J. Biochem., 1983, 130, 509 (Chem. Abstr., 1983,98,68 999). 47 S. Forsen, T. Andersson, T. Drakenberg, H. Lilja, and E. Thulin, Period. Bid., 1983, 85, 31 (Chem. Abstr., 1983, 99, 190019). 48 S. Forsen, T. Andersson, T. Drakenberg, E. Thulin, and M. Swaerd, Fed. Proc., Fed. Am. Soc. Exp. Biol., 1982, 41, 2981 (Chem. Abstr., 1983, 98, 1886). 49 0. Teleman, T. Drakenberg, S. Forsen, and E. Thulin, Eur. J. Biochem., 1983, 134, 453 (Chem. Abstr., 1983, 99, 135 771). 50 E. N. Rizkalla and G. R. Choppin, Inorg. Chem., 1983, 22, 1478. 51 T. Drakenberg, S. ForsCn, and H. Lilja, J. Magn. Reson., 1983,53, 412. 52 C. A. M. Vijverberg, J. A. Peters, W. M. M. J. Bovk, H. Vroon, A. P. G . Kieboom, and H. van Bekkum, Recl. Trav. Chim. Pays-Bas, 1983,102,255. 53 S . Lotjonen and P. H. Hynninen, Org. Magn. Reson., 1983,21,756. 54 R. G. Brereton and J. K. M. Sanders, J. Chem. SOC.,Perkin Trans. I , 1983, 435. 55 T. Shimizu and M. Hatano, Inorg. Chim. Acta, 1983, 80, L37. 58 H. Richter, E. Fluck, H. Riffel, and H. Hess, 2. Anorg. Allg. Chem., 1983, 496, 109. 57 E. Haid, D. Koehnlein, G . Koessler, 0. Lutz, W. Messner, K. R. Mohn, G . Nothaft, B. Van Rickelen, W. Schich, and N. Steinhauser, 2. Naturforsch., Teil A, 1983, 38, 317 (Chem. Abstr., 1983, 98, 190 419). 58 C. Djordjevic, L. G. Gonshor, M. D. Schiavelli, and L. S. Angevine-Malley, J. LessCommon Met., 1983, 94, 355 (Chem. Abstr., 1983, 99, 204 922). 59 W. J. Evans, J. H. Meadows, W. E. Hunter, and J. L. Atwood, Organometallics, 1983,2, 1252. 43

44


5

or Yb; 31P),B0[(C,Me,),SmCPh], (13C),61 Cp2LuButCH2PPh3(13C, 31P),82 (C5Me5)2L~CBH4L~(C5Me5)2 (13C),63 Cp,T~[OC(=PR3)C(CHzBut)b]C1 (31P),64 [(uo2)3(co3)~]s-(13C),B5and U0,(N03),[(PriO),P(0)CH,C(O)NEt2] (13C, 31P).68 The lH chemical shifts in M(q-C5H5)(q-CSH4Me)R2 (M = Ti, Zr, or Hf) have been N.m.r. data have also been reported for (q5-C5H5),Ti(p-RCCH,)("€3, (p-CO)W(CO)(q5-C5H5) (13C, 31P)968 H-H,PMe,),](BH,), 31P),B9Cp,ZrMeRuCp(CO), (13C),70 Cp,M(CH,),CMe, (M = Ti, Zr, or Hf; (13C),72[C13TkH2CH2C(OR)=b12 18C),71Cp,TiC1(CH,CH,CHR1CR2=CH2) (13C),73[(Me3Si),N],ZrMeOCMe===CMe2 (13C),74 (q5-C5H,),Zr(Cl)CH,PPh,Cr(CO)s (31P),75 (-I+C~H~)~Z~,X(CH=CHR)(13C),76 &l(CH,SiMe,flSiMe,),(MezPCH2CH2PMe2) (13C, 31P)," (Cp2ZkOCH2CHR1kR2R3], (13C),78 Cp2ZrCH,CH=CHCH,CPh,0 (13C),79 Zr2(CH2PMe2)4(p-CPMe3)z (13C, 31P),80 {Zk(CHSiMe2kSiMe3) W(SiMe,),] }, (l 3C),81 (1) (l "), 82 (2) (13C), ZrC1,-

6o

T. D. Tilley, R. A. Andersen, and A. Zalkin, Inorg. Chem., 1983, 22, 856. J. Evans, I. Bloom, W. E. Hunter, and J. L. Atwood, J. Am. Chem. Soc., 1983, 105,

61 W.

1401.

H. Schumann, F. W. Reier, and M. Dettlaff, J. Organomet. Chem., 1983, 255, 305. 63 P. L. Watson, J. Chem. SOC.,Chem. Commun., 1983, 276. 64 K. G. Moloy, T. J. Marks, and V. W. Day, J. Am. Chem. SOC.,1983, 105, 5696. 85 M. Aberg, D. Ferri, J. Glaser, and I. Grenthe, Inorg. Chem., 1983, 22, 3981. 68 S. M. Bowen, E. N. Duesler, and R. T. Paine, Inorg. Chem., 1983, 22, 286. 67 S. Chen and Y. Liu, Huaxue Xuebao, 1982, 40,913 (Chem. Abstr., 1983, 98, 72 330). 68 R. D. Barr, M. Green, J. A. K. Howard, T. B. Marder, I. Moore, and F. G. A. Stone, J. Chem. SOC.,Chem. Commun., 1983, 746. M. D. Frymk and H. D. Williams, Organometallics, 1983, 2, 162. 70 C. P. Casey, R. F. Jordan, and A. L. Rheingold, J. Am. Chem. SOC.,1983, 105, 665. 71 J. W. F. L. Seetz, G. Schat, 0. S. Akkerman, and F. Bickelhaupt, Angew. Chem., Int. Ed. Engl., 1983, 22, 248. H. Lehmkuhl, Y.-L. Tsien, E. Janssen, and R. Mynott, Chem. Ber., 1983, 116, 2426. 73 E. Nakamura and I. Kuwajima, J. Am. Chem. SOC.,1983,105, 651. R. P. Planalp and R. A. Andersen, J. Am. Chem. SOC.,1983, 105, 7774. 76 N. E. Schore, S. J. Young, M. M. Olmstead, and P. Hofmann, Organometallics, 1983, 2, 1769.

G. Erker, K. Kropp, J. L. Atwood, and W. E. Hunter, Organometallics, 1983, 2, 1555. 77 R. P. Planalp and R. A. Andersen, Organometallics, 1983, 2, 1675. H. Takaya, M. Yamakawa, and K. Mashima, J. Chem. SOC.,Chem. Commun., 1983,1283. 7g G. Erker, K. Engel, J. L. Atwood, and W. E. Hunter, Angew. Chem., Znt. Ed. Engl., 1983, 22, 494. 8o G. W. Rice, G. B. Ansell, M. A. Modrick, and S. Zentz, Organometallics, 1983, 2, 154. R. P. Planalp, R. A. Andersen, and A. Zalkin, Organometallics, 1983, 2, 16. 8a K. Kropp, V. Skibbe, G. Erker, and C. Kriiger, J, Am. Chem. SOC.,1983, 105, 3353. E. J. Moore, D. A. Straus, J. Armantrout, B. D. Santarsiero, R. H. Grubbs, and J. E. Bercaw, J. Am. Chem. SOC.,1983, 105, 2068. 76


6

[N(SiMe2CH2PPh2),I2 (31P),84MW( pCC6H4Me-4)[p-(o-q2-CO)](CO)Cp3(M = Ti or Zr ; 13C),85CpCITi(pNPh),TiCpCl (13C),8sTi(2,4-Me2C,H,),(PF,) (13C, leF, ,lP),*' Cp,M(PR,), (M = Zr or Hf; 31P),88[M(PCy,),]- (M = Zr or Hf; 13C, 31P),89and C1,TiOCR1=CR2H (13C).90

Complexes of V, Nb, and Ta.-A review entitled 'A survey of vanadium-51 n.m.r. spectroscopy' has appeared.g1 The 51V chemical shifts of (Y)~-RCO)V(CO)~L~ correlate with the Hammett 0-constant of the substituent R.92 The g3Nb shielding increases in the order MR, = Au(PPh,) < PbPh, < GePh, < SnPh, SnBz, for [NbCp(MR,)(CO)3]-.g3N.m.r. data have also been reported for V2Zn2H4(BH4)2(PMe2Ph)4 (llB, 31P),94 (q5-C5Me,)(B~tO),HTa(y-H)2TaH,(q5-C,Me5) (31P),g5 [Ta(y6C5Me4Et)CI2H],CO(13C),96 (3) (13C, 19F),97 (C,Me5)T~(CH2CH2CH2~H,)(C4H,) (13C),9 8 Ta(PMe,),(q2-CH,PMe,)(q2-CHPMe2) (31P),gg (C, Me,)Ta(CH,NMe)Me, (l3C),looand (4) (13C).lo1 N

) ~ been The 51V and 93Nbn.m.r. spectra of CPV(CO)~and C ~ N b ( c 0 have determined in nematic liquid-crystalline matrices and in the polycrystalline M. D. Fryzuk, H. D. Williams, and S. J. Rettig, Inorg. Chem., 1983, 22, 863. G. M. Dawkins, M. Green, K. A. Mead, J. Y. Salaun, F. G. A. Stone, andP. Woodward, J . Chem. SOC.,Dalton Trans., 1983, 527. *6 C. T. Vroegop, J. H. Teuben, F. van Bolhuis, and J. G. M. van der Linden, J. Chem. SOC.,Chem. Commun., 1983, 550. 87 R. D. Ernst, J.-Z. Liu, and D. R. Wilson, J. Organomef. Chem., 1983, 250, 257. 8 8 R. T. Baker, J. F. Whitney, and S. S. Wreford, Organometallics, 1983, 2, 1049. 89 R. T. Baker, P. J. Krusic, T. H. Tulip, J. C. Calabrese, and S. S. Wreford, J. Am. Chem. 84

85

SOC.,1983, 105, 6763.

E. Nakamura, J.4. Shimada, Y. Horiguchi, and I. Kuwajima, Tetrahedron Lett., 1983, 24, 3341. O2

O3 94 85

D. Rehder, Bull. Magn. Reson., 1982, 4, 3 3 (Chem. Abstr., 1983, 98, 45 379). J. Schiemann and E. Weiss, J. Organemet. Chem., 1983, 255, 179. I. Pforr, F. Naumann, and D. Rehder, J. Organomet. Chem., 1983, 258, 189. R. L. Bansemer, J. C. Huffman, and K. G. Caulton, J. Am. Chem. SOC.,1983, 105, 6163. J. M. Mayer, P. T. Wolczanski, B. D. Santarsiero, W. A. Olson, and J. E. Bercaw, Znorg. Chem., 1983, 22, 1149. P. A. Belmonte, F. Cloke, N. Geoffrey, and R. R. Schrock, J. Am. Chem. SOC.,1983,105, 2643.

97 O8 99

R. Mercier, J. Douglade, J. Amaudrut, J. Sala-Pala, and J. E. Guerchais, J. Organomet. Chem., 1983,244, 145. J. Blenkers, H. J. de Liefde Meijer, and J. H. Teuben, Organometallics, 1983, 2, 1483. V. C. Gibson, P. D. Grebenik, and M. L. H. Green, J. Chem. SOC.,Chem. Commun., 1983 1101.

J. M. Mayer, C. J. Curtis, and J. E. Bercaw, J. Am. Chem. SOC.,1983, 105, 2651. lol A. W. Gal and H. van der Heijden, J. Chem. SOC.,Chem. Commun.,1983,420. loo


7

state. The quadrupole-coupling constants for the two compounds are approximately the same.lo2The normal halogen dependence has been found for S(W) in [V(q5-C5H5)X(CO)3]-.103 Recent 51V n.m.r. data on [V(CO),L]- have been tabulated and presented graphically. The chemical-shift range overlaps with that observed for V5+.lM N.m.r. data have also been reported for CpNb(CO), Cp,NbClL (l3C),lO8and ( 5 ) (13C, 1°F).lo7 (p.-L)CpNb(C0)3(31P,93Nb),105

Solutions of [V(NO),CI,], in MeNO,, THF, and MeCN have been characterized by 51V n.m.r. spectroscopy.1o8In (Me,SiO),VNBu' the 51V n.m.r. spectrum shows 1J(51V,14N)= 95 Hz.loOAccording to 51V n.m.r. spectra, the reaction of VOCl, with Et,NH in MeCN is different from that in CC14.110The dependence (L = imidazole or l-substituted of the 1°F chemical shifts of truns-~aF4L2]+ benzimidazole) depends on the azole basicity.lll N.m.r. data have also been reported for [VO(O,)(NC,H,CO,),]- (13C),l12complexes between ATP and V 0 2 + (13C, ,lP),l13 [V2W8031]4-('j1V),l14a-[p2(W,V)180,,]"- (31P, W),l16 [V02FJ3(l°F, 51V),11gand Nb,Cll,(PMe,Ph),[(F,P),NMe] (1°F).l17

Complexes of Cr, Mo, and W.-A review entitled 'Overview of s 6 Mn.m.r.' ~ has appeared.l18 The use of 31Pn.m.r. spectroscopy to investigate molybdenum dithiophosphate oil additives has been reviewed.l1° D. Rehder, K. Paulsen, and W. Basler, J. Magn. Reson., 1983, 53, 500. R. Talay and D. Rehder, Inorg. Chim. Acra, 1983, 77, L175. lo4D. Rehder and K. Ihmels, Inorg. Chim. Acta, 1983, 76, L313. Io6 M. Hoch and 1). Rehder, 2. Naturforsch., Ted B, 1983, 38, 446 (Chem. Abstr., 1983, 99,88 315). R. Serrano and P. Royo, J. Organomet. Chem., 1983, 247, 33. lo7J.-L. Migot, J. Sala-Pala, and J.-E. Guerchais, J . Organomet. Chem., 1983, 243, 427. lo8M. Herberhold and H. Trampisch, Inorg. Chim. Act& 1983, 70, 143. looW. A. Nugent, Inorg. Chem., 1983, 22, 965. A. A. Konovalova, S. V. Bainova, V. D. Kopanev, and Yu. A. Buslaev, Koord. Khim., 1982, 8, 1364 (Chem. Abstr., 1983, 98, 45 918). 111 M. E. Ignatov, E. G. Win, A. D. Garnovskii, and Yu. A. Buslaev, Koord. Khim., 1982, 8, 1368 (Chem. Abstr., 1983, 98, 45 919). 112 H. Mimoun, L. Saussine, E. Daire, M. Postel, J. Fischer, and R. Weiss, J. Am. Chem. SOC.,1983, 105, 3101. 11* H. Sakurai, T. Goda, and S. Shimomura, Biochem. Biophys. Res. Commun., 1982, 108, 474 (Chem. Abstr., 1983, 98, 1813). 114P. Courtin, J. Lefebvre, B. Araki, and J. Livage, N o w . J. Chim., 1983, 7, 115 (Chem. Abstr., 1983, 99, 46 928). 115S. P. Harmalker, M. A. Leparulo, and M. T. Pope, J. Am. Chem. SOC.,1983, 105, 4286. ll6 R. J. Gillespie and U. R. K. Rao, J. Chem. Soc., Chem. Commun., 1983, 422. 117 L. G. Hubert-Pfalzgraf, Inorg. Chim. Actu, 1983, 76, L233. 118 J. H. Enemark, Nitrogen Fixation: Chem.-Biochem.-Genet. Interface [Proc. Int. Meet.], 1981, 1983, 329 (Chem. Abstr., 1983,98, 208 657). 11° P. C. H. Mitchell, A. R. Read, T. Colclough, and H. Spedding, Chem. Uses Molybdenum, Proc. Int. Conf.,4th, 1982, 212 (Chem. Absrr., 1983, 99, 178 446). lo2

lo3

8


(7)

The lH nuclear Overhauser enhancement has been used to determine the stereochemistry of (6).120 N.m.r. data have also been reported for CrH,(dmpe), (,lP),121 MoH,(PMe,), (31P),122 {[(PMePh,),H,Mo],( p-F),)+ (,lP),12, (7) (13C),124 [(C,Me,)W(CO),H], (13C),125 Cp2WH(p-H)Pt(PEt,),Ph (,lP),lz6Cr(CO),C(NEt,) TePh (13C),12’ [CpM(CO),(PMe,)(CROMe)]+[SO,F](M = Cr, Mo, or W; 13C,lsF, 31!?),12a (T6-C6Me6)Cr(CO)( p-CO)( p-CR)W(CO)Cp(l3c),l2’(8) (M = Cr, Cp,Mo[C(CN)=CH,](CH=CHCN) (13C),131CpMo(C0)Mo, or W ;13C,31P),130 Cl(CPhNMeCPh=NMe) (13C),132{CpMo(C0),(PPh3)[C(CH,),0]}+(13C),13, HB(N,C,H,) ,Mo(CO),(OCMe) (l 3C),134 (q5-C5H5)(C0),M [C(CN)==CHCN] (M = Mo or W; 13C),135Cp(CO),hho[CMe=CEtC(b)CMe=CHEt] (13C),136 (OC),Mk(C5H,PPh,)dh(dppe) (13C,,lP),13’C p M ( C O ) , Z m M e , (M = Mo or W; 13C),13*CpMoBr[P(OMe),],C==CHPh (13C, 31P),139(C,R,)(CO)I (PMe,)hC(OSiMe,)=CHCOR (M = Mo or W; 31P),140M(ql-CCl)(CO),H. Brunner, J. Wachter, I. Bernal, G. M. Reisner, and R. Benn, J. Organomet. Chem., 1983,243, 179. G. S. Girolami, J. E. Salt, G. Wilkinson, M. Thornton-Pett, and M. B. Hursthouse, J. Am. Chem. SOC.,1983, 105, 5954. 122 M. B. Hursthouse, D. Lyons, M. Thornton-Pett, and G. Wilkinson, J. Chem. SOC.,Chem. Commun., 1983,476. 123 R. H. Crabtree, G. G . Hlatky, and E. M. Holt, J. Am. Chem. Soc., 1983, 105, 7302. 124 C. P. Casey and R. M. Bullock, J. Organornet. Chem., 1983, 251, 245. 125 H. G. Alt, K. A. Mahmoud, and A. J. Rest, Angew. Chem., Int. Ed. Engl., 1983, 22, 544. 126 A. Albinati, R. Naegeli, A. Togni, and L. M. Venanzi, Organometallics, 1983, 2, 926. 12’ H. Fischer; E. 0. Fischer, R. Cai, and D. Himmelreich, Chem. Ber., 1983, 116, 1009. 12* G . Grotsch and W. Malisch, J. Organomet. Chem., 1983, 258, 297. lZQ J. A. Abad, L. W. Bateman, J. C. Jeffery, K. A. Mead, H. Razay, F. G. A. Stone, and P. Woodward, J. Chem. SOC.,Dalton Trans., 1983, 2075. 130 P. Thometzek and H. Werner, J. Organomet. Chem., 1983, 252, C29. 131 H. Scordia, R. Kergoat, M. M. Kubicki, and J. E. Guerchais, J. Organomet. Chem., 1983,249, 371. 132 H. Brunner, W. Meyer, and J. Wachter, J. Organomet. Chem., 1983, 243, 437. 133 N. A. Bailey, P. L. Chell, C. P. Manuel, A. Mukhopadhyay, D. Rogers, H. E. Tabbron, and M. J. Winter, J. Chem. SOC.,Dalton Trans., 1983, 2397. 134 M. D. Curtis, K.-B. Shiu, and W. M. Butler, Organometallics, 1983, 2, 1475. 135 H. Scordia, R. Kergoat, M. M. Kubicki, J. E. Guerchais, and P. L’Haridon, Organometallics, 1983, 2, 1681. 136 S. R. Allen, M. Green, N. C. Norman, K. E. Paddick, and A. G. Orpen, J . Chem. SOC., Dalton Trans., 1983, 1625. 13’ C. P. Casey, R. M. Bullock, and F. Nief, J. Am. Chem. SOC.,1983,105, 7574. 13* P. H. M. Budzelaar, H. J. Alberts-Jansen, K. Mollema, J. Boersma, G. J. M. van der Kerk, A. L. Spek, and A. J. M. Duisenberg, J. Organomet. Chem., 1983, 243, 137. 139 R. G. Beevor, M. Green, A. G. Orpen, and I. D. Williams, J. Chem. Soc., Chem. Commun., 1983, 673. 140 G . Grotsch, W. Malisch, and H. Blau, J. Organomet. Chem., 1983,252, C19. 120

9


Me

OR^

R3, I R2H4C5, /c7s, M-

oc/ 'c'

N=N

,CO M-C H R1

\c6

0

Me

(9)

[HB(3,5-MezC3HN2)J(M Mo or W; l3C),l4I (9) (M = Mo or W, R2 = H or Me; 13C),142(10) (13C),143(11) (13C),144(12) (l3c),l4' M,W(p&R)(CO),Cp, (M = Mo or W; l3C),lQe (13) (M = Mo or W; 13C),14'(PhC=C),Pt(p-dppm),Mo-2

(CO) (31P),14 W(C,Et,)(CH,Bu ') ,Cl (13C),140 W,O ,(CH,Bu ' ) 6 (13C),160 (+ C6Me5)W(CO)3CH2SiMe,H (13C),151 (dppe)W(CO),C==CH (13C, 31P),1az Cl,W=CH, (13C),163CpCl,W=CBu'CMe=CHBu' (13C),164(14) (13C, 31P),1b6

T. Desmond, F. J. Lalor, G. Ferguson, and M. Parvez, J. Chem. SOC.,Chem. Commun., 1983, 457.

H. Alper, F. W. B. Einstein, R. Nagai, J. -F. Petrignani, and A. C. Willis, Organometallics, 1983, 2, 1291. lra M. Green, A. G. Orpen, C. J. Schaverien, and I. D. Williams, J. Chem. SOC.,Chem. Commun., 1983, 181. I r 4 W. A. Herrmann, G. W. Kreichbaum, R. D a r n e l , H. Bock, M. L. Ziegler, and H. Hsterer, J. Organomet. Chem., 1983, 254, 219. 145 H. Brunner, B. Hoffmann, and J. Wachter, J. Organomet. Chem., 1983, 252, C35. lr6 M. Green, S. J. Porter, and F. G. A. Stone, J. Chem. SOC.,Dalton Trans., 1983, 513. 14' M. Green, K. Marsden, I. D. Salter, F. G. A. Stone, and P. Woodward, J. Chem. SOC., Chem. Commun., 1983, 446. 148 A. Blagg, A. T. Hutton, P. G. Pringle, and B. L. Shaw, Znorg. Chim. Actu, 1983, 76, L265. 149 K. H. Theopold, S. J. Holmes, and R.R. Schrock, Angew. Chem., Int. Ed. Engl., 1983,22, 142

1010.

I. Feinstein-Jaffe, S. F. Pedersen, and R. R. Schrock, J. Am. Chem. Soc., 1983,105, 7176. lJ1C. Lewis and M. S. Wrighton, J. Am. Chem. SOC.,1983, 105, 7768. 152 K. R. Birdwhistell, S. J. N. Burgmayer, and J. L. Templeton, J. Am. Chem. Soc., 1983, 150

105, 7789

Gilet, A. Mortreux, J.-C. Folest, and F. Petit, J. Am. Chem. SOC.,1983, 105, 3876. L. G. McCullough, M. L. Listemann, R. R. Schrock, M.R. Churchill, and J. W. Ziller, J. Am. Chem. SOC.,1983,105, 6729. 155 F. R. Kreissl, M. Wolfgruber, W. Sieber, and K. Ackermann, J. Organomet. Chem., 1983, 252, c39. 15, F. Y. Petillon, J.-L. Le Quere, F. Le Floch-Perennou, J.-E. Guerchais, M.-B. Gomes de Lima, Lj. Manojlovid-Muir, K. W. Muir, and D. W. A. Sharp, J. Organomet. Chem., lS3M. 154

1983, 255, 231.

10


(13C),157 [(OC),W(COPh)(p-PPh,),IrH(CO)(PPh,)]- (31P),158 [(Me,P),&(p-CRMe)+(CO),Cp]+ (13C, 31P,195Pt),159 PtW[ p-C(OMe)R](p-dppm)(CO), (13C,31P,19sPt),160 PtW[p-C(OMe)Me](CO),(cod) (13C,31P,195Pt),16r PhCW(CO)4co(Co), (l3C),l6, FeW(p-CR)(CO),Cp ("c, 31P),163CuPtW(p-C-p-tol)(CO),(PMe3)(q6-C,H5)(q6-C5Me5) (13C, 31P),164 and (1 5 ) (13C, 31P, le5Pt).lss

The 19Fn.m.r. spectrum of Cr(r16-C6H6)(Tj6-C6F5PPh2) shows enormous increases in J(lgF,l9F)relative to those in the free arene. The 31Pn.m.r. spectrum was also reported.166The g 5 M and ~ 14Nn.m.r. spectra of CpMo(CO),(NO) have provided the first example of J(95Mo,14N)= 46 Hz. The 1 7 0 n.m.r. N.m.r. data have also been reported for Mo,( pS)spectrum was also rep0~fed.l~~ (p-EtC=CEt)(S2CNMe,),(SCNMe,) (13C),168MoCI[C(CF,)C(CF,)L](CF,C= CCFJCp (19F),16' Cp2M02(C0)4(R1C=CR2) (13C),170 Mo(SBU')~(CNBU'),(R1C=CR2) (l3C),I7lCp(Et,P)M(p-CF3C~CCF3),Co(C0)PEt3 (M = Mo or W; 19F, 31P).172[CpW(CO)(PMe,)(ROCH=CHC,H,Me)]+ (13C, 31P),173 J. Kress and J. A. Osborn, J. Am. Chem. SOC.,1983, 105, 6346. M. J. Breen, G. L. Geoffroy, A. L. Rheingold, and W. C. Fultz, J , Am. Chem. SOC.,1983, 105, 1069. lS9 M. R. Awang, J. C. Jeffery, and F. G. A. Stone, J. Chem. Soc., Chem. Commun., 1983, 1426. 160 K. A. Mead, I. Moore, F. G. A. Stone, and P. Woodward, J. Chem. SOC.,Dalton Trans., 1983, 2083. 181 M. R. Awang, J. C. Jeffery, and F. G. A. Stone, J. Chem. SOC.,Dalton Trans., 1983,2091. 182 E. 0. Fischer, P. Friedrich, T. L. Lindner, D. Neugebauer, F. R. Kreissl, W. Uedelhoven, N. Q. DaO, and G. Huttner, J. Organomet. Chem., 1983, 247,239. 163 L. Busetto, J. C. Jeffery, R. M. Mills, F. G. A. Stone, M. J. Went, and P. Woodward, J. Chem. SOC.,Dalton Trans., 1983, 101. lMG. A. Carriedo, J. A. K. Howard, and F. G. A. Stone, J. Organomet. Chem., 1983, 250, C28. 186 M. R. Awang, G. A. Carriedo, J. A. K. Howard, K. A. Mead, I. Moore, C. M. Nunn, and F. G. A. Stone, J. Chem. SOC.,Chem. Commun., 1983, 964. lB8R. Faggiani, N. Hao, C. J. L. Lock, B. G. Sayer, and M. J. McGlinchey, Organometallics, 1983, 2, 96. 18' M. Minelli, J. L. Hubbard, K. A. Christensen, and J. H. Enemark, Znorg. Chem., 1983, 22, 2652. lB8 R. S. Herrick, S. J. N. Burgmayer, and J. L. Templeton, J. Am. Chem. SOC.,1983, 105, 2599. lB9 J. L. Davidson, W. F. Wilson, L. Manojlovid-Muir, and K. W. Muir, J. Organomet. Chem., 1983, 254, C6. 170 R. F. Gerlach, D. N. Duffy, and M. D. Curtis, Organometallics, 1983, 2, 1172. 171 M. Kamata, K. Hirotsu, T. Higuchi, M. Kido, K. Tatsumi, T. Yoshida, and S . Otsuka, Znorg. Chem., 1983, 22, 2416. 172 J. L. Davidson, J. Chem. SOC.,Dalton Trans., 1983, 1667. 173 F. R. Kreissl, W. Sieber, and M. Wolfgruber, Angew. Chem., Int. Ed. Engl., 1983, 22, 493. 167

158


11

[CpW(CO)(C,H,)(CROEt)]+ (13C),17, (-q5-C5H5)W(CO)(NO)(q2-HC=CCOMe) (13C),17,W(PMe,)(PhC=CH), (13C, 31P),176W(q2-CHS2R)(dppe)(C0),(31P),177 MoL1L2(q ,-allyl)Cp ( 3C, ,lP), l7 CpW(C MeCBu 'CMe)CI, (l "), l7 CpW(CO),[(o-phen)(CO)(CN),W(OCCPh)]-(13C),lS1(16)(M= Cr, (q3-CHMePh)(13C),180 Mo, or W; l1B),lS2W(CO),(q4-cot) (l3C),lS3WBr,(CO)(nbd)(PMe,Ph) (31P),184 Cp,Cr(CO),S (l3C),lS5(17) (R = But or Ph; 13C,,lP),lS6(18) (l3C),lS7Hg[MeBC,H,Cr(CO),], (l1B),lS8Pd,M,(~5-C,H5)2(CO)6(PMe3), (M = Cr, Mo, or W; 13C, 31P),189[CpMo(CO),],(AsMe), (l3C),lQoCp,MoPMe, (,lP),lB1 Mo[C,(CF,),MRhp(pCO)z(CO)S(C5Me,), (M = Cr, Mo, or W; SC,H,NO]Cp (39F),192 lSC),lQ3 {CpM(CO),[(Ph,P),NCHRCO,Me]}+(M = Mo or W; 31P),394 C~(CO),M~N[C(CO,E~)=C(OE~)~]=NMO(C~)~C~ (13C),lQS (CSH3R1R2SMe)M(CO)3 (M = Mo or W; 13C),lg6CpM(CO),(AsMe,BH,)L (M = Mo or W; CpM(CO),[P(OMe)3](p-SMe)W(CO)5 (M = Mo or W; 13C, 33P),198 llB, 31P),197 H. G. Alt, J. Organomet. Chem., 1983, 256, C12. H. G. Alt and H. I. Hayen, Angew. Chem., Znt. Ed. Engl., 1983, 22, 1008. 17* K. W. Chiu, D. Lyons, G. Wilkinson, M. Thornton-Pett, and M. B. Hursthouse, Polyhedron, 1983, 2, 803. 17' W. A. Schenk and T. Schwietzke, Organometallics, 1983, 2, 1905. 178 S. R. Allen, P. K. Baker, S.G. Barnes, M. Bottrill, M. Green, A. G. Orpen, I. D. Williams, and A. J. Welch, J. Chem. SOC.,Dalton Trans., 1983, 927. 178 M. R. Churchill, J. W. Ziller, L. McCullough, S. F. Pedersen, and R. R. Schrock, Organometallics, 1983, 2, 1046. lB0 S.-C. H. Su and A. Wojcicki, Organometallics, 1983, 2, 1296. lB1 E. 0. Fischer, A. C. Filippou, H. G. Alt, and K. Ackermann, J. Organomet. Chem., 1983, 254, c 2 1 . G. E. Herberich and M. M. Kucharska-Jansen, J. Organomet. Chem., 1983, 243, 45. lB3S. Ozkar and C. G. Kreiter, 2. Anorg. Allg. Chem., 1983, 502, 215. lB4J. L. Davidson and G. Vasapollo, J. Organornet. Chem., 1983, 241, C24. lE5 L. Y.Goh, T. W. Hambley, and G. B. Robertson, J. Chem. Soc., Chem. Commun., 1983, 1458. K. Dimroth and H. Kaletsch, J. Organomet. Chem., 1983, 247,271. lB7C. Elschenbroich, J. Heck, W. Massa, and R. Schmidt, Angew. Chem., Int. Ed. Engl., 1983, 22, 330. G. E. Herberich and D. Sohnen, J. Organomet. Chem., 1983, 254, 143. R. Bender, P. Braunstein, J.-M. Jud, and Y. Dusausoy, Znorg. Chem., 1983, 22, 3394. looA. L. Rheingold and M. R. Churchill, J. Organomet. Chem., 1983, 243, 165. lg1 K. Fiederling, I. Grob, and W. Malisch, J. Organomet. Chem., 1983, 255, 299. lQ2J. L. Davidson, I. E. P. Murray, P. N. Preston, and M. V. Russo, J. Chem. Soc., Dalton Trans., 1983, 1783. lg3R. D. Barr, M. Green, K. Marsden, F. G. A. Stone, and P. Woodward, J. Chem. SOC., Dalton Trans., 1983, 507. lg4 H.-G. Fick and W. Beck, J. Organomet. Chem., 1983, 252, 83. lg5 J. J. D'Errico, L. Messerle, and M. D. Curtis, Znorg. Chem., 1983, 22, 851. L. Weber, Chem. Ber., 1983, 116, 2022. lg7 R. Janta, R. Maisch, W. Malisch, and E. Schmid, Chem. Ber., 1983, 116, 3951. lgBJ. L. Le QuM, F. Y. Petillon, J. E. Guerchais, Lj. ManojloviL-Muir, K. W. Muir, and D. W. A. Sharp, J. Organomet. Chem., 1983, 249, 127. 174

175

12

Spectroscopic?Properties of Inorganic and Organometallic Compounds

(19)

(19) (13C),lQ 9 (C,H,Me),Mo,(CO),( p-CI3H8) (l3C),,Oo CUM(CO)~(PP~~),CP (M = Mo or W; 13C, 31P),201(C,Me,),Mo,(pNCMe,)(CO),(NCO)(13C),202 I ) (I", 31P),203 (~5-C,H,)Mo(CO),(OAc),CuL Mo,(~~-C~M~~)(CO)~(PNBU~PNBU (13C),2M C O M O R ~ ( ~ C ~ ) ~ ( C O ) , ( C , M (13C),,05 ~,), [W(CO)(PMe,)(q-MeC,e3c, 31p),206 CpW(C0),AsBut2CSO (13C),207 OMe)Cp]+ [CpW(CO)(PMe3)AsMe,C(p-tol)=C(PMe3)d]+ (13C, 31P),208 CpW(CO)(PMe,)Cl(PMe,CR=CO) (13C, ,lP),,09 CpW(CO)(PMe,)PMe,CH(p-tol)CO, (I3C, 31P),210(q5-C,H,)W(CO)(PMe,)I[Me,AsC(p-tol)=C=O](13C),,11 (arene)Cr(CO), (13C),212(6,6-R2-fulvene)Cr(C0), (l3C),,I3 (9-Ph-anthracene)Cr(CO)3 (13c)7214(20) (I", 31P),215 [C6H3( si Me 3)( 0Me)(E-2hexenyl) ]Cr ( c o ) , ( 'c), (21) (,lP),,17 (q6-C13H18)Cr(C0)3 (l3C),,l8 (22) (13C),,lQexo-{C,H,[CH(SPh),]Cr(CO),}- (13C),220 q6-(Me2C5H,N)Cr(CO),PPh, (31P),221Mo(+PhP[RhCI(cod)]MePh)(PR,),L (31P),222 (23) (13C)7223 and [Cp,Mo2(C8H7CH2)]+ (13C).224 R. DuBois, J. Am. Chem. SOC., 1983, 105, 3710. J. J. D'Errico and N. D. Curtis, J. Am. Chem. SOC., 1983, 105, 4479. 201 L. Carlton, W. E. Lindsell, K. J. McCullough, and P. N. Preston, J. Chem. SOC., Chem. Commun., 1983, 216. 202 W. A. Herrmann, L. K. Bell, M. L. Ziegler, H. Pfisterer, and C. Pahl, J. Organomet. Chem., 1983, 247, 39. 203 D. A. Dubois, E. N. Duesler, and R. T. Paine, Organometallics, 1983, 2, 1903. 204 H. Werner, J. Roll, K. Linse, and M. L. Ziegler, Angew. Chem., Znt. Ed. Engl., 1983, 22, 982. 205 R. D. Barr, M. Green, J. A. K. Howard, T. B. Marder. and F. G. A. Stone, J. Chem. SOC.,Chem. Commun., 1983, 759. 206 J. C. Jeffery, J. C. V. Laurie, I. Moore, and F. G. A. Stone, J . Organomet. Chem., 1983, 258, C37. 207 M. Luksza, S. Himmel, and W. Malisch, Angew. Chem., Znt. Ed. Engl., 1983, 22, 416. 208 F. R. Kreissl, M. Wolfgruber, and W. J. Sleber, Organometallics, 1983, 2, 1266. ,OB F. R. Kreissl, M. Wolfgruber, W. Sieber, and H. G. Alt, Angew. Chem., In?. Ed. Engl., 1983, 22, 149. alo M. Wolfgruber and F. R. Kreissl, J. Organomet. Chem., 1983, 258, C9. 211 F. R. Kreissl, M. Wolfgruber, and W. Sieber, Angew. Chem., In?. Ed. Engl., 1983, 22, 1001. E. A. Domogatskaya, V. N. Setkina, N. K. Baranetskaya, V. N. Trembovler, B. M. Yavorskii, A. Ya. Shteinshneider, and P. V. Petrovskii, J. Organomet. Chem., 1983, 248, 161. 213 B. Lubke, F. Edelmann, and U. Behrens, Chem. Ber., 1983,116, 1 1 . 214 S . D. Cunningham, K. Ofele, and B. R. Willeford, J. Am. Chem. SOC.,1983, 105, 3725. 216 M. Yoshifuji and N. Inamoto, Tetrahedron Lett., 1983, 24, 4855. M. F. Semmelhack and A. Zask, J. Am. Chem. SOC.,1983, 105, 2034. 217 T. E. Bitterwolf, J. Organomet. Chem., 1983, 252, 305. A. D. Hunter and P. Legzdins, Organometallics, 1983, 2, 525. 21B C. G. Kreiter and H. Kurz, Chem. Ber., 1983, 116, 1494. a20 W. P. Henry and R. D. Rieke, J. Am. Chem. SOC., 1983, 105, 6314. 221 H. W. Choi and M. S. Sollberger, J. Organomet. Chem., 1983, 243, C39. 22a R. Luck and R. H. Morris, J. Organomet. Chem., 1983, 255, 221. 223 E. Michels and C. G. Kreiter, J. Organornet. Chem., 1983, 252, C1. 224 S. G. Bott, N. G. Connelly, M. Green, N. C. Norman, A. G. Orpen, J. F. Paxton, and C. J. Schaverien, J. Chem. SOC.,Chem. Commun., 1982, 378. lVQ M. 2oo

13

Nuclear Magnetic Resonance Spectroscopy But But

._*

0 But

p =p

\ /

Ph2P,

,PPh2 C H2

R'

Co-ordination of L to Hg{PPh2[M(CO)5])2L,(L = Me2S0, bipy, or phen, M = Cr, Mo, or W) causes drastic changes in 1J(1g9Hg,31P)and chemical shifts to low frequencies.225The complete coupling parameters of (OC),W(Br,PPBr,)W(CO), have been deduced from the 183Wsatellite lines of the 31P n.m.r. spectrum.22sA series of mononuclear Moo species Mo(CO),, Mo(CO),L, cis-Mo(CO),L,, andfac-Mo(CO),L, exhibit 05M0n.m.r. resonances in the range - 1090 to - 1870 p.p.m. For [MOJ,CO)~~H]lJ(05Mo,lH) = 15 Hz.2279228 For Mo(CO),(PPh2XR) (X = 0 or NH) the steric effect of substitution at the ct-C of the R groups affects the chemical shifts of the aromatic C-1 13C,,lP, and 05M0 resonances but not the chemical shifts of the carbonyl 13Cand 170 resonances.229 The 183Wn.m.r. spectra of W(CO)6, W(CO),PPh3, and W(C0),PPhn(CH= CH2)3-, have been determined and cover a chemical-shift range of 210 ~ . p . m . ~ ~ O N.m.r. data have also been reported for (OC),CrPPh=PPhCr(CO), (31P),231 Cr(CO),[PCH(SiMe,),], (31P),232(24) (31P),233M(CO),P(C=CPh), (M = Cr or W; 31P),234 (OC),MRXPPRXM(CO), (M = Cr or W; 31P),235(OC),MP2M( c o ) ~ c o ~ ( c o(M ) ~= Cr or W; 31P),236(OC),M1PPh2C2H4PPh[M2(C0)61P. Peringer, Polyhedron, 1982, 1, 819. A. Hinke and W. Kuchen, Z. Naturforsch., Teil B, 1982,37, 1543 (Chem. Abstr., 1983,98, 100 182). 227 A. F. Masters, G. E. Bosbard, T. A. George, R. T. C. Brownlee, M. J. O'Connor, and A. G. Wedd, Inorg. Chem., i983, 22, 908. 228 E. C. Alyea and A. Somogyvari, Chem. Uses Molybdenum, Proc. Znt. Conf., 4th. 1982, 46 (Chem. Abstr., 1983, 99, 186 168). 229 G . M. Gray and R. J. Gray, Organometallics, 1983, 2, 1026. 280 R. L. Keiter and D. G. V. Velde, J. Organomet. Chem., 1983, 258, C34. 2s1 J. Borm, L. Zsolnai, and G. Huttner, Angew. Chem., Znt. Ed. Engl., 1983,22,977; Suppl., 1477. OS2 K. M. Flynn, H. Hope, B. D. Murray, M. M. Olmstead, and P. P. Power, J. Am. Chem. SOC.,1983,105, 7750. 233 H. W. Roesky and D. Amirzadeh-Asl, Z. Naturforsch., Teil B, 1983, 38, 460 (Chem. Abstr., 1983, 99, 105 346). 234 A. Hengefeld, J. Kopf, and D. Rehder, Organomerallics, 1983, 2, 114. 2s5 A.-M. Hinke, A. Hinke, and W. Kuchen, J. Organornet. Chem., 1983,258, 307. 336 H. Lang, L. Zsolnai, and G. Huttner, Angew. Chem., Int. Ed. Engl., 1983,22, 976; Suppl., 1463. 226

226

14

SpectroscopicProperties of Inorganic and Organometallic Compounds

M(CO),L (M = Cr or C2H,M3(CO), (M1, M2, M3 = Cr, Mo, or W; 31P),237 Mo, L = 2,4,6,8-tetramethyl-2,4,6,8-tetra-aza-1~3-5A3-diphosphabicyclo[3.3.0]octan-3,7-dione; 31P),238M(CO),Me2E1E2Me(El = P or As, E2 = S or Se, M = Cr, Mo, or W ; 31P),239 Mo(CO),P(tol), (,lP, 95Mo),240 PtMo(p-Ph,Ppy),I (P-CO)(CO)~CI~ ("P), 241 (25) (l 3C),242{ (OC)5 W[SC=CF(CFZ) 3CFJ }- (13C, 19F),243(OC),WTe=CPh, ( 3C),244and (OC) W[Ph,P==C(CN)CS,R] ( W , Up).246 I

,

0

..,Me

4~

0 (24)

The 13Cn.m.r. spectrum of Cr(CO),( 1,4,5,8-tetra-azaphenanthrene)has been assigned using selective lH d e c o ~ p l i n g For . ~ ~ ~c~s-Mo(CO),(PP~~X)~ good to excellent correlations between the 13Cand 170chemical shifts of the carbonyl ligands trans to the phosphovls donor ligands were found. The 13C and chemical shifts also correlln .e well. 31P chemical shifts were For Mo(CO),(PR~)~ a model cxplaining the relationship between changes in the x-donor character of the "-donor ligands and the observed 9 5 Mn.m.r. ~ chemical n.m.r. spectra of 38 complexes of the type cis- and shifts was ~ P ~ ~ S - W ~ ( C O ) ~have ( P Rbeen ~ ) L presented. A trans-effect series for octahedral Wo is SbPh, < AsPh, < PPh, P(OPh), < C0.249N.m.r. data have also been cis-M(CO),(subst. reported for Cr(CO),[Bu'N(BBu'),NBu'] ("B, 13C, 14N),250 bipy) (M = Cr, Mo, or W ; 13C, 15N, 95Mo),251M(C0),(2,2'-bipyrimidine) (M = Cr or W; 13C),252 M(C0)4(Ph2PCHRPPh2)(M = Cr, Mo, or W; 31P),253 Cr(C0)4(Me2PCH2PMe2) (31P),254 M(CO)JPh,P(CH,),PPh,] (13C, ,IP, 183W),255 R. L. Keiter, R. D. Borger, M. J. Madigan, S. L. Kaiser, and D. L. Rowley, Inorg. Chtm.

-

Acta, 1983,76, L5.

W.S. Sheldrick, H. W. Roesky, and D. Amirzadeh-Asl, Phosphorus Sulfur, 1983,14,161. a3e M. C.Boehm, R. Gleiter, J. Grobe, and D. Le Van, J. Organomet. Chem., 1983,247,203. 240 E. C. Alyea, G. Ferguson, and A. Somogyvari, Organometallics, 1983,2,668. 241 J. P. F u r , M. M. Olmstead, N. M. Rutherford, F. E. Wood, and A. L. Balch, Orguno238

a4a

metallics, 1983,2, 1758. K. H. Pannell, A. J. Mayr, R. Hoggard, J. S. McKennis, and J. C. Dawson, Chem. Ber.,

1983,116,230. R. J. Angelici and R. G. W. Gingerich, Organometallics, 1983,2,89. a44 H.Fischer and S . Zeuner, J. Organomet. Chem., 1983,252,C63. 245 U. Kunze, R. Merkel, and M. Moll, J. Organomet. Chem., 1983,248, 205. a48 N. Defay, D. Maetens, and R. Nasielski-Hinkens, J. Organomet. Chem., 1983,251, 317. 847 G.M.Gray and C. S. Kraihanzel, J. Organomet. Chem., 1983,241, 201. 248 G. M. Gray and C. S . Kraihanzel, Znorg. Chem., 1983, 22, 2959. a48 W.A. Schenk and W. Buchner, Znorg. Chim. Acta, 1983,70, 189. a50 K. Delpy, D. Schmitz, and P. Paetzold, Chem. Ber., 1983,116,2994. J. A. Connor and C. Overton, J. Organomet. Chem., 1983,249,165. K.J. Moore and J. D. Petersen, Polyhedron, 1983,2,279. a53 S. Al-Jibori and B. L. Shaw, Inorg. Chim. Acta, 1983,74,235. H . H.Karsch, Chem. Ber., 1983,116, 1643. 255 G. T. Andrews, I. J. Colquhoun, and W. McFarlane, Polyhedron, 1983,2, 783. 243

15


(26)

(26) (lac, 31P),26e[(OC),M(Ph,PO),H]- (M = Cr, Mo, or W; 31P),267 M(CO),[2-Me2PC,H,Si(PMea)Mea] (M = Cr, Mo, or W; M(CO),[(o-tOl)aPCH,P(o-tol),] (M = Cr, Mo, or W; 13C,31P),26e M(CO),P(OCH,),P], (M = Cr, Mo, or W; 31P),260 [Cp(CO)(Me,P)FeEMe,]Mo(CO), (E = As, Sb,or Bi; 31P),gd1 ~~Luzs-[(OC),MO(P~~PCH,)~PP~,]~R~(CO)C~ (31P),a62 and M(CO),[PPh,(CH,),SMe] (M = Mo or W; 31P).2e3 An n.m.r. spectrochemical series (PF, phosphite CO > aryl phosphine alkyl phosphine > MeCN > pyridine piperidine > N2 > NO) has been reported from the e 6 Mchemical ~ shifts in octahedral complexes. 1J(e6M~,31P) values contain information on the relative electron-donor abilities of the CO and N2 ligand~.~~, N.m.r. data have also been reported for Cr(+PhEPh2)(C0), (E = P or As; leF, 31P),aea(0C),Mo(P2[MeNC(0)NMe],},Mo(C0), (81P),Bb6 P(NPhPF,),Mo(CO), (lgF, 31P),M7M(CO)3(dmpe)S02(M = Cry Mo, or W; s1P),2e8Mo(CO),(PPh,),(CNR)(SO,) ( 1 7 0 , 31P),86e[C~CO(~-PR~O)~MO(CO)~], (31P),270 (C6Me6)MeRh( p-PMe2)aMo(CO)31 (31P),271 (Pri2NPO),MOa(CO)8 Mo(S,CNMe,)(OCMe)(CO)(PMe,), (13C),273WBra(CO)(R1C=CR2)[P(OMe),l2(31P),274 and [(Pr'O),W( p-CO)( p-OPri)W(OFV')2py]2(13C).276 The first high-resolution 1 7 0 n.m.r. spectra of peroxidic oxygen atoms bonded to transition metals are reported for Mo(CN),O(O,) and related A 'triple-resonance' experiment combining lH broad-band decoupling with

=-

--

-

K.H. Dotz, I. Pruskil, U. Schubert, and K. Ackermann, Chem. Ber., 1983, 116, 2337. E. H. Wong, F. C. Bradley, and E. J. Gabe, J. Organomet. Chem., 1983,244,235. as8 P. Aslanidis and J. Grobe, J. Organomet. Chem., 1983,219, 103. G.R. Clark and P. W. Clark, J. Organomet. Chem., 1983, 255, 205. P. M. Stricklen, E. J. Volcko, and J. G. Verkade, J. Am. Chem. SOC.,1983, 105, 2494. a61 D. Greissinger, W. Malisch, and H.-A. Kaul, J. Organomet. Chem., 1983, 2!52, C23. R. R. Guimerans, M. M. Olmstead, and A. L. Balch, Inorg. Chem., 1983, 22,2223. *uI R. D. Adams, C. Blankenship, B. E. Segmiiller, and M. Shiralian, J. Am. Chem. Soc., 467

1983, 105,4319. aa S. Donovan-Mtunzi, M. Hughes, G. J. Leigh, H. M. Ali, R. L. Richards, and J. Mason, J. Organomet. Chem., 1983, 246, C1. T. E. Bitterwolf, Polyhedron, 1983, 2, 675. H. W. Roesky, D. Aminadeh-Asl, W. Clegg, M. Noltemeyer, and G. M. Sheldrick, J. Chem. SOC.,Dalton Trans., 1983, 855. R. B. King and M. Shimura, J. Organomet. Chem., 1983, 256, 71. W. A. Schenk and F.-E. Baumann, J. Organomet. Chem., 1983,256,261. G . J. Kubas, G. D. Jarvinen, and R. R. Ryan, J. Am. Chem. Soc., 1983,105, 1883. *?OW. Klilui, A. Muller, and M. Scotti, J. Organomet. Chem., 1983,253, 45. a71 R. G. Finke, G. Gaughan, C. Pierpont, and J. H. Noordik, Organometallics, 1983,2, 1481. a7a E. H.Wong, M. M. Turnbull, E. J. Gabe, F. L. Lee, and Y.Le Page, J. Chem. SOC., Chem. Commun., 1983, 776. a78 E. Carmona, L. Shnchez, M. L. Poveda, J. M. Marin, J. L. Atwood, and R. D. Rogers, J. Chem. SOC.,Chem. Commun., 1983, 161. a74 J. L. Davidson and G. Vasapollo, Polyhedron. 1983, 2, 305. a75 F. A. Cotton and W. Schwotzer, J. Am. Chem. SOC.,1983, 105,4955. 976 M. Postel, C. Brevard, H. Arzoumanian, and J. G. Riess, J. Am. Chem. SOC.,1983, 105, 4922.


16

selective homonuclear decoupling has been developed and applied to the 31P n.m.r. spectra of M o ~ ( P E ~ ~ ) , C ~ , I , The - , . ~ 13C ~ ~ n.m.r. spectrum of PhN= WC1,(EtCN) shows that the nitrogen is strongly electron-withdrawing from the phenyl The 1 7 0 n.m.r. spectrum of Mo,05(Me,NCH2CHzNHCHzCH,S), shows three different oxygen 9 5 Mn.m.r. ~ studies have been reported on spin-coupled polynuclear systems of Mo", Mo", and Mo", e.g. (M030,[(02CCH2)zNMe]3 12-. The resonances occur at high frequency compared to mononuclear species.280g 5 Mn.m.r. ~ spectra of a series of compounds containing the fac-[Mov'03] and cis-[MoV'02] units have been reported and trends discussed. 13Cn.m.r. spectra were used to assist structure assignment.281v282 The heteropolyanions [P2M~18062]6and a- and p-[Pzw18062]6- were studied using 1 7 0 , 05M0, and lg3Wn.m.r. For MoXY(ONHR),, change of the terminal group from 0 to S to Se causes deshielding of g 5 Min~ the order 0 < S < Se.284The lS3Wchemical shift of W,(02CCF3), is 6760 p.p.m. with respect to [W0412--.The 19Fn.m.r. spectrum was also recorded.285The 31P n.m.r. spectrum of W2(0CH2But),(PMe3), shows J(31P,31P)= 5.4 Hz.~**The structures of [TizWloP040]7-and {[CpFe(CO),Sn],W 10P038}5-were determined using two-dimensional J-correlated le3Wn.m.r. ~ p e ~ t r ~ A~ ~ detailed ~ p y . ~ ~ assignment of the lg3W resonances has been made for ~iW11P04,J5-using J(183W,183W).288 la3W COSY and two-dimensional INADEQUATE have been used to determine the structure of Li7PW11039,Na7PWl103g,Na8SiW11039, and Na5PPbWl103g.289 N.m.r. data have also been reported for M(S,EMe,),(NO), (M = Cr, Mo, or W; E = P or As; 13C, 31P),290MO(N,)~(PM~,)~ (31P),29192B2 { Mo(NC,H 4 Me)[S,P(OEt)2lM P - W P-SH)( PM o ( N O ) ~ ( P P ~ ~ ) ~ (31P),2939294 CI, R. Nunlist and J. D. Arenivar, J. Magn. Reson., 1983, 52, 305. A. J. Nielson and J. M. Waters, A m . J. Chem., 1983, 36, 243. 278 C. P. Marabella, J. H. Enemark, K. F. Miller, A. E. Bruce, N. Pariyadath, J. L. Corbin, and E. I. Stiefel, Znorg. Chem., 1983, 22, 3456. 280S. F. Gheller, T. W. Hambley, T. T. C. Brownlee, M. J. O'Connor, M. R. Snow, and A. G. Wedd, J. Am. Chem. SOC.,1983, 105, 1527. 281 S. F. Gheller, T. W. Hambley, P. R. Traill, R. T. C. Brownlee, M. J. O'Connor, M. R. Snow, and A. G. Wedd, Aust. J. Chem., 1982, 35, 2183. S. F. Gheller, R. T. C. Brownlee, M. J. O'Connor, and A. G. Wedd, Chem. Uses Molybdenum, Proc. Znt. Conf., 4th, 1982, 67 (Chem. Abstr., 1983, 99, 186 169). 283 R. I. Maksimovskaya, M. A. Fedotov, and G. M. Maksimov, I n . Akad. Nauk SSSR, Ser. Khim., 1983, 247 (Chem. Abstr., 1983, 98, 136 436). 284 M. Minelli, J. H. Enemark, K. Wieghardt, and M. Hahn, Inorg. Chem., 1983, 22, 3952. 285 D. J. Santure, K. W. McLaughlin, J. C. Huffman, and A. P. Sattelberger, Znorg. Chem., 277

278

1983,22, 1877.

M. J. Chetcuti, M. H. Chisholm, J. C. Huffman,and J. Leonelli, J. Am. Chem. SOC.,1983, 105, 292. 287 288

P. J. Domaille and W. H. Knoth, Znorg. Chem., 1983, 22, 818. W. H. Knoth, P. J. Domaille, and D. C. Roe, Inorg. Chem., 1983, 22, 198. C. Brevard, R. Schimpf, G. Tourne, and C. M. Tourne, J . Am. Chem. SOC.,1983, 105, 7059.

291

M. Herberhold and L. Haumaier, Chem. Ber., 1983, 116, 2896. E. Carmona, J. M. Marin, M. L. Poveda, J. L. Atwood, and R. D. Rogers, Polyhedron,

282

E. Carmona, J. M. Marin, M. L. Poveda, J. L. Atwood, and R. D. Rogers, J. Am. Chem.

2g0

1983, 2, 185.

SOC.,1983, 105, 3014. 293

284

D. Ballivet-Tkatchenko, and C. Bremard, J. Chem. SOC.,Chem. Cummun., 1983, 1143. D. Ballivet-Tkatchenko, C. Bremard, F. Abraham, and G. Nowogrocki, J. Chem. SOC., Dalton Trans., 1983, 1137.


17

O2CCF3) ('OF, 31P),296 Mo~( /.L-Bu'~P)~(Bu'~P)~ (31P),2wMo(CO2)2(dp~)2(13C, 31P),207[W(SBu'),(PMe,Ph)],( P-S)~ (31P),298WCl4(PMeS), (31P)y20eW2C14(170),s01 [Mo202( P B u ~ )(13C, ~ 31P),300Moz06(Me2NCH2CH2NHCH2CH,S), (Sh)6(OMe)]- (06M0),302 (MoO[S2P(OPri),]),( pO)( pS)( pPy) (31P),303 MoE1E2(C6HloNO), (E = 0 or S; 13C, asM0),304[MOO(S~CNE~~)~]+ (13C, 31P),306 [(PhS)CuS2M~S212(06M0),30sMo(S,CPh), (13C),307 Mo2(S2CR2)4* 2THF (13C),308 H3PW12040-.n(02)n (31P),300 tungsten citrates (13C),310P-[P4W30M4(OH2)20112]16(M = Co, Cu, or Zn; 31P,183W),311 WOF,(butanediolate) (loF),,l2and WF,(2,4dinitrophenylhydrazinate)(10F).313

Complexes of Mn, Tc, and Re.-The 31Pn.m.r. spectrum of Mn,(CO),[pC(O)CH2N2](pdppm)ahas been analysed as [AB]2.314lH nuclear Overhauser enhancement measurements have been used to show which methyl group is deuteriated in [CpRe(NO)(PPh,)(CHCHMeCD,)]+.316 N.m.r. data have also been reported for Mn,(CO)4( p-dppm),( pH)(31P),316Mn,( pH)( p-PPh,)(CO),L (13C),317 [Re,H,(PPh,),(CNBu'),]+ (31P),318[R~,(P,-H),C(C~),,]~-(1sc),319

M. E. Noble, J. C. Huffman, and R. A. D. Wentworth, Znorg. Chem., 1983, 22, 1756. R. A. Jones, J. G. Lasch, N. C. Norman, B. R. Whittlesey, and T. C. Wright, J. Am. Chem. SOC.,1983, 105, 6184. 187 J. Chatt, W. Hussain, and G. J. Leigh, Transition Met. Chem., 1983,.8, 383. 208 J. R. Dilworth, R. L. Richards, P. Dahlstrom, J. Hutchinson, S. Kumar, and J. Zubieta, J. Chem. SOC.,Dalton Trans., 1983, 1489. E. Carmona, L. Shnchez, M. L. Poveda, R. A. Jones, and J. G. Hefner, Polyhedron, 1983, *85

2, 797.

R. R. Schrock, L. G. Sturgeoff, and P. R. Sharp, Inorg. Chem., 1983, 22, 2801. C. P. Marabella, J. H. Enemark, K. F. Miller, A. E. Bruce, N. Pariyadath, J. L. Corbin, and E. I. Stiefel, Inorg. Chem., 1983, 22, 3456. 30% I. Buchanan, W. Clegg, C. D. Garner, and G. M. Sheldrick, Znorg. Chem., 1983,22,3657. 303 M. G. B. Drew, P. J. Baricelli, P. C. H. Mitchell, and A. R. Read, J. Chem. SOC.,Dalton Trans., 1983, 649. 804 S . Bristow, D. Collison, C. D. Garner, and W. Clegg, J. Chem. SOC.,Dalton Trans., 1983, 3oo 301

2495. C. G. Young, J. A. Broomhead, and C. J. Boreham, J. Chem. SOC.,Dalton Trans., 1983, 2135. aoe S . R. Acott, C . D. Garner, J. R. Nicholson, and W. Clegg, J. Chem. SOC.,Dalton Trans., 1983,713. 307 J. Selbin, Znorg. Chim. Acta, 1983, 71, 201. 308 R. D. Bereman, D. M. Baird, and C. G. Moreland, Polyhedron, 1983, 2, 59. 306

L. I. Kuznetsova, R. I. Maksimovskaya, M. A. Fedotov, and K. I. Mateev, Zzv. Akad.

Nauk SSSR, Ser. Khim., 1983, 733. 310 Yu. K. Tselinskii, Koord. Khim., 1983, 9, 1495 (Chem. Abstr., 1983, 99, 219 724). 311

R. G. Finke and M. W. Droege, Znorg. Chem., 1983, 22, 1006.

31a

Yu. V. Kokunov, V. A. Bochkareva, and Yu. A. Buslaev, Koord. Khim., 1982, 8, 1567

(Chem. Abstr., 1983, 98, 64 639). S. G. Sakharov, Yu. V. Kokunov, M. P. Gustyakova, and Yu. A. Buslaev, Koord. Khim., 1982, 8, 1669 (Chem. Abstr., 1983, 98, 118 542). *14 G. Ferguson, W. J. Laws, M. Parvez, and R. J. Puddephatt, Organometallics, 1983,2, 276. 316 W. G. Hatton and J. A. Gladysz, J. Am. Chem. Soc., 1983, 105, 6157. 316 H.C. Aspinall and A. J. Deeming, J. Chem. SOC.,Chem. Commun., 1983, 838. 317 J. A. Iggo, M. J. Mays, P. R. Raithby, and K. Hendrick, J. Chem. SOC.,Dalton Trans., *13

1983, 205. 318 J. D. Allison and R. A. 319 G. Ciani, G. D'Alfonso,

244, C27.

Walton, J. Chem. SOC.,Chem. Commun., 1983, 401. P. Romiti, A. Sironi, and M. Freni, J. Organomet. Chem., 1983,


18

I Et

H\Re(C0)4

R~(T~-M~CH=CHCHO)(PP~,)~H(1°C)

320

(27) ('3C), 321 (OC)4MhPPh20CH2C(0)kH2 (31P),322CsF7M(C0), (M = Mn or Re; 13C, 10F),323 (OC)4Mn~HOA1Et2NBut~Ph2 (13C, 31P),324[(OC),MnS],(p-CR=CR) (10F),326 (C,H,Me)(CO),Mn=C(OMe)CMe=PEt, (13C, 31P),326 Cpde(C0)2CH2CH2CH2~H2 (13C)9327R ~ ( N B U ' ) ~ ( C H ~ S ~ M(13C),328 ~,), (q6C,H,)Re(NO)(PPh,)(COR) (13C),32 * Re2CI3(Ph2Ppy)2C8H4P(py)Ph(,lP), 30 Re(NO)(PMe,),C(O)kCH=CHCH=CH (13C, 31P),331[CpRe(NO)(PPh,)(H2C=O)]+ (13C),332 (OC),Re[ p C ( SiPh,)CO(OEt)]R~(CO),[C(OEt)SiPh,l (13C),333 (CF,),GeMn(CO), (l°F, 66Mn),334 Te,[Mn(CO),Cp], (13C),336CpMn(C0)2E=CH2Mn(CO)2Cp (E = S, Se, or Te; 13C),338s337 (q3-C6H7)Mn(CO), (13C),338 ~q3-cyclohexenyl)Mn(CO),P(OMe),(13C),33s (28) (llB, 13C),340 (C6Me5)2?

1

Baudry, J.-C. Daran, Y. Dromzee, M. Ephritikhine, H. Felkin, Y. Jeannin, and J. Zakrzewski, J. Chem. SOC.,Chem. Commun., 1983, 813. s21 M. Green, A. G. Orpen, C. J. Schaverien, and I. D. Williams, J. Chem. SOC.,Chem. Commun., 1983, 1399. 322 E. Lindner, K. A. Starz, N. Pads, and W. Winter, Chem. Ber., 1983, 116, 1070. 32a S. J. Doig, R. P. Hughes, S. L. Patt, D. E. Samkoff, and W. L. Smith, J. Organomet. Chem., 1983,250, C1. s24 D. L. Grimmett, J. A. Labinger, J. N. Bonfiglio, S. T. Masuo, E. Shearin, and J. S. Miller, Organometallics, 1983, 2, 1325. 326 E. Lindner, I. P. Butz, S. Hoehne, W. Hiller, and R. Fawzi, J. Organomet. Chem., 1983, 320 D.

259, 97.

W. Malisch, H. Bau, and U. Schubert, Chem. Ber., 1983, 116, 690. G. K. Yang and R. G. Bergman, J. Am. Chem. SOC.,1983, 105, 6500. 328 D. S. Edwards, L. V. Biondi, J. W. Ziller, M. R. Churchill, and R. R. Schrock, Orgunometallics, 1983, 2, 1505. 32s W. E. Buhro, A. Wong, J. H. Merrifield, G. Y. Lin, A. C. Constable, and J. A. Gladysz, Organometallics, 1983, 2, 1852. 330 T. J. Barder, S. M. Tetrick, R. A. Walton, F. A. Cotton, and G. L. Powell, J. Am. Chem. SOC.,1983,105, 4090. 331 C . P. Casey and J. M. O'Connor, J. Am. Chem. SOC.,1983, 105, 2919. 3s2 W. E. Buhro, A. T. Patton, C. E. Strouse, J. A. Gladysz, F. B. McCormick, and M. C. Etter, J. Am. Chem. SOC.,1983, 105, 1056. 333 E. 0. Fischer, P. Rustemeyer, 0. Orama, D. Neugebauer, and U. Schubert, J. Orgunomet. Chem. 1983,247, 7. 334 D. J. Brauer and R. Eujen, Organometallics, 1983, 2, 263. 335 M. Herberhold, D. Reiner, and D. Neugebauer, Angew. Chem., Znt. Ed. Engl., 1983,22,59. 336 M. Herberhold, W. Ehrenreich, and W. Buhlmeyer, Angew. Chem., Int. Ed. Engl., 1983, 328 s27

22, 315.

W. A. Herrmann, J. Weichmann, R. Serrano, K. Blechschmitt, H. Pfisterer, and M. L. Ziegler, Angew. Chem., Znt. Ed. Engl., 1983, 22, 314; Suppl., 363. 338 M. Leyendecker and C. G. Kreiter, J. Organomet. Chem., 1983, 249, C31. 33B M. Brookhart, W. Lamanna, and A. R. Pinhas, Organometallics, 1983, 2, 638. a40 G. E. Herberich, J. Hengesbach, G. Huttner, A. Frank, and U. Schubert, J. Organomet. Chem., 1983,246, 141. 337


19

Mn,(CO), (13C),,,l (C,H,)Mn(CO),CNMMe, (M = Si, Ge, or Sn; I3C),,,, (~6-C6H6)zMn2Fe2P2(CO)lo (31P),343 and ( Y ~ - C ~ H ~ ) , R ~ ~p(SC) O(13C).344 ),( The complexes (OC),MnS,CZ exhibit 66Mnchemical-shift ranges which allow classification with respect to the mode of co-ordination of the thio ligand and the ring size of the chelate structure.346l6N n.m.r. spectra of a series of nitrosyls such as [Mn(CO),(NO),]- have been observed.348N.m.r. data have also been reported for (o-C6H,0,),PMn(CO), (13C,31P),347 (OC)6MnSCR1=CR2SMn(CO)6 (13C),348[Re(CO),(NSF)]+ (10F),340 Re,(CO)lo-n(NCR),, (13C),,,0 [(OC),MnPPh,12- (13C, 31P),351[(OC),MnPF,], ('OF, 31P),352 (OC),BrMnPPh,COR (I3C, 31P),353Re,(CO),(PPh,), (13C, 31P),364 (OC),Mn(pdppm)PdX (31P),366,366 (OC),MnL(S,CSnPh,) (13C, 31P),357 RuMn(p-PPh,)(CO),(PPh,), (31P),368 380 (30) (13C),361 [Re(CO),(NCC,H,),Mn,Br,(CO),Se,Ph, (13C), (29) (13C,31P),

But

W. A. Herrmann, R. Serrano, and J. Weichmann, J. Organomet. Chem., 1983, 246, (257. H. Behrens, G. Landgraf, P. Merbach, M. Moll, and K.-H. Trummer, J. Organornet. Chem., 1983,253, 217. a43 H. Lang, L. Zsolnai, and G. Huttner, Angew. Chem., Znt. Ed,Engl., 1983,22, 976. 944 M. Herberhold, D. Reiner, and U. Thewalt, Angew. Chem., Znr. Ed. Engl., 1983,22, 1OOO. ao6 D. Rehder, R. Kramolowsky, K. G. Steinhaeuser, U. Kunze, and A. Antoniadis, Znorg. Chim. Acta, 1983, 73, 243. 848 R. E. Stevens and W. L. Gladfelter, Znorg. Chem., 1983, 22, 2034. M. Lattman, B. N. Anand, D. R. Garrett, and M. A. Whitener, Znorg. Chim. Acta, 1983, 76, L139. E. Lindner, I. P. Butz, W. Hiller, R. Fawzi, and S. Hoehne, Angew. Chem., Znr. Ed. Engl., 1983,22, 996; Suppl., 1388. a4O R. Mews and C.-s. Liu, Angew. Chem., Znt. Ed. Engl., 1983,22, 162. L. K. Peterson, R. S. Dhami, and F. Wada, Synth. React. Znorg. Met.-Org. Chem., 1983, 13, 291. a61 E. Lindner, K. A. Starz, H.-J. Eberle, and W. Hiller, Chem. Ber., 1983, 116, 1209. 862 H. Schaefer, J. Zipfel, B. Migula, and D. Binder, Z. Anorg. Allg. Chem., 1983, 501, 111. E. Lindner and D. Hubner, Chem. Ber., 1983, 116,2574. s64 S. W. Lee, L. F. Wang, and C. P. Cheng, J. Organomet. Chem., 1983,248, 189. B. F. Hoskins, R. J. S t a n , andT. W. Turney, Znorg. Chim. Acta, 1983,77, L69. P. Braunstein, J.-M. Jud, and J. Fischer, J. Chem. Soc., Chem. Commun., 1983, 5 . U. Kunze and T. Hattich, Chem. Ber., 1983, 116, 3071. S. Sabo, B. Chaudret, and D. Gervais, J. Organomet. Chem., 1983, 258, C19. J. L. Atwood, I. Bernal, F. Calderazzo, L. G. Canada, R. Poli, R. D. Rogers, C. A. Veracini, and D. Vitali, Znorg. Chem., 1983,22,1797. 8M) 0.J. Scherer, J. Kerth, and M. L. Ziegler, Angew. Chem., Znt. Ed. Engl., 1983, 22, 503. 361 0.J. Scherer and J. Kerth, J. Organomet. Chem., 1983, 243, C33. aol


20

C,H,]+ (13C),362 (OC),Re,( p-Br)2(p-R1R2NP=NR3) (13C, 31P),363 [Mn(catecho1ate),(NCMe),l2- (13C),364 and ReCl,(NO)(NPPh,)(OPPh,) (31P).365

Complexes of Fe, Ru, and 0s.-The ratio of the g'-factors of 9 8 Rand ~ lolRu A comprehas been measured accurately by the use of n.m.r. ~pectroscopy.~~~ hensive study of the ruthenium chemical-shift scale (9100 p.p.m.) has been N.m.r . data have also been reported for FeH(y2-CH2PMe2)(PMe,), (31P),368CpFe(CO)H(dppe) (31P),3s8FeH(CO)(NO)(PPh,), (31P),370 (C,Me,)FeH(CO)(PMe,) (31P),371CpFeH(Ph2PCH2CH2)2PPh(2H, 31P),372 (rl-C6H6)R1H(CH2CHMe~~i2) (l3c, 31P),374 Fe,(CO),(p,-MeCO)(p-H) (13C),373 CpRu(PPh,),H (31P),375 ci~-[M(bipy)~(CO)H]+ (M = Ru or 0 s ; 31P),376 MHCl(CO)(PPh,),L (M = Ru or 0 s ; 31P),377[(~-C,M~,)RUH,(PR,)]~ (31P),378 [HRu,(C0)11]- (13C),379Ru,(~-H)~[~~,~~-C(OE~)=~~CH](CO)~ (13C),380Au2Ru,(p-H)(~.,-COMe)(CO)g(PPh,), ("C, 31P),381 Ru,(~-H)Z(p-PPh2)2(CO)S (31P),382M,(CO),,(p-H)(p-EtCO) (M = Ru or 0 s ; 13C),383RU,(CO)~(~,-PR)( V - H ) ~(13C, 31P),384C ~ N ~ R U ~ ( C O )(13C),385 ~H, M1M2R~4(p3-H)2(CO)12(PPh,), (M1, M2 = Cu, Ag, or Au; 31P),386[H,RU,(CO)~~]-(13C),387Os2H4-

369

D. T. Plummer, G. A. Kraus, and R. J. Angelici, Inorg. Chem., 1983,22, 3492. 0.J. Scherer, J. Kerth, R. Anselmann, and W. S. Sheldrick, Angew. Chem., Znt. Ed. Engl.,

3(lrl

D. H. Chin, D. T. Sawyer, W. P. Schaefer, and C. J. Simmons, Inorg. Chem., 1983, 72,

36a

1983, 22, 984. 752.

N. Mronga, F. Weller, and K. Dehnicke, Z. Anorg. Allg. Chem., 1983, 502, 35. C. Brevard and 0. Lutz, 2. Phys. A , 1982, 309, 119 (Chem. Abstr., 1983, 98, 45 669). 367 C. Brevard and P. Granger, Inorg. Chem., 1983, 22, 532. 3M) H. Werner and J. Gotzig, Organometallics, 1983, 2, 547. 36g S. G. Davies, J. Hibberd, S. J. Simpson, and 0. Watts, J. Organomet. Chem., 1983, 241, 366 s66

C31.

J.-L. A. Roustan, A. Forgues, J.-Y. Merour, N. D. Venayak, and B. A. Morrow, Can. J. Chem., 1983,61, 1339. 371 W. Angerer, K. Fiederling, G. Grotsch, and W. Malisch, Chem. Ber., 1983, 116, 3947. 372 S. G. Davies, S. J. Simpson, H. Felkin, F. Tadj, and 0. Watts, J. Chem. SOC.,Dalton Trans., 1983, 981. s73 W.-K. Wong, K. W. Chiu, G. Wilkinson, A. M. R. Galas, M. Thornton-Pett, and M. B. Hursthouse, J. Chem. SOC.,Dalton Trans., 1983, 1557. s74 H. Kletzin and H. Werner, Angew. Chem., Znt. Ed. Engl., 1983, 22, 873. 376 S. G. Davies, S. D. Moon, and S. J. Simpson, J. Chem. SOC.,Chem. Commun., 1983, 1278. 376 J. V. Caspar, B. P. Sullivan, and T. J. Meyer, Organometallics, 1983, 2, 551. 377 C. J. Creswell, S. D. Robinson, and A. Sahajpal, Polyhedron, 1983, 2, 517. 378 H. Werner and H. Kletzin, J. Organomet. Chem., 1983, 243, C59. 37g A. A. Bhattacharyya, C. C. Nagel, and S. G. Shore, Orgunometallics, 1983, 2, 1187. 330 C. M. Jensen and H. D. Kaesz, J. Am. Chem. SOC.,1983, 105,6969. L. J. Farrugia, M. J. Freeman, M. Green, A. G. Orpen, F. G. A. Stone, and I. D. Salter, J. Organomet. Chem., 1983, 249, 273. 38a R. P. Rosen, G. L. Geoffroy, C. Bueno, M. R. Churchill, and R. B. Ortega, J. Organomet. Chem., 1983,254, 89. 383 C. E. Kampe, N. M. Boag, and H. D. Kaesz, J. Am. Chem. SOC.,1983,105,2896. S . L. Cook and J. Evans, J. Chem. SOC.,Chem. Commun., 1983,713. M. Castiglioni, E. Sappa, M. Valle, M. Lanfranchi, and A. Tiripicchio, J. Orgunomet. Chem., 1983,241, 99. 386 M. J. Freeman, M. Green, A. G. Orpen, I. D. Salter, and F. G. A. Stone, J. Chem. SOC., Chem. Commun., 1983, 1332. 387 P. Yarrow, H. Cohen, C. Ungermann, D. Vandenberg, P. C. Ford, and R. G. Rinker, J. Mol. Catal., 1983, 22, 239. 370

-


21

(PMeZPh), (31P),388{Os(phen)[1,2-(Ph2P),C6H4](PPh3)H}+(31P),38aOs,(CO),,(p-H -q2-CH=CH,) (13C),380 [HOS~(CO)~,(CHOM~)]- (13C),301 HO 3(CO)lo(S+NCH,CH,S) (13C),392 and (p-H)3(CO),0s,BC0 (llB, 13C).383 A 13C-labelling study using [(q-CsH6)Fe(13CO)(CO)CH2]+ has shown that reaction with CO yields [(q-C6Hs)Fe(13CO)(CO)CH2CO]+ rather than [(qCSHS)Fe(C0)2CH213CO]+.384 lH and I3Cn.m.r. spectra, including the use of E ~ ( h f c ) have ~ , been used to determine the chiral purity of (q6-csH@e(co)[P(OCH,),CMe]COEt.3D6lH, ,H, and 13Cn.m.r. spectroscopy has shown that when [CpFe(C0)L(q2-MeC=CC0,Me)]+ reacts with [DBEtJ-, to give CpFe(CO)L[C(COMe)=CHMe], the deuterium is in the cyclopentadienq-l ring.386 13Cand 31Pchemical shifts have been used to differentiate between three types of products formed from the reaction of amines with Fe,(CO),( p-PPh2)(pC=CR).397N.m.r. data have also been reported for Me,M[Me,P(CH2)nPMe2] (M = Fe or Co+; 31P),388 [(CH,SiMe,C,H,)Fe(CO),Me], (13C, 31P),39a(C,H,)Fe(CO),R (13C),400-402Fe(CF,CF,CF,),(CO), (leF),403 Fe(CHPhPPh,)(CO), (13C, 31P),404{Fe(q6-C,H,)(C0),[CH(SMe)(C,H,N)]}+ (13C),406{(C,H,)(CO),(13C),407 Fe[CH(SMe)PR,]}+ (13C, 31P),408(C,H,)Fe(CO),CH[CH2N(S02Me)],S (C,Me,)Fe(CO),CH,OH (l3C);O8 (C,H,)Fe(CO)[P(biphenyl),]CH,OEt (13C),409 (C,H,)Fe(CO)[P(OPh),][(E)-CMe=CMePh] (l3C),,lo (C,H,)Fe(CO)(PMe,)(13C, 1P),4 (C,H ,)Fe( CO)(PMe,) [C(O)CH=PMe,] [C(SiMe ,)=C=O]

388

389

M. A. Green, J. C. Huffman, and K. G. Caulton, J. Organomet. Chem., 1983,243, C78. J. V. Caspar, B. P. Sullivan, and T. J. Meyer, Report, 1982, DOE/ER/06034-T6, Order

No. DE83014995, 15 pp., avail. NTIS, from Energy Res. Abstr., 1983, 8, Abstr. No. 41 763 (Chem. Abstr., 1983, 99, 224 110). 390 J. Evans and G. S. McNulty, J. C' om. SOC.,Dalton Trans., 1983, 639. 3D1 J. R. Shapley, M. E. Cree-Uchiyama, G. M. St. George, M. R. Churchill, and C. Bueno, J. Am. Chem. SOC.,1983, 105, 140. s98 A. M. Brodie, H. D. Holden, J. Lewis, and M. J. Taylor, J. Organomet. Chem., 1983,253,

c1.

S . G. Shore, D.-Y. Jan, L.-Y. Hsu, and W.-L. Hsu, J. Am. Chem. SOC.,1983, 105, 5923. T. W. Bodnar and A. R. Cutler, J. Am. Chem. SOC.,1983,105,5926. T. C. Flood, K. D. Campbell, H. H. Downs, and S . Nakanishi, Organometallics, 1983, 2, 1590. 3s6 D. L. Reger, K. A. Belmore, J. L. Atwood, and W. E. Hunter, J. Am. Chem. SOC.,1983, 3g3 394

105, 5710. G. N. Mott and A. J. Carty, Znorg. Chem., 1983, 22, 2726. H. H. Karsch, Chem. Ber., 1983, 116, 1656. 399 K. D. Janda, W. W. McConnell, G. 0.Nelson, and M. E. Wright, J. Organomet. Chem., 1983, 259, 139. 400 M. E. Wright, Organometallics, 1983, 2, 558. 401 P. Lennon and M. Rosenblum, J. Am. Chem. Soc., 1983,105, 1233. 402 G. L. Trainor and B. E. Smart, J . Org. Chem., 1983, 48, 2447. I. I. Guerus and Yu. L. Yagupol'skii, J. Organomet. Chem., 1983, 247, 81. *04 H.Nakagawa, D. L. Johnson, and J. A. Gladysz, Organometallics, 1983, 2, 1846. 405 Y. S. Yu and R. J. Angelici, Organometallics, 1983, 2, 1583. 40e Y. S. Yu and R. J. Angelici, Organometallics, 1983, 1, 1018. 407 T. W. Leung, G. G. Christoph, and A. Wojcicki, Inorg. Chim. Acta, 1983,76, L281. 408 C. Lapinte and D. Astruc, J. Chem. Soc., Chem. Commun., 1983, 430. 4w J. E. Jensen, L. L. Campbell, S. Nakanishi, and T. C. Flood, J. Organornet. Chem., 1983, 244, 61. 410 D. L. Reger, K. A. Belmore, E. Mintz, N. G. Charles, E. A. H. Griffith, and E. L. Amma, Organometallics, 1983, 2, 101. 411 S. Voran and W. Malisch, Angew. Chem. Suppl., 1983, 114. 387


22

(31)

(13C, ,lP)9412 [(C,H,)Fe(CO)(PPh,)=CHR]+ (13C),413 [(C,H,)Fe(CO),CHOMe]+ (19F,31P),416 (13C),414[(C,H,)Fe(CO)(PR,)CR(OMe)]+[SO,F]-(13C, 19F, 31P),415 Fe(CO),(PPh,)CSC(CO,Me)=C(CO,Me)S (13C),417 { M[Fe(CO)4],}2- (M = Zn, Cd, or Hg ; 13C),418(C,H,)Fe(CO),SiMe,SiPh, (13C, 29Si),419 (C,H,)Fe(CO),SiHRCl (13C, 1°F, 31P),420(31) (13C, 31P),421Fe,(CO),(pPPh,)( pMeC0)(PMePh,) (13C, 31P),422Fe,(pROCS)( P - S M ~ ) ( C O ) ~ L(13C),423 ~L~ (32) (13C, 31P),424(33) (13C, 31P),425 FeCo(CO),(MeHCC,Et) (13C),426 [Fe,(CO)o(CC0)]2-

(32)

(33)

(13C),427HM,(p-CX)(CO),, (M = Fe, Ru, or 0 s ; 13C)94,* F~CO,(CO)~C,H, Ru(C,H,)Me(Ph,(13C),429 {Fe,Ag(CO),[CHC(NR1R2)Ph(PPh2)]]+ (31P),430 PCH,CHMePPh,) (31P),431Ru(C,H,)(CO),(CH,OH) (13C),432[Ru(CHO)(CO)(dppe),]+[BEt,]- (llB, 13C, 31P),433Ru(CO),[C(CO,R)=C(CO,R)C1]C1L2 (13C, 412

113 414 415

416

417 418

A. Stasunik and W. Malisch, J. Organomet. Chem., 1983, 247,C47. M. Brookhart, J. R. Tucker, and G. R. Husk, J . Am. Chem. SOC.,1983, 105, 258. C. P. Casey and W. H. Miles, J. Organornet. Chem., 1983, 254, 333, G. Grotsch and W. Malisch, J. Organomet. Chem., 1983, 246, C42. G. Grotsch and W. Malisch, J. Organomet. Chem., 1983, 246, C49. H. Le Bozec and P. H. Dixneuf, J. Chem. SOC.,Chem. Commun., 1983, 1462. B. A. Sosinsky, R. G. Shong, B. J. Fitzgerald, N. Norem, and C. O’Rourke, Inorg. Chem., 1983,22, 3124.

L. Phrkhnyi, K. H. Pannell, and C. Hernandez, J. Organomet. Chem., 1983, 252, 127. 420 W. Ries and W. Malisch, J. Organomet. Chem., 1983, 241, 321. 421H.Umland, F. Edelmann, D. Wormsbacher, and U. Behrens, Angew. Chem., Znt. Ed. Engl., 1983, 22, 153. 422 Y.-F. Yu, J. Gallucci, and A. Wojcicki, J. Am. Chem. SOC.,1983, 105, 4826. 423 A. Darchen, E. K. Lhadi, and H. Patin. J. Organomet. Chem., 1983,259, 189. 424 J. S. McKennis and E. P. Kyba, Organometallics, 1983, 2, 1249. 425 G. M. Dawkins, M. Green, J. C. Jeffery, C. Sambale, and F. G. A. Stone, J. Chem. SOC., Dalton Trans., 1983, 499. 426 S. Aime, D. Osella, L. Milone, and A. Tiripicchio, Pol-vhedron, 1983, 2, 77. 427 J. W. Kolis, E. M. Holt, and D. F. Shriver, J. Am. Chem. SOC.,1983, 105, 7307. 428 J. B. Keister, M. W. Payne, and M. J. Muscatella, Organometallics, 1983, 2, 219. 42g J. Ros and R. Mathieu, Organometallics, 1983, 2, 771. 430 G. N. Mott, N. J. Taylor, and A. J. Carty, Organometallics, 1983, 2, 447. 431 G. Consiglio, F. Morandini, G. Ciani, and A. Sironi, Angew. Chem., Int. Ed. Engl., 1983, 419

22, 333. 432

433

Y.C. Lin, D. Milstein, and S . S . Wreford, Organometallics, 1983, 2, 1461. G. Smith, D. J. Cole-Hamilton, M. Thornton-Pett, and M. B. Hursthouse, J. Chem. SOC., Dalton Trans., 1983, 2501.


23

lsF, 31P),434(C,H,)M(CH,=CHR)(PMe,) (M = Ru or 0 s ; 13C, 31P),43s [R'u(PPh3)(PPh,~,H4)(C,H4),](34) (13C, 31P),437 (CsH6)(CO),RuCH2(31P, Ru(CO),(C,H,) (13C),"* (C5Hs)Ru(SnC13)(Phs)(Ph2PCH2CHMePPh,) 119Sn),43 Ru 3(C0)9(CsCR)(PPh,) (13C, Ru sCl(CO)B(C2Ph)(l 3C),441 Ru3(y3-CR)(y-C0)3(CSH6)3 (13c),442 Ru2(CO)2(y-CO)(~-CCH2)(?S-C6H6)2 (13C),443 AU,R~~(~~-COM~)(CO)~(PP~~), (13C, 31P),444Os(CHO)(CO)(dppe), Ok(CO),(PPh,),C(SMe)CPh=CPh (13C),447 (31P),44s Os3(CO),,(CH,CO) (13C),446 OS~(CO)~(~-PP~,)(~-P~CCCNB~') (31P),448 and (C,Hs)W03(CO),(CR1)(CR2)H (13C).449 The lH n.m.r. spectra, including the natural-abundance 13C satellites, of Fe(q4-C4H,)(CO), and its monoiodo derivatives as well as the lH and ,Hn.m.r. spectra of the monodeuteriated compound oriented in various liquid crystals have been analysed. The time-averaged structure of the cyclobutadiene ring is square.4soN.m.r. data have also been reported for [Fe(CeHll)(nbd)(CO),]+ (13C),461{Me2Si[CSH4Fe(CO),(q2-CH,=CMe,)l, )2+ (13C),462 (35) (M = Fe or

Me

OR

/

R. Holland, B. Howard, and R. J. Mawby, J. Chem. Soc., Dalton Trans., 1983, 231. R. Werner and H. Werner, Chem. Ber., 1983, 116, 2074. IS6 R. Wilczynski, W. A. Fordyce, and J. Halpern, J. Am. Chem. SOC.,1983, 105,2066. 487 H.Lehmkuhl, J. Grundke, and R. Mynott, Chem. Ber., 1983,116, 176. Y . C. Lin, J. C. Calabrese, and S. S . Wreford, J. Am. Chem. SOC.,1983,105, 1679. 4sa G. Consiglio, F. Morandini, G. Ciani, A. Sironi, and M. Kretschmer, J. Am. Chem. SOC., 1983,105, 1391. uoR. A. Jones, T. C. Wright, J. L. Atwood, and W. E. Hunter, Organometallics, 1983,2,470. u1S . Aime, D. Osella, A. J. Deeming, A. M. M. Lanfredi, and A. Tiripicchio, J. Organomet. Chem., 1983, 244, C47. 441 N. J. Forrow, S. A. R. Knox, M. J. Morris, and A. G. Orpen, J. Chem. SOC., Chem. Commun., 1983, 234. 44s R. E. Colborn, D. L. Davies, A. F. Dyke, A. Endesfelder, S. A. R. Knox, A. G. Orpen, and D. Plaas, J. Chem. SOC.,Dalton Trans., 1983, 2661. 434 P.

444

L. W. Bateman, M. Green, K. A. Mead, R. M. Mills, I. D. Salter, F. G. A. Stone, and

446

P. Woodward, J. Chem. SOC.,Dalton Trans., 1983, 2599. G. Smith, D. J. Cole-Hamilton, M.Thornton-Pett, and M. B. Hursthouse, Polyhedron,

446

u7

1983, 2, 1241. E. D. Morrison, G. R. Steinmetz, G. L. Geoffroy, W. C. Fultz, and A. L. Rheingold, J. Am. Chem. SOC.,1983,105, 4104. G. P. Elliott and W. R. Roper, J. Organomet. Chem., 1983,250, C5. S . A. MacLaughlin, J. P. Johnson, N. J. Taylor, A. J. Carty, and E. Sappa, Organo-

metallics, 1983, 2, 352.

J. T. Park, J. R. Shapley, M. R. Churchill, and C. Bueno, J. Am. Chem. SOC.,1983, 105, 6182.

P. Diehl, F. Moia, H. Boesiger, and J. Wirz, J. Mol. Struct., 1983, 98, 297. 451 Y.Ishii, T. Kagayama, A Inada, and M. Ogawa, Bull. Chem. SOC.Jpn., 1983,56,2861. 468 W. W. McConnell, G. 0. Nelson, and M. E. Wright, Znorg. Chem., 1983, 22, 1689. 460

24

Spectroscopic Properties of Inorganic and Organometallic Compounds WCQ3 I

3 I

Fe (CQ3 (36)

Ru; 13C),453 R u~(CO)~(~-O=CCHCP~NE~~)(PP~~) (31P),454[(q6-C5H,)(CO)F e ( q 3 - C H 2 C b w d F 2 ) ] (13C),455 Fe(q3-kPhCPhCPh&O)(CO)(NO)L(13C),456 (36) (13C):67 [Fe(q4-MeCH=CHCH=CHCHMePPh3)(C0)3]+ (13C),458(37) (13C),45B (38) (13C),460 Fe(C0)2[P(OMe)3](q4-CBH7N2C6H4X) (13C, (39) (31P),462Fe(C4H2PPh2)2(31P),463 Fe,(C5H,)2(C&&t2) (13C),464 (q4-C,H&6H4)Fe(CO), (13C),465 (40)(13C, 31P)9466[Ru(nbd)(PPh3)(PPh3)(C5H5)]+ (13C, 31P),4a7 Ru(nbd)(CgHlo)(r3C),468 Ru( q4-c4H6)2(PF3) ("C, 1gF),46B and R U ( C O ) ~ ( C ~ ~ H ~ ~ ) (ClBHs00) (13C).470 The 13Cn.m.r. spectrum of (41) has been assigned using 293J(13C,1H)and T1.471 13C-{67Fe}double resonance has been used to determine 57Fen.m.r. chemical shifts for ferrocene derivatives, ct-ferrocenyl carbocations, and carbonyl complexes, and substantial chemical shifts, 1200 p.p.m., were found. The shifts were interpreted in terms of rehybridization of iron non-bonding d - ~ r b i t a l s . ~ ~ ~ As the cyclopentadiene rings in ferrocene derivatives are increasingly shifted from a parallel orientation, the 57Feresonance moves to lower f r e q u e n c ~ . ~ ~ ~ l ~ T.-a. Mitsudo, Y. Ogino, Y. Komiya, H. Watanabe, and Y. Watanabe, Organometallics, 1983, 2, 1202. 454 G. N. Mott, R. Granby, S. A. MacLaughlin, N. J. Taylor, and A. J. Carty, Organometallics, 1983, 2, 189. 455 C. M. Lukehart and K. Srinivasan, Organometallics, 1983, 2, 1640. 456 K.-J. Jens, T. Valeri, and E. Weiss, Chem. Ber., 1983, 116, 2872. 457 A. Hafner, J. H. Bieri, R. Prewo, W. von Philipsborn, and A. Salzer, Angew. Chem., Znt. Ed. Engl., 1983, 22, 713. 458 A. Salzer and A. Hafner, Helv. Chim. Acta, 1983, 66, 1774. 458 U. Hsnisch, E. Tagliaferri, R. Roulet, and P. Vogel, Helv. Chim. Acta, 1983, 66, 2182. 480 N. G. Connelly, A. R. Lucy, and J. B. Sheridan, J. Chem. SOC.,Dalton Trans., 1983, 1465. 481 N. G. Connelly, A. R. Lucy, and M. W. Whiteley, J. Chem. SOC.,Dalton Trans., 1983, I l l . dm E. Luppold and W. Winter, Chem. Ber., 1983, 116, 1923. 468 B. Lukas, R. M. G. Roberts, J. Silver, and A. S . Wells, J . Organomet. Chem., 1983, 256, 103. 4u4 K. Jonas, G. Koepe, L. Schieferstein, R. Mynott, C. Kruger, and Yi-H. Tsay, Angew. Chem., Znt. Ed. Engl., 1983, 22, 620. D. Kawka, P. Mues, and E. Vogel, Angew. Chem., Int. Ed. Engl., 1983, 22, 1003. 466 S. Holand, F. Mathey, J. Fischer, and A. Mitschler, Organometallics, 1983, 2, 1234. 467 R. U s h , L. A. Oro, M. A. Ciriano, M. M. Naval, M. C. Apreda, C. Foces-Foces, F. H. Cano, and S. Garcia-Blanco, J. Organomet. Chem., 1983, 256, 331. H. Nagashima, H. Matsuda, and K. Itoh, J. Organomet. Chem., 1983, 258, C15. 469 D. Minniti and P. L. Tims, J. Organomet. Chem., 1983, 258, C12. 470 G. Gervasio, E. Sappa, A. M. M. Lanfredi, and A. Tiripicchio, Inorg. Chim. Acta, 1983, 68, 171. 471 H.-W. Fruhauf, F. Seils, M. J. Romao, and G. J. Goddard, Angew. Chem., Int. Ed. Engl., 1983, 22, 992; Suppl., 1435. 47a A. A. Koridze, N. M. Astakhova, and P. V. Petrovskii, J. Organomet. Chem., 1983, 254, 345. 478 A. A. Koridze, N. M. Astakhova, P. V. Petrovskii, N. E. Kolobova, and E. I. Fedin, Zzr.Akad. Nauk SSSR, Ser. Khim., 1983, 1928 (Chem. Abstr., 1983, 99, 194 052). 474 E. Haslinger, K. Koci, W. Robien, and K. Schloegl, Monatsh. Chem., 1983, 114, 495. 45s


25

Ph-

(39)

The charge on the cyclopentadienyl ring has been estimated on the basis of l@F chemical shifts of p-FC,H,C,H, compounds of Fe, Ru, Os, Rh, and Pd. The charge ranges from -0.19 to -0.29.476 The electron densities in some ferrocene derivatives have been determined from 13Cchemical shifts.476N.m.r. data have also been reported for [(q5-C6H,PR3)Fe(CO),]+(l3CC,31P),477[Cp(OC),F&CH2CH2$]+ (13C),r178Fe,(~-CO),(CO),(C,H,), (l3C);" Fe2(C6H,SiMe2CsH4)( V-CO)~ [PhaP(CHJ nPPhe](' 3C, 'P) ," (7-C5H6)( CO),Fe( CJ&N 3) ("C),481 (~-C,H,)Fe(CO)(PMe,Ph)(coNHMe) ( ,C) ,482 P~[F~(CO)~(C&,)]S (31P)?83 N. A. Ogorodnikova and A. A. Koridze, Polyhedron, 1983, 2, 941. A. G.Nagy and S . Toma, Hung. Acad. Sci., Cent. Res. Inst. Phys., KFKZ, 1983, KFKI1983-55,19 pp. (Chem. Abstr., 1983,99, 195 185). 477 J. A. S. Howell and M.J. Thomas, J. Chem. Soc., Dalton Trans., 1983, 1401. 478 M. M. Sin& and R. J. Angelici, Angew. Chem., Znt. Ed. Engl., 1983, 22, 163. 479 P. Brun, G. M. Dawkins, M. Green, R. M. Mills, J.-Y. Salaiin, F. G. A. Stone, and P. Woodward, J. Chem. SOC.,Dalton Trans., 1983, 1357. M. E. Wright, T. M. Mezza, G. 0.Nelson, N. R. Armstrong, V. W. Day, and M. R. Thompson, Organometallics, 1983, 2, 1711. 481 M. Yu. Antipin, G. G. Aleksandrov, Yu. T. Struchkov, Yu. A. Belousov, V. N. Babin, and N. S . Kochetkova, Znorg. Chim. Acta, 1983,68, 229. 48a R. J. Angelici and T. Formanek, Znorg. Chim. Acta, 1983, 76, L9. 488 G. Fritz, K. D. Hoppe, W. Honle, D. Weber, C. Mujica, V. Manriquez, and H.G. v. Schnering, J. Organomet. Chem., 1983,249,63. p76

478


26

Fe(PhkH=CMeCMe=dH)]+ (13C),489 Fe(q5-C5H4SCH2CH2SC5H4-q5) (13C),490ferrocenylamines (13C),491ferrocene derivatives (13C),402(q-C5H5)9 3 Fe(q-C,H ,NRBMe), (llB),, 94 [(q-R1C5H4)Fe(q-k5H,CH,CH,&H,) (13C),4 Fe[-q-C5H,(OCH,CH,),0C5H4-q] (13C),498 (q-C,H,)Fe(C,H,PPhR2)], (31P),405 Fe(q-C,H,Ph,O Me) (13C),,97 (7pC5H,)Fe( -q-k5H,PPh,)RuCl,(PPh,)NMe,~H, (31P),408[l ,l]ferrocenophane and derivatives (13C),499(q-C,H,Li)Fe[q&5H,CHMeNMe,ti(trned)] (7Li),500{[(C5H5)Fe(C5H,)],P}[AlC14](27AI,31P),601 poly-1,l'-di-isopropenylferrocene (13C),502 [(q-arene)(q-C5H5)Fe]+ (13C),,03p 6 0 4 [(q-Ci,Hiz)(q-C5Me5)FeI+ (13c),505[ R ~ Z ( C O ) ~ ( ~ - C ~(l3C)96O8 H ~ ) ~ ] Ru2(C0)3+ (q-C6H6)(P3N3F4)(lgF, 31P),507(q-C5H5)RuCl(Ph2PCH2CHMePPh2) (31P),608 (q-C5H5)Ru[q-C5(C02Me)5] (13C),509(q-C5H5)OsC1(PPh,), (13C),510and {(qC,H,)OSIIP(O)(OMe),],}- (31p).511 484 485 486

R. A. Nissan, M. S. Connolly, M. G. L. Mirabelli, R. R. Whittle, and H. R. Allcock, J. Chem. SOC.,Chem. Commun., 1983, 822. H.-A. Kaul, D. Greissinger, W. Malisch, H.-P. Klein, and U. Thewalt, Angew. Chem., Int. Ed. Engl., 1983, 22, 60. V. W. Day, M. R. Thompson, G. 0. Nelson, and M. E. Wright, Organometallics, 1983,2, 494.

T . P. Gill and K. R. Mann, Inorg. Chem., 1983,22, 1986. 488 J. M. Shreeve and S. M. Williamson, J. Organomet. Chem., 1983, 249, C13. 489 D. Catheline and D. Astruc, J. Organomet. Chem., 1983, 248, C9. 490 M. Sato, H. Watanabe, S. Ebine, and S. Akabori, Chem. Lett., 1982, 1753 (Chem. Abstr., 487

1983, 98, 89 589). 4g1 402

493 4g4

M. Herberhold, M. Ellinger, and W. Kremnitz, J. Organomet. Chem., 1983, 241, 227. H. Paulus, K. Schlogl, and W. Weissensteiner, Monatsh. Chem., 1983, 114, 799. M. Hisatome, M. Yoshihashi, and K. Yamakawa, Tetrahedron Lett., 1983, 24, 5757. G. Schmid, U. Hohner, D. Kampmann, D. Zaika, and R. Boese, Chem. Ber., 1983,116, 951.

J. D. Fellmann, P. E. Garrou, H. P. Withers, D. Seyferth, and D. D. Traficante, Organometallics, 1983, 2, 818. 4g6 S. Akabori, Y. Habata, Y. Sakamoto, M. Sato, and S. Ebine, Bull. Chem. SOC.Jpn.,

495

1983, 56, 537-

R. Ferede and N. T. Allison, Organometallics, 1983, 2, 463. G. E. Rodgers, W. R. Cullen, and B. R. James, Can. J. Chem., 1983, 61, 1314. lgO V. K. Kansal, W. E. Watts, U.T. Mueller-Westerhoff, J. Organomet. Chem., 1983,243,443. 500 I. R. Butler, W. R. Cullen, J. Reglinski, and S. J. Rettig, J. Organomet. Chem., 1983, 249, 407 ,08

183. 502

S. G. Baxter, R. L. Collins, A. H. Cowley, and S. F. Sena, Inorg. Chem., 1983, 22, 3475. A. S. Chishti and C. R. Jablonski, Makromol. Chem., 1983, 184, 1837 (Chem. Abstr.,

503

C . C. Lee, A. Piorko, B. R. Steele, U. S. Gill, and R. G. Sutherland, J. Organomet. Chem.,

504

C. C . Lee, K. J. Demchuk, U. S. Gill, and R. G. Sutherland, J. Organomet. Chem., 1983,

501

1983, 99, 176 379). 1983, 256, 303. 247, 71.

V. Guerchais and D. Astruc, J . Chem. SOC.,Chem. Commun., 1983, 1115. M. Cooke, N. J. Forrow, and S. A. R. Knox, J. Chem. Soc., Dalton Trans., 1983, 2435. 507 H. R. Allcock, L. J. Wagner, and M. L. Levin, J. Am. Chem. Soc., 1983, 105, 1321. 508 F. Morandini, G. Consiglio, B. Straub, G. Ciani, and A. Sironi, J. Chem. SOC.,Dalton Trans., 1983, 2293. 500 M. I. Bruce, R. C. Wallis, M. L. Williams, B. W. Skelton, and A. H. White, J . Chem. SOC.,Dalton Trans., 1983, 2183. 510 M. I. Bruce, M. L. Williams, J. M. Patrick, and A. H. White, Aust. J. Chem., 1983, 36, 505

5w

1353. 511

U. Schubert, R. Werner, L. Zinner, and H. Werner, J. Organomet. Chem., 1983,253, 363.


27

31Pn.m.r. spectra habe been used to show that 2J(31P,31P)in trans-Fe(CO),(dppe), is ~ma11.61~ Chemical shifts and coupling constants have been derived for Fe,(CO),(p-PHMe), as [AXY3], from the lH and 31Pn.m.r. For 13C0complexed to an iron porphyrin, the mechanisms of spin-lattice relaxation are dominated by chemical-shift a n i s o t r ~ p yThe . ~ ~ 13C ~ n.m.r. spectrum of the carbonyls of R u ( C O ) ~ S ~ is P ~a, singlet even at - 115 OC.slsThe 19Fand ,lP n.m.r. spectra of R U ( P P ~ ~ ) ~ ( F ~ P O C have ~ Hbeen ~ ) C analysed ~ as [A,MX]2.S1s N.m.r. data have also been reported for Fe(CO)4PF[OC(CF3),CN], ('"F, (C6HzBut3)2P2Fe(C0)4(31P),K18(OC),Fe[(Me,Si)2NP===PN(SiMe3)2]Fe(CO), (31P),s1 (OC)$Fe[(Me,Si),HC]P=P[CH(SiMe ,),]Fe( C0)4 (13C, 31P),6z0 MeN(PF,),Fe(CO), (31P),621FeRh( p-PPh,)(CO),(PEt,), (31P),6e2(bipy)Fe(CO), (13C),Ka3 (bipy)Fe(CO),( p-CO),Fe(CO) (13C),K24 Fe,(CO),(SCH=CRS) (13C),0B6 (CKH,)Mn(CO),PRFe,(CO),L1L2 (31P),s26Fe,(CO),(PhAsCPh=AsPh) (13C),527 Fe,(CO),(S,CHCH,COMe) (13C),628 Fe2(CO),(SR), (13C),629Fe2(CO)6(PPhCI,) (31P),s30 Fe,(CO),,(CNBut) (13C),631 Fe,(CO),( p3-SBut)(pz-PPhz) (31P),K3a Fe,(CO),[ p3-SM(CO)J(p3-PR) (M = Cr or W; 31P),633 Fe,(CO),( p3-S)(p3-PR) (31P),K34~635 Fe3(CO)8[pz-+u-C6H4CHzN(N=CHPh)] (13C),636Fe,Te,(CO),-,(PPh,), (31P, 12KTe),637 (C,H,)COFe,Te,(CO), (12aTe),S38Fe,Rh,( p-PPh,),-

512

R. L. Keiter, A. L. Rheingold, J. J. Hamerski, and C. K. Castle, Organometallics, 1983, 2, 1635.

51s 514

51s 610 617 518 510

P. M.Treichel and D. J. Berg, J. Organomet. Chem., 1983, 243, 315. T. Perkins, J. D. Satterlee, and J. H. Richards, J. Am. Chem. SOC.,1983, 105, 1350. L. R. Martin, F. W. B. Einstein, and R. K. Pomeroy, Inorg. Chem., 1983, 22, 1959. J. W. Gilje, R. Schmutzler, W. S. Sheldrick, and V. Wray, Polyhedron, 1983, 2, 603. D. P. Bauer and J. K. Ruff, Inorg. Chem., 1983, 22, 1686. A. H. Cowley, J. E. KildufT, J. G. Lasch, N. C. Norman, M. Pakulski, F. Ando, and T. C. Wright, J . Am. Chem. SOC.,1983, 105, 7751. K. M. Flynn, B. D. Murray, M.M. Olmstead, and P. P. Power, J. Am. Chem. SOC.,1983, 105, 7460.

K. M. Flynn, M. M. Olmstead, and P. P. Power, J. Am. Chem. SOC.,1983, 105, 2085. R. B. King, T. W. Lee, and J. H. Kim, Inorg. Chem., 1983, 22, 2964. 522 D. A. Roberts, G. R. Steinmetz, M. J. Breen, P. M. Shulman, E. D. Morrison, M. R. Duttera, C. W. DeBrosse, R. R. Whittle, and G. L. Geoffroy, Organometallics, 1983, 2, 580

521

846.

518

H.-W. Friihauf, J. Chem. Res. ( S ) , 1983, 218. H.-W. Friihauf, J. Chem. Res. ( S ) , 1983, 216. D. Seyferth, G. B. Womack, and L.-C. Song, Organometallics, 1983, 2, 776. J. Schneider and G. Huttner, Chem. Ber., 1983, 116, 917. G. Sennyey, F. Mathey, J. Fischer, and A. Mitschler, Organometallics, 1983, 2, 298. D. Seyferth, G. B. Womack, L.-C. Song, M. Cowle, and B. W. Hames, Organometallics,

520

A. R. Butler, C. Glidewell, A. R. Hyde, J. McGinnis, and J. E. Seymour, Polyhedron, 1983,

52s 524 525

526 527

1983, 2, 928. 2, 1045. 530

R. La1 De, J. Organomet. Chem., 1983, 243, 331.

631

M. I. Bruce, T. W. Hambley, and B. K. Nicholson, J. Chem. SOC.,Dalton Trans., 1983: 2385.

A. Winter, L. Zsolnai, and G. Huttner, J. Organomet. Chem., 1983, 250, 409. A. Winter, I. Jibril, and G. Huttner, J. Organomet. Chem., 1983, 241, 259. 534 E. Lindner, G. A. Weiss, W. Hiller, and R. Fawzi, J. Organomet. Chem., 1983, 255, 245. E. Lindner and G. A. Weiss, J. Organomet. Chem., 1983, 244, C9. lab N. S. Nametkin, V. D. Tyurin, V. V. Trusov, and A. M. Krapivin, J. Organomet. Chem., s32 533

1983,254,243. 637 538

D. A. Lesch and T. B. Rauchfuss, Znorg. Chem., 1983, 22, 1854. L. E. Bogan, jun., D. A. Lesch, and T. B. Rauchfuss, J. Organomet. Chem., 1983,250,429.


28

(p-CO),(CO), (31P),539Fe,Te,(CO), (125Te),540 Fe,C(CO),,-,(PMe,), (13C),641 Fe(C0)(NO),PBut,(MMe3),-, (M = Si, Ge, or Sn; 13C, 31P, 119Sn),6r2 HN[PPh,Fe(CO)(NO),], (31P),543 (CO)(NO),FePPh(OCH2CH2)2NHFe(NO)21 (31P),644Rh3(CO)5(RNCHCNNRCOCH2COkH,) (13C),s46Ru(CO),(MeCN),(NC6H6)2(03SCF,)2 (19F),646 Ru(CO),R,(PMe,Ph), (13C),547 [RU(CO)~(R~PCH~Ru(CO),Cl,(RkH=CMeCMe=CH), (13C, CHaCHa)2PPh][BF& ('OF, 31P),5aa 31P),640 RuC~(CO),(COC~H~)(PP~& (13C),550 R U ~ ( C O ) ~ ( P ~ - P P(31P),6s1 ~~)Z RU,(CO)~[M~S~(PR,),] (31P),652M3(CO)1,-,(CNR), (M = Ru or 0 s ; 13C),653 RU~C(CO)~,(PM~P (13C, ~ , ) ~31P),554Ru,(CO),,( p-PPh,)( P6-P) (31P),555[Ru6N(CO)16]- (13C, 15N),556 and Os,(CO)l,(AuPEt,)(NCO) (13C).567*558

c;) SR > OR > organyls > halogens.2188N.m.r. data have been reported 2172

Y. Sasaki, M. Takizawa, and A. I. Popov, Tokyo Kogei Daigaku Kogakubu Kiyo, 1982, 5, 39 (Chem. Abstr., 1983, 99, 22 534).

G. Klebe, K. Hensen, and J. von Jouanne, J. Organomet. Chem., 1983, 250, 137. B. M. Mikhailov, M. E. Gurskii, and D. G. Pershin, J . Organomet. Chem., 1983,246, 19. 2175 B. M. Mikhailov, T. A. Shchegoleva, E. M. Shashkova, and V. G. Kiselev, J. Organomet. Chem., 1983, 250, 23. 2178 M. E. Gurskii, S. V. Baranin, A. S. Shashkov, A. I. Lutsenko, and B. M. Mikhailov, J. Organomet. Chem., 1983,246, 129. 2177 S. M. van der Kerk, P. H. M. Budzelaar, A. van der Kerk-van Hoof, G. J. M. van der Kerk, and P. von R. Schleyer, Angew. Chem., Int. Ed. Engl., 1983,22,48. 2178 H.-0. Berger and H. Noth, J. Orgunomet. Chem., 1983,250, 33. *17* C. D. Blue and D. J. Nelson, J. Org. Chem., 1983,48,4542. 2180 H. Klusik and A. Berndt, Angew. Chem.. Int. Ed. Engl., 1983, 22, 877. llel C. D. Blue and D. J. Nelson, J. Org. Chem., 1983, 48,4538. *leaB. M. Mikhailov and K. L. Cherkasova, J. Organomet. Chem., 1983, 246, 9. a183 H. C. Brown and P. K. Jadhav, J. Am. Chem. Soc., 1983,105,2093. *lE4 R. Appel and W. Paulen, Chem. Bet., 1983,116, 109. A. J. Ashe, tert., S. T. Abu-Orabi, 0.Eisenstein, and H. F. Sandford, J. Org. Chem., 2173 2174

1983,48,901. ,lac

*le7

B. Wrackmeyer, C. Bihlmayer, and M. Schilling, Chem. Ber., 1983, 116, 3182. H. C. Brown, D. Basavalah, and N. G. Bhat, Organometallics, 1983, 2, 1468. R. H. Cragg and T. J. Miller, J. Organomet. Chem., 1983, 241, 289.

122


for (PhCH=NBMe,), (11B),218e CH,(CH,BR),NMe (11B),21go R2R3B1 (N2C3H2R1),BR2R3 (lOB, 11B),21e1 Me,C=kBEt,OBEtO (11B),2182 and Ph2BNR=CHC6H40(llB, 13C).21 N.m.r. data 13C n.m.r. spectra of (102) have been completely

R I

R I

0

\

0

B I

R

I R

(103)

have also been reported for ArBN,PhAr (llB, 1gF),21esR1N(CH,CH20)2BR2 (llB, 13C),21gs I'hMe2CH,C6H,B(0H), (11B),21e7 EtB(OR), (13C),2108 Bu"B(OPr'), (11B),21e0 CsHl3B(OCH2),CH2(llB, 13C),2200 (103) ("B, 13C),,,01 (104) (llB, 13C),2202 (R1B0)3NR23(11B),,,03 O(PhBONR)2CH2 (11B),2204 PhB(OCHR)2PPh (31P),2206 CF2=C(BF,)CF, (1gF),220 R1CH=CR2BXY 6 (llB, 13C),2207 and (n-hexyl)BBr, (llB).2208 The INEPT 16N n.m.r. spectrum of B(NHMe)3 has been recorded, and lJ(16N,11B)is ca. -45 B203has been used as a lH and 13Cshift reagent 2189

J. R. Jennings, R. Snaith, M. M. Mahmoud, S. C. Wallwork, S. J. Bryan, J. Halfpenny,

E. A. Petch, and K. Wade, J. Organomet. Chem., 1983, 249, C1. 2190

21s6

21s6

W. Haubold, A. Gemmler, and U. Kraatz, Z. Anorg. Allg. Chem., 1983, 507, 222. K. Niedenzu and H. Noth, Chem. Ber., 1983, 116, 1132. W. Kliegel, D. Nanninga, S. J. Rettig, and J. Trotter, Can. J. Chem., 1983, 61, 2329. E. Hohaus, Z. Anorg. Allg. Chem., 1983, 506, 185. S. Alloud, H. Bitar, M. El Mouhtadi, and B. Frange, J. Organomet. Chem., 1983,248,123. P. Paetzold and R. Truppat, Chem. Ber., 1983, 116, 1531. R. Contreras, C. Garcia, T. Mancilla, and B. Wrackmeyer, J. Organornet. Chem., 1983, 246, 213.

M. Lauer and G. Wulff,J. Organomet. Chem., 1983, 256, 1. R. Koster, K. Taba, and W. V. Dahlhoff, Annalen, 1983, 1422. H. C. Brown and T. E. Cole, Organometallics, 1983, 2, 1316. 2200 H. C. Brown and T. Imai, J. Am. Chem. SOC.,1983, 105, 6285. 2201 M. Yalpani, R. Koster, and G. Wilke, Chem. Ber., 1983, 116, 1336. 2202 M.Yalpani and R. Koster, Chem. Ber., 1983, 116, 3332. 2203 M. Yalpani and R. Boese, Chem. Ber., 1983, 116, 3347. 2204 W. Kliegel, J. Organomet. Chem., 1983, 253, 9 220s B. A. Arbuzov, 0. A. Erastov, G. N. Nikonov, I. P. Romanova, R. P. Arshinova, and R. A. Kadyrov, Zzv. Akad. Nauk SSSR, Ser. Khim., 1983, 1374 (Chem. Abstr., 1983, 99, 21s7

21s8

175 913). 2206

R. D. Wilson, W. Maya, D. Pilipovich, and K. 0. Christe, Organometallics, 1983, 22,

2207

R.-J. Binnewirtz, H. Klingenberger, R. Welte, and P. Paetzold, Chem. Ber., 1983, 116,

1355. 1271.

H. C. Brown, D. Basavalah, and N. G. Bhat, Organometallics, 1983, 2, 1309. 220Q B. Wrackmeyer, J. Magn. Reson., 1983, 54, 174.

2208


123

for a-D-glucose.2210N.m.r. data have also been reported for CH2(CH2NR)2B(NaC8Ha)ZH ("B, 13C),2211[(CF3)2CHO]But2PBC13("F, 31P),2212[(1,5-M%-2Ph-3H-pyrazol-3-0ne),B]~+[SbCl 6] (llB, 3C),2213 B[OTeF,(OMe)], ("B, lgF, 126Te),2214 boromycin (13C),2215 (AcO)2B(4-acetyl-3-methyl-l-phenyl-2-pyrazolin5-one) (11B),2216 BCl, adducts of POR1R22(llB, 13C,31P),2217 [BOC(0)CR1R201](11B),z21e B(OCH2CsHaCH20)SB (11B),221s(SCH&HaS)B(OC6HaCH=NCeH,SH) (11B),2220 B2F4 (llB, 1*F),2221 cyanopyridine BX8 (X = F or Br; 11B),2222 and H2BoC1,(11B).2223

,-

Complexes of Other Group IIIB Elernent~.-~~Aln.m.r. spectroscopy has been used as a probe for three-, four-, five, and six-co-ordinate aluminium in organoaluminium compounds.2224The 13C, 170,and 27Al n.m.r. chemical-shielding tensors have been calculated for the Al+/CO complex.2a26N.m.r. data have also been reported for [AlH ,R]- (27Al),2226 AIR 3( bipy) (13C),2227 [Me,AlN(CH=CH),CMeCMe(CH=CH)2NA1Me3]2- (13C, 27A1),222s[Me,AlNC,H,Me], (lac, 27Al),a22B [R2MN(PPh2)2]2 (M = A1 or Ga; 13C, 31P),2230 R2T1+complexes with an 'N6' macrocyclic ligand (13C),2231Me2{dibenzo[b,k](1,4,7,10,13,16-hexaoxacyclo-0ctadecin))Tl (13C),2232 and R2TIX and RTIX, (13C).223s 2oaTln.m.r. spectroscopy has been shown to monitor the occupancy of the two available sites for thallium binding to t r a n ~ f e r r i n . ~ ~ ~ ~ H. Asaoka, Carbohydr. Res., 1983, 118, 302 (Chem. Abstr., 1983, 99, 105 593). F. Alam and K. Niedenzu, J. Organomet. Chem., 1983,243, 19. D. Dakternieks and G.-V. Roschenthaler, Z. Anorg. Allg. Chem., 1983, 504, 135. E. Akguen, Chem.-Ztg., 1982, 106, 371 (Chern. Absrr., 1983, 98, 82 717). aa14 W. Toetsch, H. Aichinger, and F. Sladky, Z. Naturforsch., Teil B, 1983, 38, 332 (Chem. Abstr., 1983, 98, 190 624). 2216 H. G. Floss, C. J. Chang, T. S. S. Chen, and C. P. Gorst-Allman, Chern. Nut. Prod., Proc. Sino-Am. Symp., 1980, 1982, 135 (Chem. Abstr., 1983, 98, 175 942). 221s Y . Singh, S. Saxena, and A. K. Rai, Indian J. Chem., Sect. A , 1983, 22, 298 (Chem. Abstr., 1983, 99, 32 198). aa17 R. Bravo and J. P. Laurent, J. Chem. Res. (S), 1983, 61. a218 D. Boyer, L. Lamand6, B. Garrigues, and A. M u o z , Phosphorus Sulphur, 1983, 14, 335. V. J. Heintz, W. A. Freeman, and T . A. Keiderling, Znorg. Chem., 1983, 22, 2319. a*ao L. Bhal, R. V. Singh, and J. P. Tandon, Synth. React. Znorg. Met.-Org. Chem., 1983, 13, aalo

613.

W. Haubold and P. Jacob, 2. Anorg. Allg. Chem., 1983, 507, 231. D. R. Martin, J. U. Mondal, R. D. Williams, J. B. Iwamoto, N. C. Massey, D. M. Nuss, and P. L. Scott, Inorg. Chim. Acta, 1983, 70, 47. m8D. A. Saulys, N. A. Kutz, and J. A. Morrison, Inorg. Chern., 1983, 22, 1821. R. Benn, A. Rufinska, H. Lehmkuhl, E. Janssen, and C. Kriiger, Angew. Chem., Int. Ed. Engl., 1983, 22, 179. **a6 T. Weller, W. Meiler, H. J. Koehler, H. Lischka, and R. Hoeller, Chem. Phys. Lett., 1983, 98, 541. Pa*(

V. V. Gavrilenko, M. I. Vinnikova, V. A. Antonovich, and L. I. Zakharkin, Zzv. Akud.

aaa7

Nauk SSSR, Ser. Khim., 1982, 2367 (Chem. Abstr., 1983,98, 126 186). A. Yu. Fisenko, V. A. Grindin, B. A. Ershov, A. I. Kol'tsov, A. G. Boldyrev, E. B. Milovskaya, and E. P. Skvortsevich, Zh. Obshch. Khim., 1983, 53, 483 (Chem. Abstr., 1983, 98, 198 316).

*asa W. E. Dorogy, jun. and E. P. Schram, Znorg. Chim. Acta, 1983,73, 31. ***O W. E. Dorogy and E. P. Schram, Znorg. Chim. Acta, 1983, 72, 187. *maH. Schmidbauer, S. Lauteschlager, and B. Milewski-Mahrla, Chem. Ber., 1983,116, 1403. Y.Kawasaki and N. Okuda, Chem. Lett., 1982, 1161. J. Crowder, K. Hendrick, R. W. Matthews, and B. L. Podejma,J. Chem. Res. (S), 1983,82. F. Brady, R. W. Matthews, M. M. Thakur, and D. G. Gillies, J. Organomet. Chem., 1983, 252, 1.

I. Bertini, C. Luchinat, and L. Messori, J. Am. Chem. Soc., 1983, 105, 1347.

124


The interactions of A13+with the carbonylated headgroups of K dodecanoate contained in a bilayer membrane have been studied by 27Aln.m.r. N.m.r. data have also been reported for T1' with gramicidin (13C, 205Tl),2236 [ClA(NMeSiMe,),NMe], (13C, 27Al, 29Si),2237 (Et2N)2PCl=NPhAlC13 (27Al, 31P),2238 R1R2SiNButA1C13(27Al,29Si),2239 Al(OPr'),. en (27Al),2240 [A11304(OH)24' (27A1),2246 A1CI3 complex (OH2)1217- (27A1),2241-2244 [Ge04A112(0H)24(OH2)12]8complexes with tetramethyl-1,4-benzoquinone (13C),2246C,Me,OH-AlBr, (a7A1),2247 Al(S2CNR2)3(13C, 27Al),2248 molten InCl, (11aIn),224e and [(Rl2W2P= CR'J+[AIClJ- (27Al,31P).2260

7 Group IVB Elements One review has appeared: 'Solution-state n.m.r. studies of Group IV elements (other than carbon)'.2251Regression analysis for 13C, 29Si, l19Sn, and 207Pb chemical shifts shows a reasonable 13C/29Sishift correlation, Y = 0.825, a very shift correlation, good 2eSi/119Snshift correlation, Y = 0.990, and 119Sn/207Pb r = 0.975. In the latter two cases the observed shift ratios correspond fairly closely to the < r d 3 > nP ratios for the element pairs.2252 The dependences of 29Si chemical shifts of Si2Ph6-,C1,, Si,Ph,-,H,, and Si2Cl,+nH, have been measured.225313C n.m.r. spectra of Ph,GeH,-, and PhnGeH3_.Na as well as (p-tol),GeM have been assigned. Comparison of the chemical shifts with those of analogous Group VB compounds has demonstrated that the extent of delocalization of the negative charge of the germyl anions into the aromatic rings is significantly less than that found in the anions of A. S. Tracey and T. L. Boivin, J . Am. Chem. Soc., 1983, 105, 4901. G . L. Turner, J. F. Hinton, R. E. Koeppe, jun., J. A. Parli, and F. S. Millett, Biochim. Biophys. Acta, 1983, 756, 133 (Chem. Abstr., 1983, 98, 156 671). U. Wannagat, T. Blumenthal, D. J. Brauer, and H. Burger, J . Organomet. Chem., 1983, 249, 33. 2238 M. Sanchez, M. R. Marre, J. F. Brazier, J. Bellan, and R. Wolf, Phosphorus Sulphur, 1983, 14, 331. 2239 W. Clegg, U. Klingebiel, J. Neemann, and G . M. Sheldrick, J . Organomet. Chem., 1983, 249, 47. 2240 J. P. Laussac, R. Enjalbert, J. Galy, and J. P. Laurent, J . Coord. Chem., 1983, 12, 133. 2235 2236

D. L. Teagarden, J. F. Kozlowski, J. L. White, J. F. Radavich, and S. L. Hem, Trav. Corn. Int. Etude Bauxites, Alumine Alum., 1982, 17, 267. 2242 J. Y. Bottero, S. Partyka, and F. Fiessinger, Thermochim. Acfa, 1982, 59, 221 (Chem. Abstr., 1983, 98, 41 688). 2243 D. L. Teagarden, S. L. Hem, and J. L. White, J . SOC. Cosmef. Chem., 1982, 33, 281 (Chem. Absfr., 1983, 98, 40 407). 2244 S. Schoenherr, J. Goerz, R. Bertram, D. Muller, and W. Gessner, 2. Anorg. Allg. Chem., 1983,502, 113. S. Schonherr and H. Gorz, 2. Anorg. Allg. Chem., 1983, 503, 37. 2246 Z. Florjakzyk and E. Szymanska-Zachara, J. Organomet. Chem., 1983, 259, 127. 2247 V. I. Mamatyuk, N. F. Salakhutdinov, I. K. Korobeinicheva, and V. A. Koptyug, Zh. Org. Khim., 1982, 18, 2114 (Chem. Abstr., 1983, 98, 71 357). 2248 H. Noth and P. Konrad, Chem. Ber., 1983, 116, 3552. 2249 W. W. Warren, jun,, G . Schoenherr, and F. Hensel, Chem. Phys. Lett., 1983,96, 505. 2250 R. Appel and R. Schmitz, Chem. Ber., 1983, 116, 3521. 2251 R. K. Harris, NATO Adv. Study Inst. Ser., Ser. C, 1983, 103, 343 (Chem. Abstr., 1983, 99, 132 397). 2252 T. N. Mitchell, J. Organomet. Chem., 1983, 255, 279. 2253 H. Soellradl and E. Hengge, J. Organomet. Chem., 1983, 243, 257. 2245

125


phenyl-substituted phosphines and a r ~ i n e s .N.m.r. ~ ~ ~ ~data have also been reported for H2diCH2CH=CHCH2dH2 (13C),2265[H,SiO], (2gSi),2266 Me,SiSiH2Cl (13C, 29Si),2257 C,H,(CH,Bu')SiHPh (13C),2258k,H,Me,CHaSiH(C6H2Me3) (13C),226g (HMe,Si),CH, (FMe,Si),CH (13C, 19F, 29Si),2260 and HF2SiCH=CButSiF,0CBut=CH2(13C, 19F).2261 A previously derived equation has been extended to 2gSin.m.r. studies with A simple method for the estimation of atomic charges Me,Si and (Me3Si)20.2262 in organosilicon compounds by the cross-correlation of 13C, 1 7 0 , and ,@Si chemical shifts with atomic charges has been elaborated.2263 From lH and 13Cn.m.r. spectra of R,MCH,CH=CHMe (M = C, Si, Ge, Sn, or Pb) the group electronegativity sequence was estimated.2es4A modified selective population-transfer experiment has been described and applied to 29Si in Me,SiCH=CH,.2265 A very good linear correlation between 13C n.m.r. chemical shifts of vinyl carbon atoms and electronic absorption maxima of polysilylethylenes has been established.2266 The 13C and 29Sin.m.r. spectra of Me,SiCH,,CH,Si(CH,CH,),N confirm the existence of a large inductive effect in the silatrane ring.2267 N.m.r. data have also been reported for Me,SiC=CC(0)MMe3 (M = Si, Ge, or Sn; 13C),2268 MMe4-,(3-fury1). (M = Si, Ge, Sn, or 1 pb; 13C, 29Si, l19Sn 207Pb),2269 (105) (13C),2270 (mesityl),SiSi(mesityl)C=CPhSiMe, 9

Me2

Ph

SiMe, Si Me,

R. J. Batchelor and T. Birchall, J. Am. Chem. SOC.,1983, 105, 3848. R. T. Conlin and R. S. Gill, J. Am. Chem. SOC.,1983,105, 618. 2256 D. Seyferth, C. Prud'homme, and G. H. Wiseman, Inorg. Chem., 1983,22,2163. 2a57 N. S. Hosmane, S. Cradock, and E. A. V. Ebsworth, Znorg. Chim. Acta, 1983, 72, 181. 2258 P. R. Jones, M. E. Lee, and L. T. Lin, Organometallics, 1983,2, 1039. 326g W.Ando, Y. Hamada, and A. Sekiguchi, J. Chem. Soc., Chem. Commun., 1983, 952. zB60 C. Eaborn, P. B. Hitchcock, and P. D. Lickiss, J. Organomet. Chem., 1983, 252, 281. Y.-B. Lu and C.4. Liu, J. Organomet. Chem., 1983, 243, 393. R. Radeglia and A. Porzel, 2. Chem., 1983, 23, 253 (Chem. Abstr., 1983,99, 195 073). 2a6a L. Maijs, L a t v . P S R Zinar. Akad. Vestis, Kim. Ser., 1982, 646 (Chem. Abstr., 1983, 98, 2264

2266

107 385). a2w E. Matarasso-Tchiroukhine and P. Cadiot, Can. f. Chem., 1983, 61, 2476.

H. J. Jakobsen, P. J. Kanyha, and W. S . Brey, J. Magn. Reson., 1983, 54, 134. H. Sakurai, H. Tobita, and Y . Nakadaira, Chem. Lett., 1982, 1251. 2267 S. N. Tandura, Yu. A. Strelenko, M. G. Voronkov, N. V. Alekseev, and 0 . G. Yarosh, Dokl. Akad. Nauk SSSR, 1982, 267, 397 (Chem. Abstr., 1983, 98, 160 790). 22e8 K. J. H. Kruithof, R. F. Schmitz, and G. W. Klumpp, J. Chem. SOC.,Chem. Commun., a265

1983, 239. 2a60

N. P. Erchak, A. Asmane, J. Popelis, and E. Lukevics, Zh. Obshch. Khim., 1983, 53, 383

2270

(Chem. Abstr., 1983, 99, 53 874). T. J. Barton and G. P. Hussmann, Organometallics, 1983, 2, 692.


126

(29si),2271 (106) (13C),2272 (C5H4SiMe3)2Pb(13C),2273 (Me,Si),CHP(NSiMe,)(CHSiMe,) (13C, ,’Si, 31P),2274 [(Me,SiCH,),MC1C(C,,H8)]- (M = Si, Ge, or Sn; 13C, 29Si, 31P),2276 [PC(SiMe3),], (13C, 31P),2276 (Me,Si),CPHPClC(SiMe,), (31P),2277 Me,SiCH=PR(NSiMe,),PR=CHSiMe, (13C, 31P),2278 (Me,Si),CHP= P(mesity1) (31P),2279 R2PCC1(SiMe,), (13C, 31P),2280 (Me,Si),HCM=P(mesityI) (P[C(SiMe,),]Ph,H}+ (13C,31P),2282 (Me,Si),CPHPClC(M = As or Sb; 31P),2281 (SiMe,), (31P),2283[(Me,Si),CH],PH ( W , 31P),2284(2,4,6-But,C,H,)P=PC(SiMe,), (13C, 31P),2285(Me,Si),CP=AsC(SiMe,), (31P),2286and Me,SiR (13C),2287-2302 (13C, 29Si).2303 The 29Sichemical shifts of R1,-,,R2,,SiSiR13-,R2, (R = H, C1, or Ph) have M. Ishikawa, H. Sugisawa, M. Kumada, T. Higuchi, K. Matsui, K. Hirotsu, and J. Iyoda, Organometallics, 1983, 2, 174. 2272 G. Mark1 and M. Horn, Tetrahedron Lett., 1983, 24, 1477. 2273 P. Jutzi and E. Schluter, J. Orgunomet. Chem., 1983, 253, 313. 2274 E. Niecke, M. Leuer, D.-A. Wildbredt, and W. W. Schoeller, J. Chem. SOC., Chem. Commun., 1983,1171. 2275 I. V. Borisova, N. N. Zemlyanskii, Yu. N. Luzikov, Yu. A. Ustynyuk, V. K. Bel’skii, N. D. Kolosova, M. M. Shtern, and I. P. Beletskaya, Dokl. Akad. Nauk. SSSR, 1983, 269, 369 (Chem. Abstr., 1983, 99, 105 383). 2276 E. Niecke, R. Ruger, M. Lysek, S. Pohl, and W. Schoeller, Angew. Chem., Int. Ed. Engl., 1983, 22,486; Suppl., 639. 2277 J. Escudie, C. Couret, H. Ranaivonjatovo, J. Satge, and J. Jaud, Phosphorus Sulphur, 2271

1983, 17, 221.

Z.-M. Xie and R. H. Neilson, Organometallics, 1983, 2, 1406. 2279 A. H. Cowley, J. E. Kilduff, S. K. Mehrotra, N. C. Norman, and M. Pakulski, J. Chem. SOC.,Chem. Commun., 1983, 528. 2280 R. Appel, M. Huppertz, and A. Westerhaus, Chem. Ber., 1983, 116, 114. 2281 A. H. Cowley, J. G. Lasch, N. C. Norman, M. M. Pakulski, and B. R. Whittlesey, J. Chem. SOC.,Chem. Commun., 1983, 881. 2282 C. Eaborn, N. Retta, and J. D. Smith, J. Chem. SOC.,Dalton Trans., 1983, 905. 2283 A. H. Cowley, J. E. Kilduff, N. C. Norman, M. Pakulski, J. L. Atwood, and W. E. Hunter, J. Am. Chem. SOC.,1983, 105, 4845. 2284 A. H. Cowley and R. A. Kemp, Znorg. Chem., 1983, 22, 547. 2285 A. H. Cowley, J. E. Kilduff, M. Pakulski, and C. A. Stewart, J. Am. Chem. SOC.,1983, 2278

105, 1655. 2286

J. Escudie, C. Couret, H. Ranaivonjatovo, and J.-G. Wolf, Tetrahedron Lett., 1983, 24, 3625.

G. Maier, M. Hoppe, and H. P. Reisenauer, Angew. Chem., Znt. Ed. Engl., 1983, 22, 990. 2288 E.A. Chernyshev, 0. V. Kuz’min, A. V. Lebedev, A. I. Gusev, M. G. Los, N. V. Alekseev, N. S. Nametkin, V. D. Tyurin, A. M. Krapivin, N. A. Kubasova, and V. G. Zaikin, J. Organomet. Chem., 1983,252, 143. G. Felix, J. Dunogues, M. Petraud, and B. Barbe, J . Organomet. Chem., 1983, 258, C49. 2290 T. J. Barton and G. P. Hussmann, J. Am. Chem. SOC.,1983, 105, 6316. 2291 E.4. Negishi and J. A. Miller, J. Am. Chem. SOC.,1983, 105, 6761. 2292 B. Ciommer and H. Schwarz, J. Organomet. Chem., 1983,244, 319. 2293 R. T. Conlin, Y.-W. Kwak, and H. B. Huffaker, Organometallics, 1983,2,343. 2294 S . D. Burke, S. M. S. Strickland, and T. H. Powner, J. Org. Chem., 1983, 48, 454. 2296 H. J. Reich, M. J. Kelly, R. E. Olson, and R. C. Holtan, Tetrahedron, 1983, 39, 949. 2a96 R. L. Danheiser, D. J. Carini, D. M. Fink, and A. Basak,-Tetrahedron, 1983,39, 935. 22B7 L. A. Paquette, G. L. Wells, K. A. Horn, and T.-H. Yan, Tetrahedron, 1983,39,913. 2298 A. L. Meyers, K. A. Babiak, A. L. Campbell, D. L. Comins, M. P. Fleming, R. Henning, M. Heuschmann, J. P. Hudspeth, J. M. Kane, P. J. Reider, D. M. Roland, K. Shimizu, K. Tomioka, and R. D. Walkup, J. Am. Chem. SOC.,1983,105, 5015. 229B B. M. Trost and D. M. T. Chan, J. Am. Chem. SOC.,1983,105,2315. 2300 B. M. Trost and D. M. T. Chan, J. Am. Chem. SOC.,1983,105,2326. 2301 G. Wickham and W. Kitching, Organometallics, 1983, 2, 541. 2302 L. A. Paquette, P. Charumilind, and J. C. Gallucci, J. Am. Chem. SOC.,1983, 105, 7364. 2303 J. Otera, T. Mandai, M. Shiba, T. Saito, K. Shimohata, K. Takemori, and Y. Kawasaki, J . Organomet. Chem., 1983, 2, 332. 2287


127

been interpreted in terms of the electronegativity of the substituents R1 and R2.2304 Bridge silicon atoms in [2.2.1] bicyclic systems, e.g. (107), display unusually large 29Sid e ~ h i e l d i n gN.m.r. . ~ ~ ~ ~data have also been reported for Me,Si(CH,CH,OH), (13C),2306 M e , m M e , (13C, 29Si),2307 Me,SkH,CRPhCH,kRPh ( W , 29Si),2309 Cl,H,SiMeR (13C, (13C),2308C4HzPhzSiMe(CHz),SiMeC4HzPhz Ph,MeSiCHCH=CHCH,CHRkH, ("'9 zgsi),2311 SOSi),2310 R2M~=CCMe2CHeSCHa~Mez (M = Si or Ge; 13C),2312 NpPhMeSiCHClMe (13C, 29Si),2313 Me,diSiMe,C=CSiMe,SiMe,C=k (13C, 29Si),2314 (PhMeSi) , (13C),2315[(CH,),Si], (13C, 2gSi),2316 EtzS(iEt2SiEt,SiEt,SiCR1=~R2 (13C),2317 (Et,Si), (13C, 2BSi),2318Si3R6 (13C),2319 (Ph,M), (M = Si, Ge, or Sn; 13C, 119Sn),2320 and (2,6-Me,C,H3),S~i(2,6-Me,C,H3),(13C).2321

The effect of X on ll9Sn shifts has been discussed for Me3SnC(CH2CH2)3CX.aaza 6(lleSn), S(13C), and 2~3J(11gSn,117Sn) have been determined for Me,SnCH2SnMe,NEt,, (Me,Sn),-,N,Me,, and (Me,Sn),N,Ph. The coupling constants are highly sensitive to one-pair interactions, with 2J(11gSn,11gSn) covering a large range (> 500 H2).232313Cand lleSn n.m.r. spectra of 34 compounds containing R. Radeglia and G. Engelhardt, J. Organomet. Chem., 1983,254, C1. H. Sakurai, Y. Nakadaira, T. Koyama, and H. Sakaba, Chem. Lett., 1983,213. a30e J. A. Soderquist and A. Hassner, J, Org. Chem., 1983, 48, 1801. 2304

4306

M.Kira, K. Sakamoto, and H. Sakurai, J. Am. Chem. Soc., 1983, 105, 7469. aso8H.Watanabe, J. Inose, T. Muraoka, M. Saito, and Y. Nagai, J. Organomet. Chem., 1983,244, 329. a309 a310

H. Sakurai, A. Nakamura, and Y. Nakadaira, Organometallics, 1983, 2, 1814. M.Ishikawa, T. Tabohashi, H. Sugisawa, K. Nishimura, and M.Kumada, J. Organomet. Chem., 1983, 250, 109. B. Laycock, W. Kitching, and G. Wickham, Tetrahedron Lett., 1983,24, 5785. A. Krebs and J. Berndt, Tetrahedron Lett., 1983, 24, 4083. G. L. Larson, S. Sandoval, F. Cartledge, and F. R. Froncdk, Organometallics, 1983, 2, 8 10.

a314

H. Sakurai, Y. Nakadaira, A. Hosomi, Y. Eriyama, and C. Kabuto, J. Am. Chem. Soc., 1983, 105, 3359. S.-M. Chen, L. D. David, K. J. Haller, C. L. Wadsworth, and R. West, Organometallics, 1983,2, 409.

C. W. Carlson, X.-H. Zhang, and R. West, Organometallics, 1983,2,453. C. W. Carlson and R. West, Organometallics, 1983, 2, 1801. p318 C. W. Carlson and R. West, Organometallics, 1983, 2, 1792. 4318S. Masamune, H. Tobita, and S . Murakami, J. Am. Chem. Soc., 1983,105,6524. M. DrZLger, B. Mathiasch, L. Ross, and M. Ross, Z. Anorg. Allg. Chem., 1983,50699. S . Masamune, S. Murakami, H. Tobita, and D. J. Williams, J. Am. Chem. Soc., 1983, 105, 7776. a3aa

W. Adcock, G. B. Kok, A. N. Abeywickrema, W. Kitching, G. M. Drew, H. A. Olszowy, and I. Scott, J. Am. Chem. SOC.,1983, 105, 290. T. Gasparis-Ebeling, H. Noth, and B. Wrackmeyer,J. Chem. SOC.,Dalron Trans., 1983,97.

128


N.rn.r. data have the Sn-C-Sn group have been presented and also been reported for RCH=C(SnMe,), (13C, 119Sn),2325 RCH=CISnMe, (11BSn),2326 Me,SnC1,-,CH,SnMe,C13-m (13C),2327 4-Me3Sn(pinene) (13C),2328 (Me,Sn),CHCH,CH,X (13C, 11QSn),2329 Me,SnR (13C),2330 Me,Sn(CH,),CMe, (13C),2331 RnSn(C=CH)4-, (13C, 119Sn),2332 Et2Sn[CH2CH2P(X)R1R2],("P, 11BSn),2333 EtOCH2SnBun, (119Sn),2334 o-Bu,SnC,H,OSiMe, (,lP, 11BSn),2336 Bu',Sn(acac), (11gSn),2336 Bu"Sn(CPh=CPh,), (13C),2337 RSnPh, (11BSn),233a Sn(CPh=CMe,), (13C),2339 [CSH4P(NPriz)2]zSn (l3CC,31P),2340 Ph,Sn(CH,CH,CH,CH,),SnPh, (13C),2341 Ph,SnCH=C=CPhH (13C),2342 CH,(SnPh,SnPh,),CH, (11BSn),2343 and p-FC6H4CH2SnR3(19F).2344 The 29Sin.m.r. spectra of (RO),Me,-,SiNHC,H,X-g have been discussed in terms of relative paramagnetic screening constants.234513C n.m.r. data for PhOMR, (M = Si, Ge, or Sn) have indicated that orbital overlap of the 2pelectrons on oxygen with the x-system of the benzene ring is practically independent of steric The influence of variable polarizability effects of (RO),Me,-,Si on the Hammett's correlation of 6(NH) of (RO)nMe,-nSiNHC,~ ~ . ~ ~ ~ ~ 6(2QSi) ~ ~ exhibits ~ ~ a~ H4X has been ~ ~ s c u sFors Me3SiOk=CR(CH2)i T. N. Mitchell, A. Amamria, B. Fabisch, H. G. Kuivila, T. J. Karol, and K. Swami, J. Organomet. Chem., 1983,259, 157. 2325 T. N. Mitchell and A. Amamria, J. Organomet. Chem., 1983,252,41. 2326 T. N. Mitchell and A. Amamria, J. Organomet. Chem., 1983, 256, 37. 2327 T. J. Karol, J. P. Hutchinson, J. R. Hyde, H. G. Kuivila, and J. A. Zubieta, Organometallics, 1983, 2, 106. 2328 A. N. Bakunin, I. P. Beletskaya, and 0. A. Reutov, Zh. Org. Khim., 1982, 18,2233 (Chem. Abstr., 9183, 98, 107 567). 232g H. G. Kuivila, T. J. Karol, and K. Swami, Organometallics, 1983, 2, 909. 2330 D. Yound and W. Kitching, Tetrahedron Lett., 1983, 24, 5793. 2331 J. W. F. L. Seetz, G. Schat, 0. S. Akkerman, and F. Bickelhaupt, J. Am. Chem. SOC., 1983, 105, 3337. 2332 B. Wrackmeyer, Z . Nuturforsch., Ted B, 1982, 37, 1524 (Chem. Abstr., 1983,98, 160 850). 2333 H. Weichmann and B. Rensch, Z. Anorg. Allg. Chem., 1983, 503, 106. 2334 J.-P. Quintard, B. Elissondo, and D. Mouka-Mpenga, J. Organomet. Chem., 1983, 251, 175. 2335 J. Heinicke, E. Nietzschmann, and A. Tzschach, J. Organomet. Chem., 1983, 243, 1. 2336 J. Otera, T. Yano, and K. Kusakabe, Bull. Chem. SOC.Jpn., 1983,56, 1057. 2337 C. J. Cardin, D. J. Cardin, R. J. Norton, H. E. Parge, and K. W. Muir, J. Chem. SOC., Dalton Trans., 1983, 665. 2338 M. Gielen, Bull. SOC.Chim. Belg., 1983, 92, 409. 2339 C. J. Cardin, D. J. Cardin, J. M. Kelly, R. J. Norton, A. Roy, B. J. Hathaway, and T. J. King, J. Chem. SOC.,Dalton Trans., 1983, 671. 2340 A. H. Cowley, J. G. Lasch, N. C. Norman, C. A. Stewart, and T. C. Wright, Organometallics, 1983, 2, 1691. 2341 M. Newcomb, Y. Azuma, and A. R. Courtney, Organometallics, 1983, 2, 175. 2342 K. Ruitenberg, H. Westmijze, J. Meijer, C. J. Elsevier, and P. Vermer, J. Organomet. Chem., 1983,241, 417. 2343 J. Meunier-Piret, M. Van Meerssche, M. Gielen, and K. Jurkschat, J. Organomet. Chem., 1983,252, 289. 2344 S . I. Pombrik, A. S. Peregudov, E. I. Fedin, and D. N. Kravtsov, Zzv. Akad. Nauk SSSR, Ser. Khim., 1982, 2375 (Chem. Abstr., 1983,98, 126 266). 2345 J. Pikies, A. Herman, and W. Wojnowski, 2. Anorg. Allg. Chem., 1983, 498, 218. 2348 L. B. Krivdin, G. A. Kalabin, R. G. Mirskov, and S. P. Solov'eva, Izv. Akad. Nauk SSSR, Ser. Khim., 1982, 2038 (Chem. Abstr., 1983,98, 54 058). 2347 L. B. Krivdin, G. A. Kalabin, R. G. Mirskov, and N. K. Yarosh, Zzv. Akad. Nauk SSSR, Ser. Khim., 1982,2829 (Chem. Abstr., 1983,98, 126 273). 2348 J. Pikies and W. Wojnowski, Z. Anorg. Allg. Chem., 1983,503, 224. 2324


129

strong dependence on the ring size.2349N.m.r. data have also been reported for (Me3Si),NPRC1 (13C, 31P),2350(C6HzBu',)P(OMe)NHSiMe, (31P),2351 (Me,Si),NPRH (13C, 31P),2362 Me,SiP[N(SiMe,),], (13C, 31P),2363 Me,SiNHCMe(13C, 29Si),2364 Me,SiNBu'CH=CHNHBu' (13C),2365 (Me,Si),=CHCR=O NP=PN(SiMe,), (13C, 29Si, 31P),2356Me,Si[N(SiMe,)],Si(NHSiMe,), (13C, 2BSi),2367 R1,PNX(MRZ3)(M = C, Si, or Ge; 31P),23s8[(Me,Si),N],PR (13C, 31P),2369 Me,SikPBu'(=NSiMe,)PBu'(=NSiMe,)fiBu (31P),23eo [(CF,),AsCIN(SiMe,)], (19F),2361 PhP=C[NR(SiMe,)]PPhSiMe, (13C, 31P),2362 Me,Si(PBu'),SiMe, (31P),2363 P(SiMe,SiMe,),P ( T i , 31P),2364 P4B~t2(SiMe3)2 (31P),2366 Lip,(SiMe,), (31P),23e6 P,(SiMe,), (31P),2367 Me3Si derivatives of @-D-xylopyranoside R3SiOC6H,R2( W , (29Si),2368 Me,Si derivatives of galactopyranosides (29SQ,2369 170),2370 silicone resins (29Si),2371 Me,SiO&PPhPPhC(OSiMe,)=CH(CH,),(!'H 1

(13C, 31P),2372Me,SiOk=C(OSiMe,)PRPR (13C, 31P),2373trimethylsilylated silicic acid (13C, 29Si),2374 Me,SiOR (13C),2375-2381 (13C, 29si),2382,2383(2 9Si),2384,2385 J. Schraml, J. Sraga, and P. Hrnciar, Org. Magn. Reson., 1983,21, 73, X.M.Xie and R. H. Neilson, Organometallics, 1983,2,921. 2351 V. D. Romanenko, A. V. Ruban, and L. N. Markovski, J. Chem. SOC.,Chem. Commun., 2349

2360

1983, 187.

H. R. O'Neal and R. H. Neilson, Znorg. Chem., 1983,22,814. V. D. Romanenko, V. F. Shul'gin, V. V. Scopenko, and L. N. Markovski, J . Chem. Soc., Chem. Commun., 1983,808. 2364 T. Pro11 and W. Walter, Chem. Ber., 1983, 116, 1564. 2366 H. tom Dieck, B. Bruder, and K.-D. Franz, Chem. Ber., 1983, 116, 136. 2866 E. Niecke and R. Ruger, Angew. Chem., Znt. Ed. Engl., 1983,22, 155. a3s7 H. Burger, W. Geschwandtner, and G. R. Liewald, J. Organomet. Chem., 1983, 259, 145. 2358 I. F. Lutsenko, V. L. FOSS, Yu. A. Veits, and T. E. Chernykh, Vestn. Mosk. Univ., Ser. 2: Khim., 1982,23, 593 (Chem. Abstr., 1983,98, 143 539). 2359 B.-L. Li, J. S. Engenito, jun., R. H. Neilson, and P. Wisian-Neilson, Znorg. Chem., 1983, 2362

22, 575. 2360

E. Niecke, R. Ruger, B. Krebs, and M. Dartmann, Angew. Chem., Znt. Ed. Engl., 1983, 22, 552.

R. Bohra, H. W. Roesky, J. Lucas, M. Noltemeyer, and G. M. Sheldrick, J . Chem. SOC., Dalton Trans., 1983, 1011. 2982 R. Appel, F. Knoch, B. Laubach, and R. Sievers, Chem. Ber., 1983,116, 1873. M. Baudler, G. Reuschenbach, and J. Hahn, Chem. Ber., 1983, 116, 847. 2w K. Hassler, J. Organomet. Chem., 1983, 246, C31. 2366 G. Fritz, J. Harer, and K. Stoll, Z. Anorg. Allg. Chem., 1983, 504, 47. 33w G. Fritz, J. Harer, and E. Matern, 2. Anorg. Allg. Chem., 1983, 504, 38. 8887 G. Fritz and J. Harer, Z. Anorg. Allg. Chem., 1983, 504, 23. J. Schraml, E. Petrikova, 0. Pihar, J. Hirsch, and V. Chvalovskf, Org. Magn. Reson., 2881

1983, 21, 666.

D. J. Gale and N. A. Evans, Org. Magn. Reson., 1983, 21, 567. 2370 E. Liepins, I. Zicmane, E. Lukevics, E. I. Dubinskaya, and M. G. Voronkov, Zh. Obshch. Khim., 1983, 53, 1092 (Chem. Abstr., 1983, 99, 88 263). 2371 H. Jancke, G. Engelhardt, and H. Grosse-Ruyken, J. Organomet. Chem., 1983, 247, 139. 2372 R. Appel, J. Hunerbein, and F. Knoch, Angew. Chem., Znt. Ed. Engl., 1983, 22, 61. 2373 R. Appel, V. Barth, and F. Knoch, Chem. Ber., 1983,116,938. H. Inoue and S. Kohama, J. Appl. Polym. Sci., 1983, 28, 2499 (Chem. Abstr., 1983, 99, 2369

88 678).

E. L. Clennan and R. P. L'Esperance, Tetrahedron Lett., 1983,24,4291. 2376 A. Sakarai and Y. Okumura, Bull. Chem. SOC. Jpn., 1983,56, 542. a377 K. G. Gasanov, V. S. Akhmedov, N. G. Radzhabov, E. G. Airapetov, and F. A. Alimirzoev, Azerb. Khim. Zh., 1982, 47 (Chem. Abstr., 1983, 99, 212 571). 2378 J. Schraml, E. PetrBkovB, 0. Pihar, J. Hirsch, and V. Chvalovsky, Collect. Czech. Chem, Commun., 1983, 48, 1829. 2379 P. L. Rinaldi and R. G. Salomon, J. Org. Chem., 1983, 48, 3182. 2876


130

Me,Bu 'SiOR (l ,C), MeOSi Me2R (13C),,,* PhaPI (CH,).SiMe,Cl (13C,31P),2380 Me2&XCH2ZCR(0)(Z = 0 or NR; 1°F, 20Si),a3so (R1R2SiF),kSiMe,NButN=CMe (13C, 1°F, 20Si),2391 Me(RFP)31P),a303 CSiMe,NBu'N=&Me ('OF, 31P),2302 RMe,SiCF,SiMe,F (13C, leF, Me,ShBu'NH=CMeCH, (13C, 20Si),2304(ButMe,Si),O (13C),230s(Me0)PhSiMeCH,CH,Bu' (13C),2306 Ph,SiMeOAc (13C),2307S(SiEt,SiEt,),S (13C, 20Si),2308 and [Me,SiF,]- (13C).2300 For some four- and five-co-ordinate Ph,Sn-containing compounds the llsSn chemical shifts and 1.1(110Sn,13C) depend markedly on the co-ordination number. 13C, 14N,1°F, and 31Pn.m.r. spectra were also The values of 8(13C), 8(l1°Sn),and 1.1(110Sn,13C) of Ph,SnOCOR provide evidence that the compounds are monomeric in N.m.r. data have also been reported for (CF3),Me,SnS,POCMe,CMe,b GeX,-, (13C, 10F),2402 Ph,GkGePh,PBu'+Bu' (31P),2403 (13C, Me,SnkC(0)CH,CH2&O)(13C),2405 Me3SnNHC(C,Fl5)=CHCH=CH2 (110Sn),2406 Me,Sn(oxinate) (13C, 110Sn),2407 B u ~ , S ~ O P ( S ) ( O M(,lP, ~)~

X(SiMe,) .X

( OSi),,

86

I. H. M. Wallace and T. H. Chan, Tetrahedron, 1983, 39, 847. B. M. Trost and S. J. Brickner, J . Am. Chem. Soc., 1983, 105, 568. 23a2 J. Schraml, J. Sraga, and P. Hrnciar, Collect. Czech. Chem. Commun., 1983,48, 2937. 2383 J. Schraml, J. Sraga, and P. Hrnciar, Collect. Czech. Chem. Commun., 1983,48, 3097. 2384 I. D. Kalikhman, B. A. Gostevskii, 0. B. Bannikova, M. F. Larin, 0. A. Vyazankina, and N. S . Vyazankin, Izv. Akad. Nauk SSSR, Ser. Khim., 1983, 1515 (Chem. Abstr., 1983, 2380 2381

99, 195 070).

'~E'J. Schraml, J. Vcelak, M. Cernq, and V. Chvalovsky, Collect. Czech. Chem. Commun., 1983,48, 2503.

H. G. Schuster and E. Hengge, Monatsh. Chem., 1983, 114, 1305. 2387 G. L. Larson and J. A. Prieto, Tetrahedron, 1983, 39, 855. 2388 V. J. Tortorelli, M. Jones, jun., S.-h. Wu, and Z.-h. Li, Organometallics, 1983, 2, 759. 2388 R. D. Holmes-Smith, R. D. Osei, and S. R. Stobart, J. Chem. SOC.,Perkin Trans. I , 2386

1983, 861.

23soA.I. Albanov, L. I. Gubanova, M. F. Larin, V. A. Pestunovich, and M. G. Voronkov, J. Organomet. Chem., 1983, 244, 5 . W. Clegg, 0. Graalmann, M. Haase, U. Klingebiel, G. M. Sheldrick, P. Werner, G. Henkel, and B. Krebs, Chem. Ber., 1983, 116, 282. M. Hesse and U. Klingebiel, Z. Anorg. Allg. Chem., 1983, 501, 57. 2303 G. Fritz and H. Bauer, Angew. Chem., Int. Ed. Engl., 1983,22,730. 2304 0 . Graalmann, M. Hesse, U. Klingebiel, W. Clegg, M. Haase, and G. M. Sheldrick, Angew. Chem., Int. Ed. Engl., 1983, 22, 621; Suppl., 874. S. A. Kazoura and W. P. Weber, J. Organomet. Chem., 1983,243,149. 2306 P. R. Jones and M. E. Lee, J. Am. Chem. SOC.,1983, 105, 6725. R. Tacke and H. Lange, Chem. Ber., 1983, 116, 3685. C. W. Carlson and R. West, Organometallics, 1983, 2, 1798. 2308 R. Noyori, I. Nishida, and J. Sakata, J. Am. Chem. SOC.,1983, 105, 1598. 2400 J. Holecek, M. Nddvornik, K. Handlir, and A. Lycka, J. Organomet. Chem., 1983, 241, 177. 2401 J.

Holecek, K. Handlir, M. Nadvornik, and A. Lycka, J. Organomet. Chem., 1983, 258,

147.

R. Eujen and R. Mellies, J . Fluorine Chem., 1983, 22, 263. (Chem. Abstr., 1983, 99, 5721). M. Baudler and H. Suchomel, Z. Anorg. Allg. Chem., 1983, 503, 7. 2404 R. J. Rao, G. Srivastava, and R. C. Mehrotra, J. Organomet. Chem., 1983,258, 155. 2406 F. E. Hahn, T. S. Dory, C. L. Barnes, M. B. Hossain, D. van der Helm, and J. J. Zuckerman, Organometallics, 1983, 2, 969. 2408 W. A. Nugent and B. E. Smart, J. Organomet. Chem., 1983,256, C9. a407 H. C. Clark, V. K. Jain, I. J. McMahon, and R. C. Mehrotra, J . Organomet. Chem., 1983, 2402

2403

243, 299.

F. A. K. Nasser and J. J. Zuckerman, J . Organomet. Chem., 1983, 244, 17. 2400 J. L. Lecat and M. Devaud, Polyhedron, 1983, 2, 1087. a408


131

11BSn),z40eBun,Sn organophosphates (31P),240ePhCOC,H,CO,SnR, (13C, 11eSn),z410 Ar,SnS,CR (11eSn),2411 and (Ph,Sn),Te (11eSn).2412 2eSin.m.r. chemical shifts have been measured for [Me2SiO],, and separate peaks were observed up to n = 15.2413The conformation of ArN(SiMe,),NAr has been investigated by 13Cn.m.r. s p e c t r o ~ ~ o p yThe . ~ ~n.m.r. ~ * characteristics of organometallic siloxanes have been described as functions of metal-oxygen bond energy, metal-ion-induced polarization, and standard redox Complexes of (RO),GeMe, with Ln(fod), have mainly pseudo-contact charact e r i s t i c ~ .N.m.r. ~ ~ ~ ~ data have also been reported for [Me,SiNPh], (2eSi),2417 RIRZSi(OCH,CH,),X (13C, 15N, 29Si),2418 [Me2SiO], (13C),241eMeN(SiMe,),NNHBu' ( OF, eSi),2420 p-XC,H,~=NsiMe,OSiMe,b (13C, eSi),2421Me2!% (NHC6H4-o-Cl),(13C, 2eSi),2422 Me,S?OSiMe,0SiMe,NHSiMe20SiMez6 (13C, R1N(CHzCH2O),SiR2Ph(13C, 2eSi),2424 R10SiPri20SiPr',0R2 (13C),242s Bu',SiFPBu'H (19F, 2eSi, 31P),2426 (Bu',GeO), (13C),2427 ButP(PBut),GePh, (31P),2428 MeEtSn(O,CCF,), (19F),2429 Bu,ShOCPh=CPhO (11eSn),2430 Bu2S~[OC6H4CH=lh==C(SMe)~] (13C, 11eSn),2431 Bu,Sn(OCR,),L (11eSn),a432 Bu'hPBu'SnBut,S~Bu', (31P, 119Sn),2433 b(SnBu,O),CPh=CPh (Ar2SnO), (11eSn),2435 "lo

"la

'"*

(11eSn),z4s4 and

S. W. Ng and J. J. Zuckerman, J. Organomet. Chem., 1983, 249, 18. B. Mathiasch and U. Kunze, Znorg. Chim. Acta, 1983, 75, 209. F. W. B. Einstein, C. H. W. Jones, T. Jones, and R. D. Sharma, Can. J. Chem., 1983, 61, 2611.

D. J. Burton, R. K. Harris, K. Dodgson, C. J. Pellow, and J. A. Semlyen, Polym. Commun., 1983,24, 278 (Chem. Abstr., 1983, 99, 140941). "14 A. Szollosy, L. Parkanyi, L. Bihatsi, and P. Hencsei, J. Organomet. Chem., 1983,251, 159. a416 E. A. Zharikova, Deposited Doc., 1981, VINZTZ575, 84 (Chem. Abstr., 1983,98, 144 169). V. V. Yastrebov, N. A. Yashtulov, G. Ya. Zueva, and G. V. Lipatova, Zzv. Akad. Nauk SSSR, Ser. Khim., 1983, 119 (Chem. Abstr., 1983, 98, 143 561). A. I. Albanov, M. G. Voronkov, V. V. Dorokhova, J. Kulpinski, M. F. Larin, Z. Lasocki, S. Piechucki, E. I. Brodskaya, and V. A. Pestunovich, Zzv. Akad. Nauk SSR, Ser. Khim., 1982, 1781 (Chem. Abstr., 1983,98, 53 993). E. Liepins, I. Birgele, G. Zelcans, I. Urtane, and E. Lukevics, Zh. Obshch. Khim., 1983, 53, 1076 (Chem. Abstr., 1983,99, 105 328). I. S. Alnaimi and W. P. Weber, Organometallics, 1983,2, 903. W. Clegg, M. Haase, H. Hluchy, U. Klingebiel, and G. M. Sheldrick, Chem. Ber., 1983, 116, 290. 24a1

B. Dejak and Z. Lasocki, J. Organomet. Chem., 1983,246, 151. L. PArkBnyi, A. Szollosy, L. Bihatsi, P. Hencsei, and J. Nagy, J. Organomet. Chem., 1983 256, 235.

B. D. Lavrukhin, B. A. Astapov, A. V. Kisin, and A. A. Zhdanov, Izv. Akad. Nauk SSSR, Ser. Khim., 1983, 1059 (Chem. Abstr., 1983, 99, 70 088). E. Kupce, E. Liepins, and E. Lukevics, J. Organomet. Chem., 1983,248, 131. J. J. Oltvoort, M. Kloosterman, and J. H. van Boom, Red. Trav. Chim. Pays-Bas, 1983, 102, 501.

W.Clegg, M. Haase, U. Klingebiel, and G. M. Sheldrick, Chem. Ber., 1983, 116, 146. H. puff, S. Franken, W. Schuh, and W. Schwab, J. Organomet. Chem., 1983,254,33. a4a8 M. Baudler and H. Suchomel, 2.Anorg. Allg. Chem., 1983,50622. A. Midha, R. D. Verma, K. Brown, and R. V. Parish, Monatsh. Chem., 1983,114,661. A. G . Davies and J. A. A. Hawari, J. Chem. SOC.,Perkin Trans. I , 1983, 875. am A. Saxena and J. P. Tandon, Polyhedron, 1983,2,443. a43a A. G. Davies and A. J. Rice,J. Organomet. Chem., 1983,258, 7. M. Baudler and H. Suchomel, Z. Anorg. Allg. Chem., 1983, 505, 39. A. G. Davies, J. A.-A. Hawari, and P. Hua-De, J. Organomet. Chem., 1983, 251, 203. S. Masamune, L. R. Sita, and D. J. Williams, J. Am. Chem. SOC.,1983, 105, 630. 5M46

a4a7

132


The effects of structure on 29Si n.m.r. signals for [MeSiO,.,], have been discussed on the basis of model 'H, 13C, 15N, and 29Sin.m.r. spectra of RM(OCOCH2),(OCH2CH2),-nN indicate that an increase in the number of CO groups in the atrane framework enhances charge transfer along the donor-acceptor N -+ M bond.2437N.m.r. data have also been reported for Bu'SiF,NHSiFBu'NHSiFBu"H, (13C, 19F, 29Si),2438 (108) (13C, T i , 31P),a439 (EtO),Si(CH,),SSnPhCIO-borne01(119Sn),2440 RM(OCH2CH2),N(M = Si or Ge; (109) (19F),2443RGe(OCH,CH,),(OCH,CH,170),2441[RSiO, . 5 ] n (29Si),2442 CH2),-,N (13C,15N,73Ge),2444 (Bu'Ge),o, (13C),2445 and CI(CH,),SnCl, (35C1).2446

F (108)

(109)

29Si n.m.r. spectroscopy has been used to distinguish between isomers of s i l ~ x a n e s Aqueous . ~ ~ ~ ~ silicate solutions have been characterized using both 29Si and 29Si-(29Si} n.m.r. ~ p e ~ t r a The . ~ concentration ~ ~ ~ 9 ~ ~distribution ~ ~ of silicate anions has been determined by 29Sin.m.r. s p e c t r o ~ c o p yl19Sn . ~ ~ and ~ ~ ~207Pb ~~~~ n.m.r. spectra of complexes of Sn2+and Pb2+with dppe, PhP(CH2CH,PPh2)2, MeC(CH2PPh2),,and P(CH,PPh,), have been measured and discussed in terms of d e n t i ~ i t y 23Na . ~ ~ ~n.m.r. ~ spectra have been recorded for some stannate s 0 1 u t i o n s . ~229Sn ~ ~ ~and 31Pn.m.r. spectra have been used to characterize mixed2436 2437

H. Jancke and G. Engelhardt, Z. Chem., 1983, 23, 253 (Chem. Abstr., 1983,99, 159 115). E. Kupce, E. Liepins, A. Lapsina, G . Zelchan, and E. Lukevics, J. Organomet. Chem., 1983, 251, 15.

U. Klingebiel and N. Vater, Chem. Ber., 1983, 116, 3277. 2430 M. Baudler, T. Pontzen, U. Schings, K.-F. Tebbe, and M. Feher, Angew, Chem., Znt. Ed. Engl., 1983, 22, 775. 2440 H. Schumann and B. Pachaly, J. Organomet. Chem., 1983,243, C75. 2441 E. Liepins, I. Zicmane, G. Zelcans, and E. Lukevics, Zh. Obshch. Khim., 1983, 53, 245 (Chem. Abstr., 1983,98, 215 699). 2442 G. Engelhardt, D. Zeigan, D. Hoebbel, A. Samoson, and E. Lippmaa, 2. Chem., 1982,22, 314 (Chem. Absrr., 1983, 98, 53 985.) 2443 V. A. Pestunovich, M. F. Larin, A. I. Albanov, L. I. Gubanova, V. M. Kopylov, and M. G. Voronov, Zzv. Akad. Nauk SSSR, Ser. Khim., 1983, 1931 (Chem. Abstr., 1983,99, 2438

212 580). 2444

G.Zelcans, A. Lapsina, I. I. Solomennikova, E. Lukevics, E. Liepins, and E. Kupce, Zh.

Obshch. Khim., 1983, 53, 1069 (Chem. Abstr., 1983,99, 195 118). H. Puff,S. Franken, and W. Schuh, J. Organomet. Chem., 1983,256,23. 2446 V. I. Shiryaev, T. G. Basanina, S. N. Gurkova, A. I. Gusev, G. V. Dolgushin, V. P. Feshin, V. P. Anosov, G. M. Apal'kova, and V. S. Nikitin, Koord. Khim., 1983, 9, 780 (Chem. Abstr., 1983,99, 105 392). 2447 H. C. Marsmann, E. Meyer, M. Vongehr, and E. F. Weber, Makromol. Chem., 1983, 184, 1817 (Chem. Abstr., 1983,99, 159 118). 2448 R. K. Harris and C. T. G. Knight, J. Chem. SOC., Faraday Trans. 2, 1983,79, 1525. 2440 R. K. Harris and C. T. G. Knight, J. Chem. SOC.,Faraday Trans. 2, 1983, 79, 1539. 2450 G. Engelhardt and D. Hoebbel, Z . Chem., 1983, 23, 33 (Chem. Abstr., 1983,98, 150 396). 2451 G. M. Barvinok, E. V. Morozova, V. 1. Korneev, A. M. Sazonov, and V. B. Lebedev, Zh. Prikl. Khim. (Leningrad), 1983, 56, 1090 (Chem. Abstr., 1983, 99, 44 234). 2452 P. A. W. Dean, Can. J. Chem., 1983, 61, 1795. 2453 G. M. Barvinok, S. R. Kasabyan, M. K. Khripun, M. M. Sychev, and V. B. Lebedev, Zh. Prikl. Khim. (Leningrad), 1983, 56, 1238 (Chern. Abstr., 1983,99, 111 631). 2445


133

halo species [SnClnBr,L6-,-,]4-”-”.2454 The 207Pbn.m.r. spectra of Pb2(ATP).2H20 show two different signals. The 13C and 31P n.m.r. spectra were also given.2455N.m.r. data have also been reported for [(Pr’S),Si]+ (13C),2466 [Si2Fl1l3-(1QF),2457 [GeF6I2-(1eF),2468 tin pyrophosphate (31P),2459 SnCl, - (methyl4,6-O-benzylidene-a-~-glucopyranoside)(’”, 11eSn),2460[SnF6-,(0,H),]2(1QF),2461 Sn(SCH2CH2CH,),NMe (13C, 11SSn),246292463 Sn’” xanthates (13C, l1 eSn),2464 and As(SPh)JSePh) - ,,, [Sn(SPh)“(SePh)3- ,,I-, and [Pb(SePh),] - (13C, 77&, llgsn, 207Pb).2465 8 Compounds of Group VB Elements

Several reviews have appeared: ‘Group V atom n.m.r. spectroscopy other than nitrogen’,2M6 “on biological aspects of 31Pn.m.r. s p e c t r o ~ ~ o p y‘Carbon-1 ’ , ~ ~ ~ ~3 nuclear magnetic resonance spectral data for heterocyclic phosphorus comp o u n d ~ ’ ,‘Isotope ~ ~ ~ ~ effects on phosphorus chemical shifts : applications to ‘Use of 31P(180),31P(170)and 1 7 0 n.m.r. methods to enzyme study enzyme mechanisms involving and ‘Study of in vivo cellular metabolism by 31Pn.m.r.’.2471 ,H and 14N quadrupole splittings of NH4N0, and Me,NNO, have been measured in Ni, cromoglycatewater liquid 14N and 16N chemical shifts have been reported for ”OF,]+, [NF41+,”€I4]+, [NO2]+, [NO]+, and mH3F]+and interpreted in terms of x- and a-fluoro 1J(31P,31P) has been calculated as a function of The solvent dependence of the 31P R. Colton and D. Dakternieks, Inorg. Chim. Acta. 1983, 71, 101. P. G. Harrison and M. A. Healy, Inorg. Chim. Acta, 1983, 80, 279. J. B. Lambert and W. J. Schulz, jun., J. Am. Chem. SOC.,1983, 105, 1671. *467 V. 0. Gel’mboldt, L. A. Gavrilova, and A. A. Ennan Zh. Neorg. Khim., 1983, 28, 2693 (Chem. Abstr., 1983, 99, 224 021). a468 V. I. Sergienko, V. L. Pershin, and L. N. Ignat’eva, Zh. Strukr. Khim., 1983,24,46 (Chem. Abstr., 1983, 98, 167 164). 8459 P. Thivolle, L. Mathieu, and M. Berger, Nucl. Med. Biol. Adv., Proc. World Congr., 3rd 1982, 1983, 2, 1628 (Chem. Abstr., 1983, 99, 15 414). *Mo S. J. Blunden, P. A. Cusack, P. J. Smith, and P. W. C. Barnard, Inorg. Chim. Acts, 1983, 72, 217. B. N. Chernyshov, N. A. Didenko, and E. G . Ippolitov, Koord. Khim., 1983,9,210 (Chem. Abstr., 1983, 98, 171 878. a46a A. Tzschach, K. Jurkschat, and M. Scheer, Z . Anorg. Allg. Chem., 1983, 507, 196. A. Tzschach, M. Scheer, K. Jurkschat, A. Zschunke, and C. Mugge, 2. Anorg. Allg. Chem. *454

8466

1983, 502, 158.

a w D. Dakternieks, R. W. Gable, and G. Winter, Inorg. Chim. Acta, 1983,75, 185. *485 J. J. I. Arsenault and P. A. W. Dean, Can. J. Chem., 1983,61, 1516. a408 R. G. Kidd, NATO Adv. Study Znst. Ser., Ser. C , 1983, 103, 379 (Chem. Abstr.. 1983,99, 132 399).

D. G. Gorenstein, Prog. Nucl. Magn. Reson. Spectrosc., 1983, 16, 1. am L. D. Quin, ‘Carbon-13 Nuclear Magnetic Resonance Spectral Data of Heterocyclic Phosphorus Compounds’, 1982, 75 pp. (Chem. Abstr., 1983,99, 88 362). aMg C. W. DeBrosse and J. J. Villafranca, Magn. Reson. Biol., 1983, 1, 1 (Chem. Abstr., 1983, a467

99, 208 446). a470 a471

M.D. Tsai, Methods Enzymol., 1982,87,235 (Chem. Abstr., 1983,98, 30 060). M.Bernard, P. Canioni, and P. J. Cozzone, Biochimie, 1983,65,449 (Chem. Abstr., 99, 208 993).

H. Gilboa and A. Loewenstein, Israel J . Chem., 1983,23, 295. J. Mason and K. 0. Christe, Inorg. Chem., 1983, 22, 1849. 8474 S. Duangthai and G. A. Webb, Org. Magn. Reson., 1983, 21, 199. 3475

1983,

134


chemical shifts has been calculated for PH3, PH,Me, PHMe,, PF,, and POF3.2475 The 31P n.m.r. spectra of HPBu'(PBu'),PHBu' have been analysed as [ABI2or ABCD.2476 N.m.r. data have also been reported for C6H2Bu',PH2S(13C, 31P),2477 Bu'PHCH2CH2PHBu' (31P),2478 (1 10) ("C, 31P),247g CH2=CHCH2CH2-NCH,CHMePHkH, (31P),2480 P(PHBu'), (31P),z481 MeHP(0)Cl (31P),2482 CHPH(O)(OEt) (13C, 31P),z483 ArPHOCHPh, (31P),2484 and [P2HS5]3-.2485

The relationship between I5N, 170,3LP,and 77Sen.m.r. spectral parameters and the electronic structure of a number of polyfluoroaromatic compounds has been N.m.r. data have also been reported for (1 11) (13C, 31P),3487 1 [R2PCH,CX=CYkH,]+ (13C, 31P),2488Bu3P(HCCOEt) (31P),z4*9[(Ph,P),CPPh,]+ (13C, 31P),2490 [Ph,P]+[Ph4PF,]- (lgF,31P),z491 [(P~,P),CSSS~C(PP~,),]~+ (31P),2492 Ph,P=CCH,CH,CH, ("C, 31P),2493 R13P=C=NR22NR32 (13C,31P),24s4 Ph3P=CR1R2 (31P),2495 and [R4P]+(13C, 31P),z496-2500 (13C),2501-2503 (31p) 2504-2505

-

Y

(l 9F).2506 B. NaLamphun and G. A. Webb, Org. Magn. Reson., 1983, 21, 399. M. Baudler, G. Reuschenbach, J. Hellmann, and J. Hahn, Z. Anorg. Allg. Chem., 1983, 499, 89. 2477 M. Yoshifuji, K. Shibayama. K. Toyota, and N. Inamoto, Tetrahedron Lett., 1983, 24, 4227. 2478 R. Weisheit, R. Stendel, B. Messbauer, C . Langer, and B. Walther, Z . Anorg. Alfg. Chem., 1983,504, 147. 2479 A. H. Cowley and S. K. Mehrotra, J. Am. Chem. SOC.,1983,105, 2074. 2480 K. Issleib, U. Kiihne, and F. Krech, Phosphorus Sulphur, 1983, 17, 73. M. Baudler, J. Hellmann, and T. Schmidt, Z . Naturforsch., Teif B, 1983, 38, 537 (Chem. Abstr., 1983, 99, 88 274). 2482 N. A. Kardanov, N. N. Godovikov, P. V. Petrovskii, and E. I. Fedin, Dokl. Akad. Nauk SSSR, 1983, 268, 364 (Chem. Abstr., 1983, 99, 5690). 2483 L. Maier and G. Rist, Phosphorus Sulphur, 1983, 17,21. 2484 Th. A. van der Knaap, Th. C. Klebach, R. Lourens, M. Vos, and F. Bickelhaupt, J. Am. Chem. SOC., 1983,105,4026. 2485 W. Krause and H. Falius, Z. Anorg. Allg. Chem., 1983, 496, 94. 2486 G. G. Furin, A. I. Rezvukhin, M. A. Fedotov, and G. G. Yakobson, J. Fluorine Chem., 1983, 22, 231 (Chem. Abstr., 1983, 98, 197 492). 2487 G. A. Bowmaker, R. Herr, and H. Schmidbaur, Chem. Ber., 1983,116, 3567. 2488 C. K. SooHoo and S. G. Baxter, J. Am. Chem. SOC.,1983,105, 7443. 248g G . G. Minasyan, G. Ts. Gasparyan, A. M. Torgomyan, M. Zh. Ovakimyan, and M. G. Indzhikyan, Arm. Khim. Zh., 1982, 35, 583 (Chern. Absrr., 1983, 98, 4614). 24g0 H. Schmidbaur, S. Strunk, and C. E. Zybill, Chem. Ber., 1983, 116, 3559. a481 S. J. Brown and J. H. Clark, J. Chem. SOC.,Chem. Commun., 1983, 1256. 2492 H. Schmidbaur, C. E. Zybill, and D. Neugebauer, Angew. Chem., Int. Ed. Engf., 1983,22, 156; Suppl., 169. 2493 H. Schmidbaur, A. Schier, and D. Neugebauer, Chem. Ber., 1983, 116, 2173. 24Q4 R. Appel, U. Baumeister, and F. Knoch, Chem. Ber., 1983, 116, 2275. 2495 A. M. Caminade, F. El. Khatib, and M. Koenig, Phosphorus Sulphur, 1983, 14, 381. 24g8 H. J. Bestmann and L. Kisielowski, Chem. Ber., 1983, 116, 1320. 2497 C. C. Hanstock and J. C. Tebby, Phosphorus Sulphur, 1983,15,239. 2475

2478


135

31P Tl values have been shown to be much longer for phosphines than phosphine A linear correlation between 6(lH) of the ethylenic P-hydrogen and 31Pnuclei, respectively, and the Hammett up of the R in the 4 position for diphenylphosphinyl trans-styrenes and analogous diphenylthiophosphinyl trans-styrenes has been 13Cand 31Pn.m.r. spectra have shown that in general MPR,-cryptands give separate ion pairs, except for LiPPh2where 13CTI data indicate a tetrameric N.m.r. data have also been reported for (CF,),Me,-,E (E = P, Sn, Bi, Hg, or Pb; 1gF),2510 1,2-(PMez)2C,H,(13C,31P),2511 C6H4(CH2)2PMe(13C, 31P),2512EtP(CH2C02H)2 (31P),2513some phospholes (13C, 31P),2514(1 12) (31P),2515CF3P(CF,),PCF3 (1gF),251sP(C=CPh)nPh,-, (31P),2517(2,2-dimethylpr0pionyl)~phosphine (13C, 31P),2518P ~ I P ( C M ~ ~ ) ~ C H , (13C),251g O(CH2CH2PPhCH2CH2PPhCH2CH2)20 (31P),2520 benzophosphole(13C, Me \

P

Ph

H. J. Meeuwissen, Th. A. van der Knaap, and F. Bickelhaupt, Tetrahedron, 1983, 39, 4225. 2488 J. P. Henichart, R. Houssin, C. Vaccher, M. Foulon, and F. Baert, J. Mol. Struct., 1983, 99,283. a600 H. Schmidbaur and S. Schnatterer, Chem. Ber., 1983, 116, 1947. aaolT.Minami, H. Sako, T. Ikehira, T. Hanamoto, and I. Hirao, J. Org. Chem., 1983, 48, 2569. asoa S. Sat0 and S. Tanaka, Bunseki Kagaku, 1983,32,246 (Chem. Abstr., 1983,99, 53 853). 2609 L. Capuano, T. Triesch, and A. Willmes, Chem. Ber., 1983, 116, 3767. 26mYu. P. Makovetskii, V. E. Didkovskii, I. E. Boldeskul, N. G. Feshchenko, and N. N. Kalibabchuk, Zh. Obshch. Khim., 1982, 52, 2235 (Chem. Abstr., 1983, 98, 89 482). a606 H. Schmidbaur, C. Zybill, C. Krueger, and H. J. Kraus, Chem. Ber., 1983,116, 1955. a 6 D. ~ J. Burton and D. G. Cox, J. Am. Chem. Soc., 1983,105, 650. a607 A. B. Shortt, L. J. Durham, and H. S. Mosher, J. Org. Chem., 1983,48, 3125. 2608 D. Gloyna, H. Koppel, K.-D. Schleinitz, K.-G. Berndt, and R. Radeglia, J. Prukt. Chem., 1983, 325, 269. a509 A. Zschunke, E. Bauer, H. Schmidt, and K. Issleib, 2. Anorg. Allg. Chem., 1982,495, 115. aslo M. A. Guerra, R. L. Armstrong, W. I. Bailey, jun., and R. J. Lagow, J. Organomet. Chem., 1983, 254, 53. E. P. Kyba, S.-T. Liu, and R. L. Harris, Organometaflics, 1983, 2, 1877. H. Schmidbaur and A. Mortl, J. Organomet. Chem., 1983,250, 171. D. Noskovii and J. PodlahovB, Polyhedron, 1983, 2, 349. 2514 C. Charnier, H. Bonnard, G. de Lauzon, and F. Mathey, J. Am. Chem. SOC.,1983, 105, 6871. K. C. Caster and L. D. Quin, Tetrahedron Lett., 1983,24,5831. A. B. Burg, Inorg. Chem., 1983,22, 2573. a617 A. Hengefeld and R. Nast, Chem. Ber., 1983, 116, 2035. G. Becker, M. Roessler, and G. Uhl,Z. Anorg. Aflg. Chem., 1982, 495, 73. E. L. Clennan and P. C. Heah, J. Org. Chem., 1983,48,2621. 2620 M. Ciampolini, N. Nardi, F. Zanobini, R. Chi, and P. L. Orioli, Inorg. Chim. Acta, 1983, 76, L17. a408

136


31P),2521 (1 13) (13C, 31P),2522 C6H4(CH=CH)2PPh (13C, 31P),2523 RPh2P (31P),2524 Ph,PC(S)NMeR (13C,31P),2525 (Ph2P),CH-2-pyridyl(31P),2526 Ar,PPh,-, (31P),2527 (1 14) ( W , 31~),2528(1 15) (13C),252QBi(mesityl)(p-C~C,H,)(~-~~~~~Pr') (13C),2530 (1 16) (31P),2531 some phosphabenzenes (31P),253292533 (13C, 3lp),2534 [P(kNMeCH,CH,&Me),]+ (13C, 31P),2535 ArP=CRNMe, (13C, 31P),2536 C&(117) (E = N or P; 13C, 31P),2538 [(C,Me,),E]+ (E = As Buf3P=C==0 (31P),2537 t or Sb; llB, 13C, 1QF),2539 C6H4NR1CR2=A$ (13C),2540 and Bu'CP (31P).2541

L. D. Quin and N. S. Rao, J. Org. Chem., 1983,48, 3754. L. D. Quin, A. N. Hughes, H. F. Lawson, and A. L. Good, Tetrahedron, 1983,39, 401. 2523 G. Markl and W. Burger, Tetrahedron Lett., 1983. 24,2545. 2524 H.-J. Cristau, L. Labaudiniere, and H. Christol, Phosphorus Sulphur, 1983, 15, 359. 2525 A. Antoniadis, A. Bruno, and U. Kunze, Phosphorus Sulphur, 1983, 15, 317. 2526 M. P. Anderson, B. M. Mattson, and L. H. Pignolet, Znorg. Chem., 1983,22, 2644. 2527 L. Horner and G. Simons, Phosphorus Sulphur, 1953, 14, 189. 2528 J. Bakos, B. Heil, and L. Marko, J. Organornet. Chem., 1983, 253, 249. 2529 0. Mundt and G. Becker, 2. Anorg. Allg. Chem., 1983, 496, 58. 2530 P. Bras, A. van der Gen, and J. Wolters, J . Organomet. Chem., 1983,256, C1. 2531 G. Markl, E. Siedl, and I. Trotsch, Angew. Chem., Int. Ed. Engl., 1983, 22, 879. 2532 G. Markl and K. Hock, Tetrahedron Lett., 1983, 24, 5051. 2533 G. Markl and K. Hock, Tetrahedron.Lett., 1983, 24, 2645. 2534 G. Markl and K. Hock, Chem. Ber., 1983, 116, 1756. 2535 A. Schmidpeter, S. Lochschmidt, and A. Willhalm, Angew. Chem., Znt. Ed. Engl., 1983, 22, 545; Suppl., 710. 2536 J. Navech, J. P. Majorel, and R. Kraemer, Tetrahedron Lett., 1983,24, 5885. 2537 R. Appel and W. Paulen, Angew. Chem., Int. Ed. Engl., 1983,22, 785. 2538 Y. Y. C. Y. L. KO, R. Carrie, F. de Sarlo, and A. Brandi, Can. J . Chem., 1983, 61, 1105. 2539 P. Jutzi, T. Wippermann, C. Kruger, and H.-J. Kraus, Angew. Chem., Int. Ed. Engl., 2521 2522

1983, 22, 250.

J. Heinicke, A. Petrasch, and A. Tzschach, J. Organomet. Chem., 1983, 258, 257. 2541 J. C. T. R. Burckett-St. Laurent, M. A. King, H. W. Kroto, J. F. Nixon, and R. J. Suffolk, J. Chem. Soc., Dalton Trans., 1983, 755.

2540


137

The low-frequency 31P shift of (EtO),PEtO and PhMe,PO in the presence of cyclodextrins in water has been interpreted in terms of inclusion complex 1J(31P,13C)and 1J(31P,10F)have been calculated for a selection of tri- and penta-valent phosphorus N.m.r. data have also been reported for Ph,POCRHCHMe (31P),2644 Ph3P=NR (13C),2K45 (118) (13C, 31P),2646 Ph4PzSzN4 (31P),2647 [Ph6P2NIf (31P),z548 [Ph3P=N=C=NR]+ (13C),aK4* Ph 3(31P),2560 [Ph,PN(CH,Ph),]+ ("C, 31P),2KK1 Ph(X)P(CHPr'O)&HPr' PNS3N3C7H8 (13C),2KK2 Ph3P(OR')N(C0,R2)NHC0,R2 (31P),2553 MePhP(O)CH,CMe=CMeCOPh (31P),25K4 3-C-phosphonates, -phosphinates, and -phosphine oxides of branched-chain sugars (13C, 31P),2555Ph,P(O)R (13C, 31P),2KK6 (31P),2KK7 1 (13C),2K58 Me(E)hCH,CH=CHCH, (r3C),26K0 R(E)P(CH,CH,),CO Ph,P(O)CH(OAc)Ph (13C, 31P),2560 Ph,P(O)CHMeCHPhOLi (31P),2K61 Me(0)eCH2k(OH)CH&H,CHa&=qH2 (13C, 31P),2562C&P(O)Ph (13C, 31P),2K63Ph,P(O)CH(OH)CHPh(CH,),Me (31P),zK64PhP(OMe)CHMeNMe, (33P),zss5Ph(O)hCMe=CMeCMe===kMe (13C, 31P),2586 Ph3P(OaBut), (31P),w7 Et2P(O)CH,CHRCOSEt (31P),2K68 Ph2P(O)(CH,),P(O)Ph*PFK ("F, 31P),8M)g

-

B. L. Poh and W. Saenger, Spectrochim. Acta, Part A , 1983,39,305. S. Duangthai and G. A. Webb, Org. Magn. Reson., 1983, 21, 125. aK44 E. Vedejs and G. P. Meier, Angew. Chem., Int. Ed. Engl., 1983, 22, 56. 2545 H. Wamhoff, G. Haffmanns, and H. Schmidt, Chem. Ber., 1983,116, 1691. 8546 G. Wax R. Haller, H. B. Stegmann, K. Scheffler,T. Butters, and W. Winter, Chem. Ber., 854a

1983, 116,1914.

N. Burford, T. Chivers, and J. F. Richardson, Inorg. Chem., 1983, 22, 1482. F. A. Cotton, L. R. Falvello, G. N. Mott, R. R. Schrock, and L. G. Sturgeoff, Znorg. Chem., 1983, 22, 2621. 264B J. C. Jochims, M. A. Rahman, L. Zsolnai, S. Herzberger, and G . Huttner, Chem. Ber.

a647

1983, 116, 3692. a5soS.W.Liblong, R. T. Oakley, A. W. Cordes, and M. C. Noble, Can. J. Chem., 1983, 61, 2062. H. J. Cristau, J. Coste, A. Truchon, and H. Christol, J . Organomet. Chem., 1983, 241, C1. 86K8

B. A. Arbuzov, A. V. Il'yasov, T. A. Zvablikova, K. M. Enikeev. 0.A. Erastov, and I. P. Romanova, Zzv. Akad. Nauk SSSR, Ser. Khim., 1983, 1309 (Chem. Abstr., 1983, 99, 157 476).

8668

M.v. Itzstein and I. D. Jenkins, Aurt. J. Chem., 1983, 36, 557.

C. C. Santini and F. Mathey, Can. J. Chem., 1983,61,21. J.-R. Neeser, J. M. J. Tronchet, and E. J. Charollais, Can. J. Chem., 1983, 61, 21 12. E. Lindner, E. Tamoutsidis, W. Hiller, and R. Fawzi, Chem. Ber., 1983,116, 3151. E. Lindner and E. Tamoutsidis, Chem. Ber., 1983,116,3141. p668 J. A. Hirsch and K. Banasiak, Org. Magn. Reson., 1983, 21, 457. G. W. Buchanan and V. L. Webb, Org. Magn. Reson., 1983,21,436. *6M) M. Yoshifuji, Y. J. Choi, and N. Inamoto, Phosphorus Sulphur, 1983, 16, 3. R. 0. Larsen and G. Aksnes, Phosphorus Sulphur, 1983,15,229. *so8 L. D. Quin and H. F. Lawson, Phosphorus Sulphur, 1983,15,195. 8sea N. S. Rao and L. D. Quin, J. Am. Chem. SOC.,1983,105, 5960. 8564 M.Matsumoto and M. Tamura, J. Mol. Catal., 1983,19, 365. 8#K A. Meriem, J.-P. Majoral, M. Revel, and J. Navech, Tetrahedron Lett., 1983,24, 1975. 8m K. S. Fongers, H. Hogeveen, and R. F. Kingma, TetrahedronLett., 1983,24,1423. 8~3' M. v. Itzstein and I. D. Jenkins, J. Chem. SOC.,Chem. Commun., 1983,164. 8M8 0. G. Sinyashin, T. N. Sinyashina, E. S. Batyeva, A. N. Pudovik, and E. N. Ofitserov, Zh. Obshch. Khim., 1982, 52, 2438 (Chem. Abstr., 1983, 98, 107404). 866B E. G. I l k , M. N. Shcherbakova, Yu. A. Buslaev, T. Ya. Medved, N. P. Nesterova, and M. I. Kabachnik, Dokl. Akad. Nauk SSSR, 1983, 269, 147 (Chem. Abstr., 1983, 99, 86M

8666

105 354).

138


Ph,P(O)CHRCONEt, (1sF),2570 Ph2PCH2C(OH)=NNH2 ("C, 31P),2571 RP(S)Ph2 (13C),2572 [Ph,PSeMe]+ (31P),2573 R 1 B R 3 C I (13C, 31P),2674 and PhC5H,PBu'CI (13C).2676 Literature data have been used to find relations between 2J(31PCH)in comI pounds such as Me(O)POCH,CH,NMekHPh and angles between the P===O bond axis and the P-C-3-H plane and 3J(31POCH).2676 For (119) the short 13C Tl associated with the arsenic-bearing quaternary carbon atoms has been

N.m.r. data have interpreted in terms of an 75A~-13C dipolar also been reported for Et2NPR(CH2),PRNEt2 (31P),2578 (120) (13C, 31P),2579 R2PNMeCH2C=CH (31P),2580 (Pri2N),PCHR1CR2=CR3CHR"(13C, 31P),2581 Et,P(O)NHP(O)(OPh), (31P),2582 P3N3R3F3(13C),2583 MeS(NR1)NR2PPh2(13C, 31P),2a84(Ph,PN),HCl (31P),2585(Ph2PN)4(NSNMe2)2(31P),258s(Ph2PN),N2S R1R2PPMeEt (31P),2588 [Li2(v3-But2P)( p2-But2P)(thf)],(31P),2589 RP(PBu*),CO (13C, 33P),2590 (121) (13C, 31P),2591 (CH2=CH)4Sb2(13C),2592 Me2P02H a570

E. G. I l k , M. N. Shcherbakova, Yu. A. Buslaev, T. Ya. Medved, N. P. Nesterova, and M. I. Kabachnik, Dokl. Akad. Nauk SSSR, 1983, 271, 373 (Chem. Abstr., 1983, 99, 224 107).

2571V. I. Molostov, T. V. Zykova,

A. S. Mikheeva, R. I. Tarasova, and A. I. Razumov, Deposited Doc., 1981, SPSTL 416 Khp-D81, 11 pp., avail. SPSTL (Chem. Abstr., 1983,

98, 89 501).

J.-C. Fiaud, J. Chem. SOC.,Chem. Commun., 1983, 1055. a573 J. Omelanczuk and M. Mikolajczyk, Phosphorus Sulphur, 1983, 15, 321. 2574 K. S. Fongers, H. Hogeveen, and R. F. Kingma, Tetrahedron Lett., 1983,24, 643. a575 G. Markl, K. Hock, and D. Matthes, Chem. Ber., 1983,116, 445. 8676 Yu. Yu. Samitov, Zh. Obshch. Khim., 1982, 52, 221 1 (Chem. Abstr., 1983,98, 72 269). 2577 M. Jay and G. E. Martin, J . Heterocycl. Chem., 1983, 20, 527. 2578 K. Diemert, W. Kuchen, and J. Kutter, Phosphorus Sulphur, 1983,15, 155. 2570 Y. Y. C. Yeung Lam KO, F. Tonnard, R. Carrie, F. De Sarlo,,and A. Brandi, Tetrahedron, 2572

1983, 39, 1507.

C. M. Angelov and 0. Dahl, Tetrahedron Lett., 1983,24, 1643. a581 A. H. Cowley, R. A. Kemp, J. G. Lasch. N. C. Norman, and C. A. Stewart, J. Am. Chem. SOC.,1983, 105, 7444. 258a E. Fluck, H. Richter, and W. Schwarz, Z. Anorg. Allg. Chem., 1983,498 161. a583 C. W. Allen and R. P. Bright, Report, 1982, TR-12, order no. AD-A122591, 28 pp., avail. NTIS, from Gov. Rep. Announce. Index (U.S.), 1983, 83, 1512 (Chem. Abstr., 1983, 99, 105498). a584 D. Hanssgen and R. Steffens, 2. Anorg. Allg. Chem., 1983, 507, 178. a585 T. Chivers and M. N. S. Rao, Can. J. Chem., 1983, 61, 1957. 2586 T. Chivers, M. N. S. Rao, and J. F. Richardson, J. Chem. SOC.,Chem. Commun., 1983, 2680

702. 2587

T. Chivers, M. N. S. Rao, and J. F. Richardson, J. Chem. SOC.,Chem. Commun., 1983,

2588

A. A. M. Ali and R. K. Harris, J. Chem. SOC.,Dalton Trans., 1983, 583. R. A. Jones, A. L. Stuart, and T. C. Wright, J. Am. Chem. SOC.,1983, 105, 7459.

700. 2580

139


(31P),2593(RO),P(O)CCI,CHO (13C, ,lP) 2594 {[Me(CH,),I,PO I- (31p),2595 RP(CH,CH,Cl)O,Et (31P),2596 (122) (13C, 31P),2597 [Ph,P(O)(CHCO,Me)]- (13C, 31P),2598 diphenylphosphinic mixed anhydrides (13C, 31P),2599 Ph2POR (31P),2soo [HOCH,CH,PPh(S)], (31P),2601R1R2P(S)Br (31P),2aozC6H,Me,P(Se)=CPh2 R2PCl ( 31P),2605 and (123) (31P).2606 (13C, 31P),2603 Ph,PS,AsR, ( 9

But

P

Me Me

But (121)

i123)

For p-RC6H4P,N3C14Xan excellent correlation between the Hammett o-parameter and the 31P chemical shift has been lH, 13C, and 31P n.m.r. spectra have been used to study phenylphosphonic dichloride in a liquid crystal. The dipolar coupling constants, the hydrogen and phosphorus nuclei co-ordinates, the chemical-shift anisotropy, and the directly bonded phosphorus-carbon distance were calculated.2608Two-dimensional n.m.r. spectroscopy has been used to determine the lH n.m.r. parameters for L-menthyldichlorophosphine. 13C n.m.r. data were also given.26og N.m.r. data have also been reported for P,N,Me,Cl, (31P),2610 CF,PX(NEt,) (lgF, 31P),2611 N3P3F6-,,[C(OR)=CH,], (13C, l9F, 31P),2612 P=C(NHPh)CMe=NhMe (13C, 31P),2613 R. Appel and W. Paulen, Chem. Ber., 1983, 116, 2371. M. Baudler and W. Leonhardt, Angew. Chem., I n t . Ed. Engl., 1983, 22, 632. a592 A. J. Ashe, tert., E. G. Ludwig, jun., and H. Pommerening, Organometallics, 1983,2, 1573. 2593 P. J. Harris and C. L. Fadeley, Znorg. Chem., 1983,22, 561. 25g4 V. M. Ismailov, V. V. Moskva, L. A. Dadasheva, T. V. Zykova, and F. I. Guseinov, Zh. Obshch. Khim., 1982, 52, 2140 (Chem. Abstr., 1983, 98, 54 033). 25g5 S. Raynal, W. Bergeret, J. C. Gautier, and A. Breque, Tetrahedron Lett., 1983,24, 1791. 2596 L. Maier and P. J. Lea, Phosphorus Sulphur, 1983, 17, 1. 25g7 J. Heinicke and A. Tzschach, Tetrahedron Lett., 1983,24, 5481. 26g8 T. Bottin-Strzalko, G. Etemad-Moghadam, J. Seyden-Penne, M. J. Pouet, and M. P. Simonnin, Nouv. J. Chim., 1983,7, 155 (Chem. Abstr., 1983,99, 53 860). 2599 I. J. Galpin, A. E. Robinson, and R. G. Tyson, Pept., Proc. Eur. Pept. Symp., 16th, 1980, 1981, 169 (Chem. Abstr., 1983, 98, 54 438). 2600 E. Cesarotti, A. Chiesa, G. Ciani, and A. Sironi, J. Organomet. Chem., 1983,251, 79. 2601 T. Kawashima, T. Tomita, and N. Inamoto, Phosphorus Sulphur, 1983, 16, 9. 2602 W. Peters and G . Haegele, 2, Naturforsch., Ted B, 1983, 38, 96 (Chem. Abstr., 1983, 98, 215 680). 2w3Th. A. van der Knaap, M. Vos, and F. Bickelhaupt, J. Organomet. Chem., 1983,244, 363. 2604 L. Silaghi-Dumitrescu and I. Haiduc, J . Organomet. Chem., 1983, 252, 295. 2605 A. Hinke and W. Kuchen, Phosphorus Sulphur, 1983, 15, 93. M. Yoshifuji, I. Shima, K. Ando, and N. Inamoto, Tetrahedron Lett., 1983 24, 933. 2607 P. J. Harris, Inorg. Chirn. Acta, 1983, 71, 233. atxis H. Ye and B. M. Fung, J. Magn. Reson., 1983,51, 313. 260e M. Fiegel, G. Haegele, A. Hinke, and G. Tossing, Z. Naturforsch., Teil B, 1982, 37, 1661 (Chem. Abstr., 1983, 98, 179 654). 2610 P. J. Harris and L. A. Jackson, Organometallics, 1983, 2, 1477. W. Volbach and I. Ruppert, Tetrahedron Lett., 1983, 24, 5509. aslaC. W. Allen and R. P. Bright, Znorg. Chem., 1983, 22, 1291. 2613 H. Hogel, A. Schmidpeter, and W. S. Sheldrick, Chem. Ber., 1983, 116, 549. 2590

2591

140


(MeO)(S)PCPh,CH,CMe=NlhPh (31P),2614 N3P3C14XR(31P),2615 C6H4O2PR1I (NR2),PR102C6H4(31P),2616Ph(O)PNMePPhPPh(S)kMe (31P),2617(Me,N),PC,H,NMeP(NMe,), (31P),2618 S2N6P4Ph8(31P),2619 Ar1P==PAr2 (31P),2620-2622 P3Pri3(31P),2625 PsR6 (l3C, C6H2But,As=PCH(SiMe3), (31P),2623 P7Me3(31P),2624 31P),2626 P13Pri5 (31P),2627P3But3Te (31P, 125Te),2628PoPri3 (31P),2629 RPCH,CH2-PR (31P)72630 (PPh)5 (31P),2631PhBrPPBrPh (31P),2632 [(C6H,But3)P],S (31P),2633 MeP(O)(OMe)-L-Phe (l3CC,31P),2634 MeP(S)(OMe)L-PheOMe (13C, 31P),2635MeP03R, (13C, 31P),2636(C6H4O2),PR (31P),2637 H(CF,CF,),CH(OH)P(O)(OCH,R) (lgF,31P),2638 Ar1P(0)(OMe)02CAr2(31P),2630 (EtO),P(O)R (13C),2640 (EtO),P(O)C(=NCy)CHRP(O)(OEt), (31P),2641(Et0)P(02H)R(13C),2642 RP(OPh),O (13C),2643 R1P(0)(OR2)2(13C),2644 Ph0B. A. Arbuzov, E. N. Dianova, and Yu. Yu. Samitov, Zzv. Akad. Nauk SSSR, Ser. Khim. 1982,2730 (Chem. Abstr., 1983, 98, 126 255). 2615 H. R. Allcock, M. S. Connolly, and R. R. Whittle, Organometallics, 1983, 2, 1514. 2616 V. P. Kukhar, E. V. Grishkun, and N. N. Kalibabchuk, Zh. Obshch. Khim., 1982, 52, 2227 (Chem. Abstr., 1983, 98, 89 481). 2617 S. Kleemann, E. Fluck, H. Riffel, and H. Hess, Phosphorus Sulphur, 1983,17,245. J. Heinicke and A. Tzschach, J. Prakt. Chem., 1983,325, 232. 2619 T. Chivers, M. N. Sudheendra Rao, and J. F. Richardson, J. Chem. SOC.,Chem. Commun., 1983, 186.

2622

M. Yoshifuji, K. Shibayama, N. Inamoto, T. Matsushita, and K. Nishimoto, J. Am. Chem. SOC.,1983, 105, 2495. C. N. Smit, Th. A. van der Knaap, and F. Bickelhaupt, Tetrahedron Lett., 1983,24,2031. M. Yoshifuji, I. Shima, N. Inamoto, M. Yamada, and H. Kuroda, Phosphorus Sulphur,

2623

A. H. Cowley, J. G. Lasch, N. C. Norman, and M. Pakulski, J. Am. Chem. SOC.,1983,

2620 2621

1983, 16, 157. 105, 5506. 2624

M. Baudler and T. Pontzen, 2 . Nuturforsch., Teil B, 1983, 38, 955. (Chem. Abstr., 1983, 99, 195 105).

2625

M. Baudler, G. Furstenberg, H. Suchomel, and J. Hahn, 2. Anorg. Allg. Chem., 1983, 498, 57.

2626 2627 2628

M. Baudler and Y. Aktalay, 2. Anorg. Allg. Chem., 1983, 496, 29. M. Baudler, Y. Aktalay, V. Amdt, K.-F. Tebbe, and M. Feher, Angew. Chem., In?. Ed. Engl., 1983, 22, 1002. W.-W. du Mont, T. Severengiz, and B. Meyer, Angew. Chem., In?. Ed. Engl., 1983, 22, 983.

2628

M. Baudler, Y. Aktalay, K. Kazmierczak, and J. Hahn, 2. Nutwforsch., Teil B, 1983, 38.

428 (Chem. Abstr., 1983, 99, 105 345). 2630 M. Baudler and S. Esat, Chem. Ber., 1983, 116, 2711.

M. Veith, V. Huch, J.-P. Majoral, G. Bertrand, and G. Manuel, Tetrahedron Lett., 1983, 24,4219. 2632 A. Hinke and W. Kuchen, Chem. Ber., 1983, 116, 3003. 2633 M. Yoshifuji, K. Ando, K. Shibayama, N. Inamoto, K. Hirotsu, and T. Higuchi, Angew. Chem., In?. Ed. Engl., 1983, 22, 418. 2634 N. E. Jacobsen and P. A. Bartlett, J. Am. Chem. SOC.,1983,105, 1613. 2635 N. E. Jacobsen and P. A. Bartlett, J. Am. Chem. SOC.,1983,105, 1619. 2636 W. G. Wadsworth and W. S. Wadsworth, jun., J. Am. Chem. SOC.,1983,105,1631. 2637 J. Gloede, 2. Anorg. Allg. Chem., 1983, 500, 59. 2638 S. F. Aleinikov, I. G. Maslennikov, and A. N. Lavrent'ev, Zh. Obshch. Khim., 1982,52, 2134 (Chem. Abstr., 1983, 98, 54 032). 2631

M. Yoshifuji, K. Ando, K. Toyota, I. Shima, and N. Inamoto, J. Chem. SOC.,Chem. Commun., 1983, 419. 2840 T. Minami, T. Yamanouchi, S. Takenaka, and I. Hirao, Tetrahedron Lett., 1983,24, 767. 2841 M. A. Whitesell and E. P. Kyba, Tetrahedron Lett., 1983,24, 1679. 2842 T. Maruyama, Z. Taira, M. Horikawa, Y. Sato, and M. Honjo, TefrahedronLett., 1983, 2639

24, 2571. 2843

2844

R. W. McChard, Tetrahedron Lett., 1983,24,2631. C.-P. Mak, C. Mayerl, and H. Fliri, Tetrahedron Lett., 1983, 24, 347.


141

(31P),2s45 Ar(O)(OEt), (31P),2646 PhP(OCH2CH2b)(S2C8H,)(31P),2647 RPO,Et, (124) (13C),2660 Me02hCMe2CH2C(31P),2s48 [(RO),PCH,COPh]+ (13C, 31P),2e4e MeOH (13C),2651(EtO),P(O)R (13C, 31P),2652(EtO),P(O)CH,CH,SR (13C, 31P),2663 HzO3PCR(NH&(CH2).CR(NH2)POsH2 (31P),2664 P(0)R1(OR2)2(31P),2666 R1P(OR2)2 (31P),2668H2N(CHJ,N(CH,PO,H2)2 ("C, 31P),8067 (R1O)(0)IbCR2R3CR4XCCI=kH (31P),2658 R A s (13C),2669 ~ ArP(S)=P=S (l9F, 31P, 77Se),2862 (31P),2860 CsH2But3M2 (31P),2661 EtP(Se)F, Cl2PbHCH2CH2CH2kHPCl2 (13C),2663 and ClP(CHPr'0)2CPri (31P).2664 Ph

H02P,

,PO,H 0

( 124)

For phosphirane E("P) is 40 467 515.97(8) Hz. The 13Cn.m.r. spectrum was also recorded.2666 The 31Pn.m.r. spectra of PC1,=N[PC12=N],PC12=S undergo significant changes in linewidth and 4J(31P,31P)when the temperature is lowered.2666P3N3CI, has been proposed as the external reference for 31P in 2w6

S. Bracher, J. I. G. Cadogan, I. Gosney, and S. Yaslak, J. Chem. SOC.,Chem. Commun.,

aw6

G. D. Ewen, M. A. K. El-Deek, D. J. H. Smith, and S. Trippett, J. Chem. Res. (S),

1983, 857. 1983, 14.

Y. Kimura, T. Kokura, and T. Saegusa, J . Org. Chem., 1983,48, 3815. a&48 H. Gross and S . Ozegowski, J. Prakt. Chem., 1983, 225,437. 2&4g I. Petnehazy, G. Szakzil, L. Toke, H. R. Hudson, L. Powroznyk, and C. J. Cooksey, Tetrahedron, 1983, 39, 4229. 2060 A. Rudi, D. Reichman, I. Goldberg, and Y. Kashman, Tetrahedron, 1983,39, 3965. A. E. Wroblewski, Tetrahedron, 1983, 39, 1809. 2662 J. M. Villanueva, N. Collignon, A. Guy, and Ph. Savignac, Tetrahedron, 1983, 39, 1299. a65s M. Mikolajczyk, B. Costisella, and S. Grzejszczak, Tetrahedron, 1983,39, 1189. a66p K. Issleib, K.-P. Dopfer, and A. Balszuweit, Phosphorus Sulphur, 1983, 14, 171. 2666 D. Bouchu, Phosphorus Sulphur, 1983, 15, 33. 2666 S. D. Pastor, J. D. Spivack, L. P. Steinhuebl, and C. M a m a , Phosphorus Sulphur, 1983, 2w7

15, 253.

D. Redmore and B. Dhawan, Phosphorus Sulphur, 1983,16,233. 2668 C. M. Angelov, V. Ch. Christov, J. Petrova, and M. Kirilov, Phosphorus Sulphur, 1983, a657

17, 37.

D. W. Aksnes and A. Lie, Org. Magn. Reson., 1983,21,417. M. Yoshifuji, K. Shibayama, N. Inamoto, K. Hirotsu, and T. Higuchi, J. Chem. Soc., Chem. Commun., 1983, 862. 2w1 R. Appel, F. Knoch, and H. Kunze, Angew. Chem., In?. Ed. Engl., 1983,22, 1004. K. M. Enikeev, I. E. Ismaev, A. V. Il'yasov, and I. A. Nuretdinov, In. Akad. Nauk SSSR, Ser. Khim., 1983,479 (Chem. Abstr., 1983, 99,22 563). am D. L. Allen, V. C. Gibson, M. L.H. Green, J. F. Skinner, J. Bashkin, and P. D. Grebenik, J. Chem. SOC.,Chem. Commun., 1983, 895. B. A. Arbuzov, 0. A. Erastov, S. N. Ignat'eva, I. P. Romanova, R. P. Arshinova, and R. A. Kadyrov, Izv. Akad. Nauk S S S R , Ser. Khim., 1983, 420 (Chem. Abstr., 1983, 98, 160 840). H. Goldwhite, D. Rowsell, L. E. Vertal, M. T. Bowers, M. A. Cooper, and S . L. Manatt, Org. Magn. Reson., 1983, 21, 494. 9066 G. Schilling, C. W. Rabener, and W. Lehr, Z. Naturforsch., Teil B, 1982,37, 1489 (Chem. Abstr., 1983, 98, 64 450).

142


intact biological From the 15N and 31P n.m.r. spectra of N,P,Cl,(NHPh), the relative signs of coupling constants have been determined and the Karplus equation has been derived.2668 N.m.r. data have also been reported for [p(CN).F6- .]- ('OF, 31P),2660 p(CN) ,x6-,]- (31P),2670 OC(NMe),PNEt, (13C, [(tetraphenylporphinato)PX,]+ (I3C, 31P),2671[(Ph3P)2N]+[S3N30]-(15N),2672 31P),2673 R22NP(NR1)2PNR22 (llB, 13C, 31P),2674 P,(NMe,), (13C),2675 P4(NPri,), (31P),2676 (Bu'N)~P,S~CI(31P),2677 FP(NBu'),PF (19F, 31P),2678 F4P(NHMe),PF4 ('OF, 31P),2679N 3 P 3 ( N m H 2 ) 6 (31P),2680 N3P3(NH&(0R)4 (31P),2681 N3P3C16 (31P),2se2 N3P3C~6-,(OR),(31P),2683 P3N3C14X(OCR=CH2)(31P),2s84 N3P3CI,-,N(PCI,N),SX(O) (31P),2686 N,P,CI,-,,(OR), (31P),2687 (OCH=CH,). ("C, 31P),2685 N,P,(NMe,),(NHR)(NR) (31P),2688 (15NPF2),,(15N, 31P),2680 and poly(ch1orotrimethylsi1oxy)phosphazene (31P).2690 15Nand 1 7 0 n.m.r. spectroscopy has been used to study lH binding sites in imidodiphosphate, tetraethyl imidodiphosphate, and adenylyl imidodiphos~hate.,~Ol The phosphorus-nitrogen bond in phosphorimidates has been studied using 15Nand 31Pn.m.r. ~ p e c t r o ~ c o pThe y . ~strong ~ ~ ~ influence of a phosphorusJ. K. Gard and J. J. H. Ackerman, J. Magn. Reson., 1983, 51, 124. B. Thomas, G. Grossmann, W. Bieger, and A. Porzel, 2. Anorg. Allg. Chem., 1983, 504, 138. 2w9 K. B. Dillon and A. W. G. Platt, J. Chem. SOC., Chem. Commun., 1983, 1089. 2670 K. B. Dillon and A. W. G. Platt, Polyhedron, 1983,2,641. 2671 E. Fluck and H. Richter, Chem. Ber., 1983,116,610. 2672 T . Chivers, A. W. Cordes, R. T. Oakley, and W. T. Pennington, Znorg. Chem., 1983, 22, 2429. 2673 C. A. Marrese and C. J. Carrano. Znorg. Chem., 1983, 22, 1858. 2674 P. Paetzold, C. von Plotho, E. Niecke, and R. Ruger, Chem. Ber., 1983,116, 1678. 2676 F. A. Cotton, J. G. Riess, and B. R. Stults, Znorg. Chem., 1983, 22, 133. 2676 R. B. King, N. D. Sadanani, and P. M. Sundaram, J. Chem. SOC., Chem. Commun., 1983, 477. 2677 0. J. Scherer, G. Wolmershauser, and H. Conrad, Angew. Chem., Znt. Ed. Engl., 1983, 22, 404. 2678 R. Keat, D. S. Rycroft, E. Niecke, H. G. Schaefer, and H. Zorn, 2. Naturforsch., Teil B, 1982, 37, 1665. 267s H. Hahn, K. Utary, and W. Meindl, Monatsh. Chem., 1983,114, 1167. 2680 A. A. van der Huizen, J. C. van de Grampel, W. Akkerman, P. Lelieveld, A. van der Meer-Kalverkamp, and H. B. Lamberts, Znorg. Chim. Acta., 1983, 78, 239. 2681 M. Kajiwara and Y. Kurachi, Pol-vhedron, 1983,2, 1211. 2682 V. V. Kireev, W. Sulkowski, G. I. Mitropol'skaya, and F. A. Bittirova, Vysokomol. Soedin., Ser. B, 1983, 25, 227 (Chem. Abstr., 1983, 98, 216 082). 2683 K. Ramachandran and C. W. Allen, Report, 1982, TR-11, order no. AD-A122598,21 pp., avail. NTIS, from Gov. Rep. Announce. Index (US.), 1983, 83, 1639 (Chem. Abstr., 1983, 99, 105 499). 2684 P. J. Harris, M. A. Schwalke, V. Liu, and B. L. Fisher, Znorg. Chem., 1983, 22, 1812. 268s K. Ramachandran and C. W. Allen, Znorg. Chem., 1983,22, 1445. 2686 B. De Ruiter, G. Kuipers, J. H. Bijlaart, and J. C. Van de Grampel, 2.Naturforsch., Teil B, 1982, 37, 1425 (Chem. Abstr., 1983,98, 107 401). 2687 H. G. Horn and F. Kolkmann, Makromol. Chem., 1982, 183, 2427 (Chem. Abstr., 1983, 98, 4856). 268s P. Ramabrahmam, K. S. Dhathathreyan, and S. S. Krishnamurthy, Indian J. Chem., Sect. A , 1983, 22, 1. 2688 B. Thomas and G. Grossmann, Z. Chem., 1983, 23, 27 (Chem. Abstr., 1983, 99, 5692). 2600 T. A. Chakra, R. De Jaeger, C. Baillet, L. Delfosse, J. P. Cavrot, and F. Rietsch, Makromol. Chem., 1983, 184, 991 (Chem. Abstr., 1983, 99, 38 845). 2601 M. A. Reynolds, J. A. Gerlt, P. C. Demou, N. J. Oppenheimer, and G. L. Kenyon, J. Am. Chem. SOC.,1983, 105, 6475. 2692 G. J. Martin, M. Sanchez, and M.-R. Marre, Tetrahedron Lett., 1983, 24, 4989. 2668


143

bonded oxygen, sulphur, or selenium atom on 1J(31P,15N)in 16N-phenylN.m.r. data have also been reaminodioxaphorinanes has been 4 ported for (ClCH2CH,),d(0)OCH2CH2CHR1NR2 (31P),2sg4 (C1CH2CH2),NP(O)(NH,)OH (31P),2696 (PhO)2P(O)NHP(O)(OPh),.PF,("F, 31P),2se8[C5H5NP(OPr),(OH)Cl]+ (31P),2697 2-(aryloxy)-2-oxo-l,3,2-dioxaphosphorinane(31P),wg8 C1CH2CH2NH(0)hN(CH,CHzCl)CH,CH2CH2b (3lp),2699

-

~CH2CMe,0POCMe,CH2kCH,CMe20~OCMe,CH, (31P),2700 [(Me,N),P(O)-

-

NMeCH,], (13C),,'01 PhC(=NR)NMeP(OEt), (13C,31P),2702 R1R2NP(OMe)(OR3) NCCH~CH~OPCINR~R~ (31~),2704 ( R O ) , P N ~ ( O ) ( O R )(31~),2705 (RFO)2~N(CH2CH2CH,0)2 (13C, leF, 31P),2706 (Me,N)3POCArCAr0 (13C),2707 Y,P(X)NHR (13C),2708 2-R-2-oxo-1,3,2-dioxaphosphorinanes (170),270e (RW)*P= NRa ("C, 31P),2710HN[P(O)Cl2I2 (31P),2711(EtO),P(O)N=P(OEt), (31P),271a RIN=C(SR2)NMeP(0)(0R 3, ( 3C, 'P) , (MeO),P(O)N=C(OE t)Ph ( 3C),27l4 {(NC)(F3C)20AsN=dN=C[O~(CF3)~]C(CF3)20z)2 (1gF),2715 F6SNPCI3 ("F, (31~),2703

,

W. Gombler, R. W. Kinas, and W. J. Stec, Z. Naturforsch., Teil B, 1983, 38, 815 (Chem. Abstr., 1983, 99, 212 594). G. Zon, S. M. Ludeman, G. Ozkan, S. Chandrasegaran, C. F. Hammer, R. Dickerson, K. Mizuta, and W. Egan, J. Pharm. Sci.,1983, 72, 687 (Chem. Abstr., 1983,99, 140 037). a886 S. M. Ludeman, K. L. Shao, G. Zon, V. L. Himes, A. D. Mighell, S. Takagi, and K. Mizuta, J. Med. Chem., 1983, 26, 1788 (Chem. Abstr., 1983, 99, 195 102). E. G. Il'in, M. N. Shcherbakova, Yu. A. Buslaev, L. Riesel, and J. Pauli, Dokl. Akad. Nauk SSSR, 1983,271, 892 (Chem. Abstr., 1983,99, 224 122). aa97 A. K. Akhlebinin, E. V. Borisov, and E. E. Nifant'ev, Zh. Obshch. Khim., 1982, 52, 2640 (Chem. Abstr., 1983, 98, 72 283). ldOB R. 0. Day, D. G. Gorenstein, and R. R. Holmes, Inorg. Chem., 1983, 22, 2192. aeg9 K. Misiura, A. Okruszek, K. Pankiewicz, W. J. Stec, Z. Czownicki, and B. Utracka, J. Med. Chem., 1983, 26, 674 (Chem. Abstr., 1983, 98, 154 861). a700 C.Bonnigue, D. Houalla, R. Wolf, and J. Jaud, J. Chem. SOC., Perkin Trans. 2, 1983,773. a701 G. Nee,T. Bottin-Strzalko, J. Seyden-Penne, M. Beaujean, and H. Viehe, J. Org. Chem., aa99

1983,48, 1111. V. V. Negrebetskii, A. D. Sinitsa, V. I. Kal'chenko, L. I. Atamas, and L. N. Markovskii, Zh. Obshch. Khim., 1983, 53, 343 (Chem. Abstr., 1983, 98, 198 350). a708 S. P. Adams, K. S. Kavka, E. J. Wykes, S. B. Holder, and G. R. Galluppi, J. Am. Chem. Soc., 1983, 105, 661. a704 N. D. Sinha, J. Biernat, and H. Koster, Tetrahedron Lett., 1983, 24, 5843. a706 E. S. Gubnitskaya, V. S. Parkhomenko, Z. T. Semashko, and L. I. Samaray, Phosphorus Sulphur, 1983, 15, 257. a706 D. B. Denney, D. Z. Denney, P. J. Hammond, C. Huang, La-T. Liu, and K.4. Tseng, Phosphorus Sulphur, 1983, 15, 281. D. B. Denney and S. D. Pastor, Phosphorus Sulphur, 1983, 16, 239. 1708 J. M. A. Al-Rawi, C. Q. Benham, and N. Ayed, Org. Magn. Reson., 1983, 21, 75. 4709 P. L. Bock, J. A. Mosbo, and J. L. Redmon, Org. Magn. Reson., 1983, 21, 491. 2710 A. Willeit, E. P. Muller, and P. Peringer, Helv. Chim. Acta, 1983, 66, 2467. a711 T. A. Chaktra, R. de Jaeger, and J. Heubel, 2. Anorg. Allg. Chem., 1983,501, 191. a718 L. Riesel, J. Steinbach, and E. Herrmann, 2.Anorg. Allg. Chem., 1983, 502,21. 4715 V. V. Negrebetskii, A. F. Grapov, V. N. Zontova, V. I. Ivanchenko, and N. N. Mel'nikov, Zh. Obshch. Khim., 1983, 53, 312 (Chem. Abstr., 1983,99, 53 843). 2714 V. Mizrahi, T. Hendrickse, and T. A. Modro, Can. J. Chem., 1983,61, 118. a716 H. W. Roesky, H. Djarrah, J. Lucas, M. Noltemeyer, and G. M.Sheldrick, Angew. Chem., Znt. Ed. Engl., 1983, 22, 1006. 870a

144


31P),2716[F,PN==C(SH)Me]- (19F, 31P),2717 H3NPF5 ('OF, 31P),2718 fluorophosphine derivatives (13C, 15N, 19F,31P),2719 and [AsF,(Et,NH),]+ (1sF).2720 A theoretical study of the shielding of lzOXeand 31P solvent effect of P,O, in CC14, CS2, and alkanes has been l9Fand 31Pn.m.r. spectra have been used to investigate P4Ol0, HP02F2,and PF, in fuming nitric acid, and various species were identified.2722 R1CH(C6H40)2POR2shows 5J(31P,1H)of 2.4 Hz; 31P n.m.r. data were also given.2723 1J(31P,31P)of diphosphate anions has been shown to depend on the electronegativity of the substituent at phosp h o r ~ N.m.r. ~ . ~ ~data ~ ~ have also been reported for CF30NF2 (1gF),2725 FO$OCF,NFOSO,F (1sF),2726F3CS02N=S(NSEt2N),SSO2CF3 (1gF),2727 (1") 2728 [(R10)P(0)(OR2)ONEt3]+ (31p),272 O (CF3SN)4 I (R1C,H,0)(X)POCH2CH2CHR2b (13C),2730 C6HdN02)2O~(0)OCH,~HCH(b)CH2CH2CH2CH2 (31P),2731 (Pri0)2POCHFCH2CH=CH2 (31P),2732 (R10)P(OR2)2 (31P),2733 (PhCH,O)(O)fiOCH,CH,CMeHb (31P),2734 r 1 (MeO)P(O)(OR), (31P),2735 {P[OC(CF3)2C(CF3)20]2}- (l9F, 31P),2736 {Ob[OC(CF,)2C(CF3)26]2}- (l9F, 31P),2737 P40 6 + ( 'P) ,27 [P308(OAC)~] 33

2718 2717

J. S. Thrasher and K. Seppelt, 2. Anorg. Allg. Chem., 1983, 507, 7. L. Kolditz, U. Calov, Yu. A. Buslaev, and E. G. Win, 2. Anorg. Allg. Chem., 1983, 500, 65.

W. Storzer, D. Schomburg, G. V. Roeschenthaler, and R. Schmutzler, Chem. Ber., 1983, 116, 367. 2710 P. D. Blair, J . Mol. Strucr., 1983, 97, 147. 2720 E. G. Il'in, Yu. A. Buslaev, U. Calov, and L. Kolditz, Dokl. Akud. Nuuk SSSR, 1983, 270, 1146 (Chem. Abstr., 1983, 99, 111 598). 2721 U. Pohle and G. Grossmann, Actu Chim. Acud. Sci. Hung., 1982, 110, 381 (Chem. Abstr., 1983, 98, 64 474). 2722 C. C. Addison, J. W. Bailey, S. H. Bruce, M. F. A. Dove, R. C. Hibbert, and N. Logan, Polyhedron, 1983, 2, 651. 2723 P. A. Odorisio, S. D. Pastor, J. D. Spivack, L. Steinhuebel, and R. K. Rodebaugh, Phosphorus Sulphur, 1983, 15, 9. 2724 W. Krause and H. Falius, 2. Anorg. Allg. Chem., 1983, 496, 105. 2725 W. Maya, D. Pilipovich, M. G. Warner, R. D. Wilson, and K. 0. Christe, Inorg. Chem., 1983,22,810. 2728 S.-C. Chang and D. D. DesMarteau, Znorg. Chem., 1983, 22, 805. 2727 A. Gieren, H. W. Roesky, and L. Schonfelder, 2. Anorg. Allg. Chem., 1983, 495, 158. 2728 D. Bielefeldt and A. Haas, Chem. Ber., 1983, 116, 1257. 272s V. F. Zarytova, E. M. Ivanova, and V. P. Romanenko, Dokl. Akad. Nuuk SSSR, 1982, 265, 878 (Chem. Abstr., 1983, 98, 54 377). 2730 B. A. Arbuzov, R. P. Arshinova, V. S. Vinogradova, and P. P. Chernov, Zh. Obshch Khim., 1982, 52, 2176 (Chem. Abstr., 1983, 98, 72 263). 2731 D. 0.Shah, D. Kallick, R. Rowell, R. Chen, and D. G. Gorenstein, J . Am. Chem. SOC. 1983, 105, 6942. 2732 G. M. Blackburn and M. J. Parratt, J. Chem. SOC.,Chem. Commun., 1983, 886. 2733 K. A. Nelson, A. E. Sopchik, and W. G. Bentrude, J. Am. Chem. SOC., 1983, 105, 7752. 2734 P. Guga and W. J. Stec, Tetrahedron Lett., 1983, 24, 3899. 2735 P. M. Cullis, Tetrahedron Lett., 1983, 24, 5677. 2738 D. Schomburg, W. Storzer, R. Bohlen, W. Kuhn, and G.-V. Roschenthaler, Chern. Ber., 1983, 116, 3301. 2737 G.-V. Roschenthaler, R. Bohlen, W. Storzer, A. E. Sopchik, and W. G. Bentrude, 2. Anorg. Allg. Chem., 1983, 507, 93. 2738 M. Loeper and U. Schiilke, 2. Anorg. Allg. Chem., 1983, 500, 40. 2718


145

(31P),2738 tetraphosphoric acid trimethylsilyl esters (31P),2740 (R10)(R20),P0 (31P),2741 [(R10)(R20)P0,]- (13C),2742 and [diacetylphosphatel- (31P).2743

A correlation of 31Pchemical shifts with v(P=O) has been found for organic and nucleotide lgF and 31P n.m.r. spectroscopy has been used for the analysis of coal-derived Intramolecular lH3lP n.0.e. has been studied using two-dimensional n.m.r. for ATP.2740 lH-{lH} n.0.e. has been used to map the conformation of purine m ~ n ~ n ~ ~ l e The ~ t i170 d echemical ~ . ~ ~ ~ ~ shifts of bridging and non-bridging oxygen of pyrophosphate have been unambiguously assigned.2748 1 7 0 and 31Pn.m.r. spectra have been used to investigate enzyme-catalysed positional isotope exchange in ATP, 1 7 0 or l80 labelled.8749 Asymmetric incorporation of l 8 0 into pyrophosphate produces an isotope shift and an AB spectrum giving 2J(31P,31P) = 21.1 H z . An ~ ~approx~ ~ imately linear relation between the l80isotope effect in 31Pchemical shifts and 1J(81P,170)has been A surface coil for spacial localization of high-resolution 31Pn.m.r. spectra has been N.m.r. data have also been reported for CDP choline (13C),2763 uridylyl(3’ 5’)adenosine (W, 1,Zdimet henylenephosphorochloridate (SlP),8766 170, lP),2764 h H,OPOP(O)(OH)OCH,dHCO,H (31P),2766 [ROPO3I2-(31P),2767 phosphate sugar esters (13C, 31P),2768 poly(dialky1phosphoric acid) (13C, 31P),275g oil additives --+

J. Neels, Z . Anorg. Allg. Chem., 1983, 500, 97. K. Yamamoto and H.Watanabe, Chem. Lett., 1982, 1225. a741 M. M. Sidky, W. M. Abdou, and N. M. Abd-el Rahman, Phosphorus Sulphur, 1983, 16, a7sg

331. J. F. Santaren, M. Rico, and A. Ribera, Org. Magn. Reson., 1983, 21, 238. J. Neels and H. Grunze, 2.Anorg. Allg. Chem., 1982, 495, 65. A. V. Lebedev, A. I. Rezvukhin, G. G. Furin, and 0 .Kh. Poleshchuk, Zh. Strukr. Khim., 1983,24, 39 (Chem. Absrr., 1983,99, 195 096). a746 J. W. Stadelhofer, K. D. Bartle, and R. S . Matthews, Proc. - Znt. Kohlenwiss. Tag., 1981, 792 (Chem. Abstr., 1983, 98, 56 837). 8746 C. Yu and G. C. Levy, J. Am. Chem. SOC.,1983, 105,6994. a747 H.Santos, A. V. Xavier, and C. F. G. C. Geraldes, Can. J. Chem., 1983, 61, 1456. a748 J. A. Gerlt, M. A. Reynolds, P. C. Demou, and G. L. Kenyon, J. Am. Chem. SOC.,1983, 105, 6469. a74n M. A. Reynolds, N. J. Oppenheimer, and G. L. Kenyon, J. Am. Chem. SOC.,1983, 105, 6663. 8760T.M. Marschner, M. A. Reynolds, N. J. Oppenheimer, and G. L. Kenyon, J. Chem. SOC.,Chem. Commun., 1983, 1289. a761 R. D. Sammons, P. A. Frey, K. Bruzik, and M. D. Tsai, J. Am. Chem. SOC.,1983,105, 5455. 476a A. Haase, C. Malloy, and G. K. Radda, J. Magn. Reson., 1983, 55, 164. a768 M. C. Sanchez, J. M. Fernandez, E. Forne, J. Castello, A. Sacristan, and J. A. Ortiz, Arzneim.-Forsch., 1983, 33, 1011 (Chem. Absrr., 1983, 99, 93 617). 8764 F. Seela, J. Ott, and B. V. L. Potter, J. Am. Chem. SOC.,1983, 105, 5879. a765 F. Ramirez and J. F. Marecek, J. Org. Chem., 1983, 48, 847. a766 S. Kanodia and M. F. Roberts, Proc. Natl. Acad. Sci. U.S.A., 1983, 80, 5217 (Chem. Absrr., 1983, 99, 172 485). K. C. Calvo and F. H. Westheimer, J. Am. Chem. SOC., 1983, 105, 2827. p7s* J.-R. Neeser, J. M. J. Tronchet, and E. J. Charollais, Can. J. Chem., 1983, 61, 1387. a7sn G. Lapienis, S. Penczek, and J. Pretula, Macromolecules, 1983, 16, 153 (Chem. Abstr. 1983, 98, 89 802). a74a a743 a744

146


(31P),2760 organophosphorus insecticides (31P),2761 and biological phosphates (SlP).2762-278 8

The 1°F and 31Pn.m.r. spectra of PO(OPF,), have been analysed as A[MX2]3.278e The analysis of the lH n.m.r. spectra of 2,8-dithia-l,5-E-bicycloG. L. Marshall, Proc. Inst. Per., London, 1982, (2, Petroanal. '81), 409 (Chem. Absrr., 1983,99, 73 400). 2761 R. Greenhalgh, B. A. Blackwell, C. M. Preston, and W. J. Murray, J. Agric. Food Chem., 1983, 31, 710 (Chem. Abstr., 1983, 99, 34 397). 2762 S. W. Hui, L. T. Boni, T. P. Stewart, and T. Isac, Biochemistry, 1983, 22, 3511 (Chem. Abstr., 1983, 99, 19 229). 2763 P. R. Allegrini, G. Van Scharrenburg, G. H. De Haas, and J. Seelig, Biochim. Biophys. Acta, 1983, 731, 448 (Chem. Abstr., 1983, 99, 49 236). 2764 J. Emsley and S. Niazi, Phosphorus Sulphur, 1983, 16, 303. 2765 K. D. Schnackerz and P. Bartholmes, Biochem. Biophys. Res. Commun., 1983, 111, 817 (Chem. Abstr., 1983, 98, 157 023). 2766 A. Pardi, R. Walker, H. Rapoport, G. Wider, and K. Wuethrich, J. Am. Chem. SOC., 1983, 105, 1652. 2767 P. H. Bolton, J. Mugn. Reson., 1983, 52, 326 (Chem. Abstr., 1983, 98, 190 446). 2768 M. Florentz and P. Granger, Environ. Technol. Lett., 1983, 4, 9 (Chem. Absrr., 1983, 98, 113 416). 276B S. J. Simpson, M. R. Bendall, A. F. Egan, R. Vink, and P. J. Rogers, Ew. J . Biochem., 1983, 136, 63 (Chem. Abstr., 1983, 99, 191 347). 2770 M. D. Tsai, R. T. Jiang, and K. Bruzik, J. Am. Chem. Soc., 1983, 105, 2478. 2771 V. V. Kupriyanov, A. Ya. Shteinshneider, E. Ruuge, V. N. Smirnov, and V. A. Saks, Biochem. Biophys. Res. Commun., 1983, 114, 1117 (Chem. Abstr., 1983,99, 101 501). 2772 R. J. Labotka and R. A. Kleps, Biochemistry, 1983, 22, 6089 (Chem. Abstr., 1983, 99, 209 118). 2773 C. E. Bulawa, J. D. Hermes, and C. R. H. Raetz, J. Biol. Chem., 1983,258, 14 974 (Chem. Abstr., 1983, 99, 208 671). 2774 G. Whitman, R. Kieval, L. Wetstein, S. Seeholzer, G. McDonald, and A. Harken, J. Surg. Res., 1983, 35, 332 (Chem. Abstr., 1983, 99, 210 724). 2775 J. M. Quashnock, J. F. Chlebowski, M. Martinez-Carrion, and L. Schirch, J. Biol. Chem., 1983, 258, 503 (Chem. Abstr., 1983, 98, 67 905). 2776 K. Beyer and M. Klingenberg, Biochemistry, 1983, 22, 639 (Chem. Abstr., 1983, 98, 67 747). 2777 D. J. Siminovitch, K. R. Jeffrey, and H. Eibl, Biochim. Biophys. Acta, 1983, 727, 122 (Chem. Absrr., 1983, 98, 67 465). 2778 T. Glonek, S. J. Kopp, E. Kot, J. W. Pettegrew, W. H. Harrison, and M. M. Cohen, J. Newochem., 1982, 39, 1210 (Chem. Abstr., 1983, 98, 30 819). 277B R. A. Burns, jun., R. E. Stark, D. A. Vidusek, and M. F. Roberts, Biochemistry, 1983,22, 5084 (Chem. Abstr., 1983, 99, 154 127). 2780 B. D. Fleming and K. M. W. Keough, Can. J. Biochem. Cell Biol., 1983, 61, 882 (Chem. Abstr., 1983, 99, 154 130). 2781 W. G. Wu and C. H. Huang, Biochemistry, 1983, 22, 5068 (Chem. Abstr., 1983, 99, 154 146). 2782 N. A. Vermue and K. Nicolay, FEBS Lett., 1983, 156, 293 (Chem. Abstr., 1983, 99, 68 195). 2783 K. J. Klaus, G. Gollin, E. J. Barrett, and R. G. Shulman, FEBS Letr., 1983, 159, 207 (Chem. Abstr., 1983, 99, 154 674). 2784 Y. Seo, M. Murakami, H. Watari, Y. Imai, K. Yoshizaki, H. Nishikawa, and T. Morimoto, J. Biochem. (Tokyo), 1983, 94, 729 (Chem. Absrr., 1983, 99, 154678). 2785 I. S . Sokolova, P. Yu. Shkarin, V. Z. Dubinskii, A. A. Samoilenko, L. A. Sibel'dina, and L. B. Gorbacheva, Dokl. Akud. Nuuk S S S R , 1983, 271, 223 (Chem. Abstr., 1983, 99, 156 206). 2786 G. M. Sorokoumova, I, A. Vasilenko, V. I. Shvets, A. A. Selishcheva, and V. L. Borovyagin, Bioorg. Khim., 1983, 9, 1106 (Chem. Abstr., 1983, 99, 208 382). 2787 P. M. Cullis, J. Am. Chem. Soc., 1983, 105, 7783. 2788 A. Gross, 0. Abril, J. M. Lewis, S. Geresh, and G. M. Whitesides, J. Am. Chem. SOC., 1983, 105, 7428. 2780 E. A. V. Ebsworth, G. M. Hunter, and D. W. H. Rankin, J . Chem. SOC.,Dalton Trans., 1983, 245. 2760

147


[3.3.0] octanes (E = P or As) has been assisted with two-dimensional J-resolved The %09Biand lgF n.m.r. spectra of [BiF,]- yield n.m.r. 1J (209B’, 1 19F) = 3823 f 3 N.m.r. data have also been reported for (EtO),P(O)(OR) (31P),27g2 chiral thiophospholipids (13C, I4N, 31P),sng3[(RO),PS,],MCls-, (M = As or Sb; 31P),27g4 [bCH,CH,CHMeO$(S)],O (s1P),2786 6CH2CEt2CHaOFk2H(31P),27se X(13C)937g7 [bCHMeCHMeOh,](s1P),2788 [PsO~-,S,I6- (31P),27gg [POS,FI2- (31P),2800 P4Ses (31P),2B01 [(RO),PS,]s-,BiCI, (31P),2802 POF,-.(OPh), (1gF),2e03 lPS2F,]- (lgF, 31P),8804HPF6(0,PF,) (lgF, 31P),2m PF,]- (31P),2eoa[AsF,]- (19F),2807 [SbC14Br2]- (1r1Sb),gso8and [BiF,]- (1gF).280g 9 Compounds of Groups VI and VII

and Xenon

Three relevant reviews have appeared: ‘N.m.r. of Group VI elements other than oxygen’,281o‘N.m.r. spectroscopy of oriented organoselenium compounds’,8811 and ‘N.m.r. of the halogens - chlorine, bromine, and iodine’.2812 The gas-phase 1 7 0 isotope shift Q(D~~~O)-Q(H,~~O) has been measured as 4.04 f 0.35 in good agreement with 1 7 0 n.m.r. spectra of [HsO]+, 2790

A. Zschunke, C. Muegge, H. Meyer, A. Tzschach, and K. Jurkschat, Org. Magn. Reson.,

2701

K.Morgan, B. G. Sayer, and G. J. Schrobilgen, J. Magn. Reson., 1983,52,

1983, 21, 315. 139.

L. Field, N. E. Heimer, R. I. McNeil, R. A. Neal, J. Swinson, and J. R. Van Wazer, Sulphur Lett., 1983, 1, 135 (Chem. Abstr., 1983, 99, 140040). a7gs K. Bruzik, R. T. Jiang, and M. D. Tsai, Biochemistry, 1983,22,2478 (Chem. Abstr., 1983, 279a

98, 175 814). 2794

279ri a79a

H. P. S. Chauhan, G. Srivastava, and R. C. Mehrotra, Polyhedron, 1983,2, 359. M. Mikolajczyk, B. Ziemnicka, J. Karolak-Wojciechowska, and M . Wieczorek, J. Chem. SOC.,Perkin Trans. 2, 1983, 501. H. P. S. Chauhan, C. P. Bhasin, G. Srivastava, and R. C. Mehrotra, Phosphorus Sulphur, 1983, 15, 99.

D. Gonbeau, G. Pfister-Guillouzo, A. Meriem, J. P. Majoral, and J. Navech, J. Mol. Sfruct., 1983, 98, 109. a798 P. Biscarini, Inorg. Chim. Acta, 1983, 74, 65. a799 W. Krause and H. Falius, Z. Anorg. Allg. Chem., 1983, 496, 80. 2800 M. Meisel and Ch. Donath, Z. Anorg. Allg. Chem., 1983, 500, 73. 2801 R. Blachnik and U. Wickel, Z. Natwforsch., Teil B, 1982, 37, 1507 (Chem. Abstr., 1983, 8797

98, 78 925). 2808

280s

H.P. S. Chauhan, G. Srivastava, and R. C. Mehrotra, Phosphorus Sulphur, 1983,17, 161. E. G. Il’in, U. Calov, L. Kolditz, and Yu. A. Buslaev, Dokl. Akad. Nauk SSSR, 1982, a66, 123 (Chem. Abstr., 1983,98, 10 690). L. Kolditz, U. Kalov, E. G. Win, and Yu. S. Buslaev, Dokl. Akad. Nauk SSSR, 1982, 267, 1392 (Chem. Abstr., 1983,99, 98 213).

a80s

E. G. Il’in, M. Meisel, M. N. Shcherbakova, and G. U. Wolf, Dokl. Akad. Nauk SSSR,

1982, 266, 878 (Chem. Abstr., 1983,98, 82 805). A. V. Kopitin, P. Gabor Klatsmanyi, V. P. Izvekov, E. Pungor, G. A. Yagodin, and E. G. Win, Magy. Kem. Foly., 1983, 89, 87 (Chem. Abstr., 1983, 98, 190 761). 4807 J. W. Bats, H. Fuess, K. L. Weber, and H. W. Roesky, Chem. Ber., 1983, 116, 1751. G. J. Goetz-Grandmont and M.J. F. Leroy, Z. Anorg. Allg. Chem., 1983,4%,40. V. F. Sukhoverkhov and A. V. Sharabarin, Zh. Neorg. Khim., 1983, 28, 629 (Chem. Abstr., 1983, 98, 190 614). 2810 0. Lutz, NATO Adv. Study Znst. Ser., Ser. C, 1983, 103, 389 (Chem. Abstr., 1983, 99, 132 400). C. L. Khetrapal, J. Indian Chem. SOC.,1982, 59, 1276 (Chem. Abstr., 1983, 99 174908). T. Drakenberg and S. Forsen NATO Adv. Study Inst. Ser., Ser. C , 1983,103,405 (Chem. Abstr., 1983, 99, 132 401). a81a W. T. Raynes, Mol. Phys., 1983, 49, 443.


148

[D30]+, [MeOH,]+, and [Me,COH]+ have been obtained and interpreted.2814 The nuclear magnetic relaxation of lH, ,H, and 1 7 0 in water has been studied.2816 Linear solvation-energy relationships have been applied to solvent effects on 6(77Se)and 8(12sTe)for Me,Se and Me,Te.2816Me,Se has been examined as a chemical-shift reference of 77Se chemical lH and 77Se spin-lattice relaxation times have been measured for MeE(CH,),EMe. The 77SeTl values are dominated by spin rotation and c.s.a. mechanisms.2818The effects of all selenium isotopes on 6(77Se)of the neighbouring atom in CF,SeSeCF,, CF,SeSeMe, and MeSeSeMe has been determined.281DLong-range J(77Se,13C)in PhSeMe, Ph,Se, Ph,Se,, and derivatives has been studied, and factors affecting it are orientation, co-ordination number, and ring formation.2820 The 13C 1 7 0 and 77Sen.m.r. spectra of some carbonyl and selenocarbonyl compounds have been studied. A correlation was found between 8(170) and 6(77Se).2821 Substituent effects in 2-substituted selenolo[2,3-b]selenophenes have been studied by lH, 13C, and 77Sen.m.r. spectroscopy.2822 PhSeCl and PhSeBr have been examined in a liquid ~ r y ~ t a 1 N.m.r. . ~ ~ data ~ ~ have - ~ also ~ ~ been ~ reported for (PhCH2),X (X = 0, S, Se, or Te; 13C),2826 R1E(CH2),CR2(C0,Et), (77Se,126Te),2827 ArSeC(CHO)=CHMe (13C),2828 R,C=Se (13C, 77Se),2829 PhER (E = S, Se, or Te; 13C),2830(125) (13C),2831 PhTe(alkeny1) (13C),2832 [H2C=CHSF4]+ (19F),2833 9

9

D. Mateescu, G. M. Benedikt, and M. P. Kelly, Synth. Appl. Zsot. Labeled Compd., Proc. Znt. Symp., 1982, 1983, 483 (Chem. Abstr., 1983, 98, 118 317). 281s C. W. R. Mulder, J. Schriever, and J. C. Leyte, J . Phys. Chem., 1983, 87, 2336. 2816 R. W. Taft and M. J. Kamlet, Znorg. Chem., 1983, 22, 250. 2817 N. P. Luthra, R. B. Dunlap, and J. D. Odom, J. Magn. Reson., 1983, 52, 318. E. W. Abel, K. G. Orrell, and A. W. G . Platt, Org. Magn. Reson., 1983, 21, 196. 281D W. Gombler, J . Magn. Reson., 1983, 53, 69. 2820 W. Nakanishi and Y. Ikeda, Bull. Chem. SOC.Jpn., 1983, 56, 1661. 2821 T. C. Wong, F. S. Guziec, jun., and C. A. Moustakis, J. Chem. SOC.,Perkin Trans. 2, 2814 G.

1983, 1471.

A. 2823 C. 2824 N. 282s N. 2826 G. 2822

2827

Konar and V. P. Litvinov, Chem. Scr., 1983, 22, 22 (Chem. Abstr., 1983, 99, 70 076). L. Khetrapal and A. C. Kunwar, Israel J . Chem., 1983, 23, 299. Surya, A. C. Kunwar, and C. L. Khetrapal, J. Organomet. Chem., 1983, 252, 301. Suryaprakash, A. C. Kunwar, and C. L. Khetrapal, J. Magn. Reson., 1983, 54, 502. Llabres, M. Baiwir, L. Christiaens, and J. L. Piette, Bull. SOC.R . Sci. Liege, 1982, 51, 365 (Chem. Abstr., 1983, 99, 212 043). R. A. Grigsby, jun., K. J. Irgolic, and F. F. Knapp, jun., J . Organornet. Chem., 1983,259, 171.

K. Uneyama, K. Takano, and S. Torii, Bull. Chem. SOC.Jpn., 1983, 56, 2867. 2829 R. Okazaki, A. Ishii, and N. Inamoto, J . Chem. SOC.,Chem. Commun., 1983, 1429. 2830 T. Kauffmann and H. Ahlers, Chem. Ber., 1983, 116, 1001. 2831 T. Laitalainen, T. Simonen, R. Kivekas, and M. Klinga, J. Chem. SOC.,Perkin Trans. I , 2828

1983, 333.

S. Uemura, S.4. Fukuzawa, and S. R. Patil, J . Organomet. Chem., 1983, 243, 9. 2833 J. Wessel, G. Kleemann, and K. Seppelt, Chem. Ber., 1983, 116, 2399. 2832


149

R,SeX, (13C),2834 RSe(O)O,Bu' (13C),2835 ArSeX (13C),283* RaTe, PhER (E = Se or Te; 77Se, 126Te),2837 ClTkOCArCHCAr (13C, 126Te),2e38MeCH(0Me)CHMeTePhBr, (13C),283Q and R1TeTeR2(126Te).2840 The [AB], spin system in (126) has been analysed using two-dimensional correlation n.m.r. The 33S spin-lattice relaxation time of [SO4I2-has been determined as a function of temperature and concentration and discussed in terms of anion-solvent and ion-pair N.m.r. data have also been reported for W(SF,),]+ (1sF),2843 (127) (13C),8844 FsP=NTeF6 (lgF, 31P),2846 TeF,N=CCl, (1eF),28uTe(OH),F,-, (19F),2e47 (126Te),B848 POFa' OTeF, (lgF, 31P),284g TeF,OF (10F),2860 and SF,Br (19F).2861 The theory for nuclear shielding, including electron correlation effects, has been derived and applied to the HF molecule.2862 1J(36837C1,1*F) has been determined for [C1F,]-.2863N.m.r. data have also been reported for F,C(CF,),BrF, (1sF),2864 IF5NR3(1eF),2866 and Xe[N(SO,F),], (15N, leF, 129Xe).28w 10 Appendix This appendix contains a list of papers in which the use of nuclei other than lH has been described. The nuclei are ordered by increasing mass. BH

a834

11, 35, 372, 396, 450, 575, 580, 586, 822, 1087, 1247, 1249, 1303, 1309, 1321, 1435, 1478, 1482, 1483, 1519, 1580, 1593, 1705, 1721, 1722, 1724, 1730, 1887, 2018, 2053, 2055, 2080, 2098, 2104, 2105, 2472, and 2815.

W. Nakanishi, Y. Yamamoto, Y. Kusuyama, Y. Ikeda, and H. Iwamura, Chem. Lett.,

1983, 675. A. J. Bloodworth and D. J. Laph m, J. Chem. Soc., Perkin Trans. 1 , 1983, 471. 288(1 G. Llabres, M. Baiwir, L. Christiaens, and J.-L. Piette, Org. Magn. Reson., 1983, 21, 461. a83s

D. H. O'Brien, N. Dereu, C. K. Huang, K. J. Irolic, and F. F. Knapp, jun., Orgunometallics, 1983, 2, 305 (Chem. Abstr., 1983, 98, 125 270). 2838 M. R. Detty, B. J. Murray, D. L. Smith, and N. Zumbulyadis, J. Am. Chem. SOC.,1983, a837

105, 875.

S. Uemura, S.-i. Fukuzawa, and A. Toshimitsu, J. Organomet. Chem., 1983, 250, 203. a840 C. H. W. Jones and R. D. Sharma, J. Organomet. Chem., 1983,255, 61. 2841 M. A. Thomas, K. V. Ramanathan, and A. Kumar, J. Magn. Reson., 1983, 55, 386. 2842 J. F. Hinton and D. Shungu, J. Magn. Reson., 1983, 54, 309. a843 W. V. F. Brooks, G. K. MacLean, J. Passmore, P. S. White, and C.-M. Wong, J. Chem. SOC.,Dalton Trans., 1983, 1961. awJ. M. Vernon, M. R. Bryce, andT. A. Dransfield, Tetrahedron, 1983,39, 835. H. Hartl, P. Huppmann, D. Lentz, and K. Seppelt, Znorg. Chem., 1983, 22, 2183. a846 J. S. Thrasher and K. Seppelt, Angew. Chem., Znt. Ed. Engl., 1983,22, 789; Suppl., 1106. 2847 Yu. A. Buslaev, Yu. V. Kokunov, M. P. Gustyakova, and Yu. D. Chubar, Koord. Khim., 1983, 9, 366 (Chem. Abstr., 1983, 98, 171 970). 28p8 W. Toetsch and F. Sladky, 2. Naturforsch., Teil B, 1983, 38, 1025 (Chem. Abstr., 1983,99, 2838

151 079).

D. Lentz and K. Seppelt, Z. Anorg. Allg. Chem., 1983, 502, 83. 28so C. J. Schack, W. W. Wilson, and K. 0. Christe, Znorg. Chem., 1983, 22, 18. a8s1 R. Rahbarnoohi and L. C. Sams, Znorg. Chem., 1983,22, 840. H. Fukui, Int. J. Quantum Chem., 1983, 23, 633 (Chem. Abstr., 1983, 98, 82 609). a863 K. 0. Christe, W. W. Wilson, and E. C. Curtis, Znorg. Chern., 1983, 22, 3056. a8s4 M. H. Habibi and L. C. Sams, J. Fluorine Chem., 1982, 21, 287 (Chem. Abstr., 1983, 98, a8ss a856

106 741). S. A. Sharkov, Yu. V. Kokunov, V. S. Neporezov, and Yu. A. Buslaev, Koord. Khim., 1982, 8, 1597 (Chem. Abstr., 1983, 98, 100 21 1). G . A. Schumacher and G. J. Schrobilgen, Inorg. Chem., 1983.22, 2178.

150


3H 6Li 'Li

1849. 23 and 1289. 23,29, 30, 32,39, 500, 1201, 1237-1239, 1241, 1242, 1286-1289, 13011303, 1312, 1651, 1677-1682, 1710, 1739, 1774, 1915, 1953, 2009, and 2027. 1773. 24 and 42. 1204, 1666,2124, and 2191. 69,94, 182, 188, 197,250, 340, 393,433,494, 614,650,662,665,666,668, 792,858,859,1204,1205, 1273,1401-1403,1405,1410,1518,1519,1621, 1666, 1736, 1802-1805, 1874, 1875, 1889, 1915, 1924-1933, 2121, 2122, 2125-2157, 2160, 2161, 2164-2167, 2171, 2172, 2174, 2176, 2178, 2180,

2183,2185-2187,2189-2193,2195-2197,2199-2204,2207,2208,2211, 2213, 2214, 2216-2223, 2539, and 2674. 13C 12,20,21,25-29,

31, 38,40,42,45,46, 52-54, 58, 59, 61-63,65,66,68, 70-74, 76-83, 85-90, 96-98, 100, 101, 106, 107, 112, 113, 124, 125, 127-139, 141-147, 149-155, 157, 159-165, 168, 170, 171, 173-176, 178-181, 183, 185-187, 189, 191, 193, 195, 196, 198-216, 218-220, 223,224,229, 242-247,250-252, 255, 256,259, 273, 275,278,281, 290, 297, 300, 304, 305, 307, 308, 310, 317, 319-321, 323, 324, 326-329, 331-333, 335-342, 344, 347, 348, 350, 351, 353, 354, 357, 359-364, 373, 374, 379-381, 383-385, 387, 390-397, 3 9 9 4 2 , 40-15, 417429, 432435, 437, 438, 440444, 446, 447, 449, 451453, 455461, 4 6 M 7 2 , 47-82, 486, 4 8 8 4 9 3 , 496, 497, 499, 502-506, 509, 510, 514, 515, 520, 523-525, 527-529, 531, 536, 541, 542, 545, 547, 549, 550, 553,554,556-558,560-563,566,567,569-572, 579, 580,583,586, 590, 593, 601-604, 606-609, 611, 612, 614-624, 627-631, 637, 640, 6 4 2 4 7 , 649, 653, 658, 659, 661-664, 667, 671, 672, 674, 675, 679,680, 682484, 687, 695, 697, 701, 718, 720-722, 724-727, 729, 731-733, 735-749, 758-760, 763, 773, 776, 788-794, 801-805, 807-812, 815, 817-822, 825, 828-830, 835-838, 841, 842, 848, 853, 854, 856-860, 862, 864, 868, 869, 873, 874, 880-884, 887, 895-897, 899,903, 904,907, 908, 911-917, 919, 928, 931-934, 936, 947, 948, 951-953, 957-960, 962, 965, 969, 976, 980, 985, 986, 990-993, 995-997, 1o00, 1001, 1004, 1005, 1014, 1015, 1019-1024, 1026-1028, 1036-1040, 1043, 1046, 1056, 1063, 1069, 1071, 1077-1081, 1083-1086, 1088, 1089, 1092-1094, 1097, 1104-1106, 1108-1112, 1117, 1119-1123, 1125, 1127-1129, 1132-1149, 1152,1154-1158, 1160--1164,1167,1180,1185,1186,11891191, 1198, 1200, 1201, 1204, 1206, 1207, 1209, 1214, 1216, 1222-1228, 1230, 1232, 1240, 1241, 1250, 1255, 1259, 1265, 1273, 1276, 1278, 1288, 1289, 1292-1294, 1297, 1298, 1301, 1312, 1318, 1327, 1342, 1343, 1347, 1353, 1359, 1361, 1362, 1366, 1368, 1382, 1386, 1389, 1395, 1411-1413, 1419, 1422, 1431, 1433-1436, 1439, 1441, 1444, 1447, 1448, 1451, 1460, 1465, 1468-1471, 1475, 1476, 1482, 1484-1486, 1490, 1495, 1498, 1499, 1502, 1503, 1509, 1514, 1532, 1526, 1552, 1558, 1560, 1570, 1572, 1573, 1575, 1577, 1588, 1593, 1602, 1605, 1609-1612, 1616, 1617, 1620, 1622,


151

1623, 1628, 1630, 1636, 1640, 1643, 1644, 1647, 1649, 1674, 1684, 1770, 1785, 1786, 1791, 1812, 1894, 1898, 1971, 1972, 1975, 2013, 2022, 2026, 2037, 2049,2077, 2078, 2081, 2086,2088, 2091,2092,2095-2097, 20992101, 2108, 2110, 2112-2116, 2119, 2127, 2130, 2134, 2136, 2138, 2146, 2147,2156,2172-2182,2184-2186,2188, 2193, 2194,2196, 2198,22& 2202, 2207, 2210, 2211, 2213, 2215, 2217, 2225, 2227-2233, 2236, 2237, 2246, 2248, 2252,2254,2255,2257-2261, 2263-2270,2272-2276,2278, 2280, 2282, 2284, 2285, 2287-2303, 2306-2321, 2323-2325, 23272332, 2337, 2339-2342, 2346, 2347, 2350, 2352-2357, 2359,2362,2370, 2372-2383,2387-2389,2391,2393-2402, 2404, 2405, 2407, 2410, 2414, 2418, 2419, 2421-2425, 2427, 2431, 2437-2439, 2444, 2445, 2455,2456, 2460, 2462-2465, 2468, 2477, 2479, 2483, 2486-2488,2490, 2493, 2494, 2496-2503, 2509,2511,2512,2514,2518,2519, 2521-2523,2525,25282530, 2534-2536,2538-2540, 2543, 2545,2546, 2549, 2551, 2552,2555, 2556, 2558-2560, 2562, 2563, 2566, 2571, 2572, 2574, 2575, 2579, 2581, 2583, 2584, 25%2592,2594, 2597-2599, 2603, 2608,2609, 2612,2613, 2626,26362636,2640, 2642-2644,2649-2653, 2657,2659, 2663,2665, 2671, 2673-2675, 2685, 2701, 2702, 2706-2708, 2710, 2713, 2714, 2719, 2730, 2742, 2753, 2754, 2756, 2758, 2759, 2793, 2797, 2820, 2821, 2826, 2828-2832, 2834-2836, 2839, and 2844. 14N 42, 167, 250, 1289, 1424, 1629, 1685, 1686, 1887, 2400, 2472, 2473, 2777, and 2793. 17N 16-18, 251, 346, 556, 631, 717, 720, 722, 734, 774, 912, 955, 956, 1033, 1430, 1579, 1629, 1759, 2033, 2037, 2083, 2084, 2086, 2087, 2107, 2127, 2138, 2173, 2209, 2418, 2437, 2444, 2473, 2486, 2668, 2672, 2689, 2691, 2692, 2719, and 2856. 13, 29, 167, 229, 247, 269, 276, 279, 283, 301, 1247, 1252, 1255, 1265, 170 1268, 1280, 1281, 1288, 1370, 1427, 1498, 1641, 1646, 1783, 1784, 2023, 2225, 2263, 2370, 2441, 2470, 2486, 2691, 2709, 2748, 2749, 2751, 2754, 2813-2815, and 2821. 1@F 22, 87, 97, 107, 111, 116, 117, 128, 156, 166, 169, 172, 192, 243, 265, 267, 285, 295, 312, 313, 323, 325, 334, 349, 352, 403, 415, 416, 420, 434, 469, 475, 507, 516, 517, 546, 548, 564, 583, 613, 649, 651, 660, 702, 705, 706, 766,782, 800, 816, 820, 821, 823, 832, 863,914,930,947,994, 1017, 1025, 1029, 1056, 1070, 1071, 1166, 1179, 1220, 1226, 1228-1231, 1235, 1244, 1283, 1311, 1322, 1416, 1427, 1430, 1443, 1463, 1465, 1517, 1539, 1565, 1566, 1647, 1681, 1687, 1710-1713, 1719, 1720, 1734, 1737, 1746, 17491752, 1757, 1762-1764, 1792, 1796, 1797, 1818, 1819, 1825, 1826, 1845, 1846, 1879, 1880, 1899, 1906, 1957, 1973, 1974, 1976, 2011, 2012, 2014, 2015, 2029, 2030, 2034, 2041, 2047, 2048, 2129, 2169, 2195, 2206, 2212, 2214, 2221, 2260, 2261, 2344, 2361, 2390-2393, 2400, 2402, 2420, 2426, 2429, 2438, 2443, 2457, 2458, 2461, 2491, 2510, 2516, 2539, 2543, 2569, 2570, 2611, 2612, 2638, 2662, 2669, 2678, 2679, 2696, 2715-2720, 2722, 2725-2728, 2736, 2737, 2745, 2789, 2791, 2803-2805, 2807, 2809, 2833, 2843, and 2845-2856. 23Na 23, 29, 33-35,40, 1238, 1249, 1250, 1290, 1291, 1293, 1303, 1305-1308,

152


1314-1316, 1352,1406,1407,1410,1638,1683,1685,1717,1739,1763, 1776-1778, 1841,1954-1956,2032,and 2453. 26Mg24,47,55, 1638,and 1783. 27Al 501, 1245,1246, 1275,1276,1404-1411, 1414,1415, 1417, 1522,1671, 1811,1934-1945, 1949,1955,1958-1970, 1995,2002,2070,2076,2122, 2224-2226, 2228,2229,2235,2237-2245, 2247,2248,and 2250. 2QSi 247,419,420,614,1214,1467,1558,1669,1671-1673, 1674,1813,1888, 1939,1949,1955,1961-1963, 1967-1970, 1977-2001,2003,2004,2021, 2024--2026,2028,2109, 2110,2116,2173,2184,2186,2237,2239,22512253,2256,2257,2260,2262,2263,2265,2267,2269,2271,2274,2275, 2303-2305, 2307,2309-23 1 1, 2313,2314,2316,2318,2345,2349,2354, 2356,2357,2364,2368,2369,2371,2374,2382-2386, 2390,2391,2393, 2394,2398,2400,2413,2417, 2418,2420-2424, 2426,2436-2439, 2442, and 2447-245 1. 31P 17,19,33, 34,40,41,50, 55, 56, 60,62,64,66,68,69,75,77,80,84, 87-89, 94,95,99,105,113, 115, 117,119,121-123, 126,128,130, 137, 139,140,148,152,155, 156,158-161, 163-166, 172,173,176-178, 184,186,189,191,194,197,198,201,203,206,208-210, 215,217,221, 222,225,226, 229,231-241,245, 247,249,253-272,274, 277,283,286, 290-300, 303,305,309,311, 314,316,318,322,324,326,330,331, 343, 347,351-358,360,361,363, 365,368-372,374-378, 381,382,384, 386, 388, 389, 397-399, 404,406,411,412,415,416,421,422,424,425, 430,431,433-437,439,440,444, 445, 448,454,461463,466,467, 477,480,483488,495,498, 501,507,508,511-513, 516-522, 526,530, 532-535, 537,539,542-544, 548,549,551, 552,554,555, 565,566,568, 573,576-585,587-589,591-597,599,600,605,608,610,625,626,630-

634,636,638,639,641,643,648,652,654--657,669,670,673,676-678, 681-694,696-708,728,750-755,761,762,764,765,767-772,775,777788,793,795-801,803,806,810,812-814, 817,818,822,826827,831, 833-836,839,840,843-856,858,859,861,862,864,865,868-872,87&

879,886-893, 898-902,905-908, 918,92&927, 929,933,935,937946,949,963,965-983, 988,989,992,994,998, 1001-1003, lW61009,1035,1041,1042,1049,1050,1057,-1062, 1080,1083,1085,1089, 1103,1105,1106,1108,1116,1125,1127,1130,1138, 1141, 1143,1147, 1152,1154,1159,1163-1168, 1170-1173, 1176,1179,1180,1182-1184, 1186,1187,1192-1194, 1201,1220,1221,1223,1225,1226,1228-1233, 1273,1301,1302,1304,1316,1319,1321-1324, 1327,1328,1330, 1331, 1343,1345,1351, 1364,1366,1371,1375,1388, 1391,1393,1394,1398, 1399,1415,1425-1427, 1442,1443,1450,1452,1453,1471-1474, 1477, 1479,1487,1489,1494,1498,1504,1506,1509, 1511, 1513, 1514,1523, 1524,1529-1539, 1569,1587,1603,1631,1793-1795, 1840,1876,1894, 1902,1903,2007,2020,2034-2041, 2043,2076,2102,2118,2129,2130, 2141,2142,2144,2155,2158-2164, 2168,2169,2178,2184,2205,2212, 2217,2230,2238,2250,2274-2286, 2333,2335,2340,2350-2353, 2356, 2358-2360, 2362-2367, 2372,2373,2389,2392,2393,2400,2403,2404, 2408,2409,2426,2428,2433,2439,2454,2455,2459,2466,2467,2469-


153

2471, 2474-2500, 2504, 2505, 2507-2509, 251 1-2515, 2517-2528, 2531-2538, 2541-2544, 2546-2548, 2550, 2551, 2553-2557, 2 5 s 2569,2571,2573,2574,2578-2582,258A2591,2593-2608,2610-2639,

2641, 2645-2649, 2652-2658, 26-2662, 2664, 2666-2671, 2673, 2674, 2676-2690, 2692-2700, 2702-2706, 2710-271 3, 2716-2719, 2721-2724, 2729, 2731-2741, 2743-2747, 2749-2752, 2754-2789, 2792-2796,2798-2802, 2804-2806, 2845, and 2849. 33S 14,2810, and 2842. 36Cl 15, 1169, 1248, 1275, 1276, 1288, 1302, 1388, 1431, 1776, 1779, 1820, 1821, 1882, 1907-1910, 2446, and 2812. 37CI 15, 1776, 1820, 1821, 1907-1910, and 2812. 39K 23, 36, 37, 1296, 1297, 1310, 1316, 1638, 1896, and 1901. 43Ca 24,47, 48, 51, 1325, and 1326. 57 and 1253. 14, 15, 91, 92, 102-104, 108-110, 114-116, 1342, 1717, 1829, 1847, 'lV 1848, 1852, 1854-1862, 1866, and 1867. 63Cr 14, 15, and 1807. 66Mn 14, 15, 334, 345, 1878, 1881, and 1883. 67Fe 4 7 2 4 7 4 , 1579, 1799, 1810, and 1892. WO 4, 614, 709-715, 723, 730, 1358, 1885, and 1891. 83Cu 991, 1682, 1735, 1904, 1905, and 1909-1912. 'Tu 1909-1912. 87Zn 1034, 1326, and 1397. 89Ga 1404 and 2122. 71Ga 1404, 1405, 1410, 1922, and 2122. 73Ge 2251 and 2444. 7 6 A ~1273 and 2466. '?Se 702, 828, 1843, 2049-2051, 2058-2059, 2465, 2486, 2662, 2810, 28162819, 2821, 2822, 2827, and 2837. 79Br 15, 1758, 1914, and 2812. 15, 1302, 1758, 1901, and 2812. 86Rb 23, 1299, 1638, and 1685. 87Rb 1685, 1780, 1895, 1916-1918, 2054, and 2055. 93Nb93, 102, 105, 1719, 1847, 1853, and 1867. 9 6 M15, ~ 118, 167, 227-229, 240, 248, 251, 264, 280-284, 302, 304, 306, and 1877. 9 9 T 15. ~ 9 9 R 3, ~ 15, 366, 367, and 563. lolRu 366. lo3Rh674, 701, 756, 757, 1162, and 1163. l13Cd 7, 20, 1010-1012, 1044-1055, 1336, 1461, 1682, and 1919-1921. l161n 1429, 1905, 2046, and 2249. l19Sn 439, 542, 601, 614, 626, 634, 802, 831, 867, 869, 870, 979, 1468-1470, 1558, 2186, 2251, 2252, 2269, 2320, 2322-2326, 2329, 2332-2336, 2338, 2343, 2400, 2401, 2406-2408, 2410-2412, 2430-2435, 2440, 2452, 2454,2460, and 2462-2465.

154


lZISb2466 and 2808. 123Te2810. lZ5Te537, 538, 540, 2214, 2628, 2810, 2816, 2827, 2837, 2838, 2840, and 2848. lZ7I 2812. lzDXe1357,2721, and 2856. 133Cs 23, 1300, 1685, 1727, 1781, 1800, 1882, 1896, and 1900. laDLa1253. 141Pr 1817. 151Eu 1809. lssHo 1807, 1822, and 1823. lseTm1814 and 1815. 18lTa 1838, 1867, and 1868. 183W 230, 255, 283, 285, 287-289, 311, and 1567. le7Re 15. lD5Pt20, 159-161, 165, 601, 767, 774, 783-788, 828, 831, 838, 858-860, 865-867, 869, 885, 886, 895, 898, 900, 902, 908, 939, 940, 943, 946, 954-957, 961, 964, 967, 971, 973, 984, 985, 987, 989, 990, 1172, 1184, 1193, 1373, 1512, and 2078. lDDHg20, 634, 893, 1013, 1015, 1018, 1023, 1033, 1059-1061, 1184, 1399, 1462, 1464, and 2170. zOsTl 1418-1421, 1713, 1867, 2005-2008, 2122, 2123, 2234, and 2236. 207Pb870, 1423, 1889, 2031, 2251, 2252, 2269, 2452, 2454, and 2465. 20*Bi 1429, 2046, and 2791.

2 Nuclear Quadrupole Resonance Spectroscopy BY K. B. DILLON

1 Introduction

This chapter reports on the pure nuclear quadrupole resonance (n.q.r.) spectra of quadrupolar (I > 4) nuclei in inorganic or organometallic solids. There have been no major significant developments during the year, although recent advances in high-sensitivity n.q.r., particularly those involving double-resonance techniques, have been reviewed.l General reviews of n.q.r.,2 of n.q.r. spectrom e t r ~ ,and ~ of the super-regenerative detection of n.q.r. signals4 have also appeared. More specialized reviews have been published on adiabatic demagnetization and two-frequency methods in 14N n.q.r. spectroscopy,b vibrational dependencies and isotope effects on nuclear quadrupole-coupling constants; the n.q.r. determination of macroscopic parameters of solids: hydrogen-bond studies (geometry and electronic structure) by n.q.r. spectroscopy,*and n.q.r. as a method for the detection of intramolecular rearrangements in solid^.^ The usual format is adopted in the more detailed sections, i.e. results for main-group elements (2H, Groups I, 111, V, Vl, and VTI), followed by those for transition metals and lanthanides. 2 Main-group Elements

Deuterium.--"O n.q.r. signals were detected from the OH- ion in a number of hydroxides of Group I and Group I1 metals and some of their monohydrates by using the technique of double resonance with coupled multiplets (d.r.c.m.).lO Data were given for all compounds at 77 K and for LiOH and LiOH.H20 at 293 K. 2Hn.q.r. signals were observed at 77 K, by means of double resonance by level crossing (d.r.l.c.), from partially deuteriated analogues. A 170-lH dipolar D. T. Edmonds, Inr. Rev. Phys. Chem., 1982,2, 103. Y . Wang, Nucl. Tech., 1983, (2), 63 (Chem. Abstr., 1983, 99, 62 837). K. Shi,Huaxue Tongbuo, 1983, (7), 32 (Chem. Abstr., 1983,99,97 876). L. Pan and Y . Yu, Wuli, 1983, 12, 476 (Chem. Abstr., 1984, 100, 28 711). i. V. S. Grechishkin, V. P. Anferov, and N. Ja Sinjavsky, Adv. Nucl. Quad. Res., 1983, 5, 1 . (I E. A. C. Lucken, Adv. Nucl. Quad. Res., 1983, 5 , 83. N. E. Ainbinder and A. S. Azheganov, Radiospektroskopiya (Perm), 1983, (1 9, 155 (Chem. Abstr., 1984, 100, 60 675). a Y . Hiyama, Bunko Kenkyu, 1982, 31, 221 (Chem. Abstr., 1983, 98, 22 373). G . E. Kibrik. I. A. Kyuntsel, E. S. Kozlov, V. A. Mokeeva, and G. B. Soifet. Ref. Zh., Fiz. (A-D), 1982, Abstr. No. 10E 1946 (Chem. Abstr., 1983,98, 226 752). lo I. J. F. Poplett, J. Magn. Reson., 1982, 50, 382.

I55

156


fine structure was resolved for the 170site in the hydroxide ion; the 1 7 0 electricfield gradient (e.f.g.) was found to be cylindrically symmetrical along the OH bond, with e2Qq/h ranging from -6055 kHz for Ba(OH), to -7590 kHz for NaOH and with low r) values throughout [max. 0.12 k 0.01 for P-Ba(OH),]. The relationship between quadrupolar-coupling constants for 1 7 0 and ,H and the OH- stretching frequency was discussed. By using similar techniques, 1 7 0 and ,H resonances were obtained from H,O molecules in several hydroxide hydrates of Group I and Group I1 metals, and in BeS0,.4H,0.11 Most results were for 77 K, but data were also give for LiOH.H20 at 294 K. Correlations between the 1 7 0 and ,H quadrupolar-coupling constants and hydrogen-bond strength were discussed. The ,H results showed that the deuteron sites were equivalent in the HzOmolecules, except for KOH - H 2 0and BeSO, - 4H20,which had two inequivalent deuteron sites.

Group I (Sodium-23 and Rubidium-85 and -87).-The effects of non-resonant magnetic fields (r.f. photons) on 23Naand 35Cln.q.r. from a single crystal of NaCIO, were investigated.12 Shifts and splittings of the 23Na resonances and lengthening of the spin-spin relaxation time T' of the 35Clsignals, due to the non-resonant fields, were observed and were analysed in terms of the theory of dressed atoms. The experimental results were found to be in good agreement with the theoretical ones. An experimental scheme has been proposed for the detection of transient pure quadrupole double resonance in the rotating frame from rare quadrupolar nuclei, involving off-resonant irradiation of abundant quadrupolar spins.13 It was applied to the detection of 23Nasignals from polycrystalline NaCIO, at 298 K. This method was claimed to reduce the power and hardware required when compared with other double-resonance techniques. A coherent pulse and double-resonance n.q.r. spectrometer has been described, and its use has been illustrated by means of the 23Nadouble-resonance spectrum of NaClO,, the 35Clfree-induction decay from CsICI,, and some Tl measurements for 3sCl nuclei in KCIO,, all at room temperature.lq The temperature ( T ) dependence of the n.q.r. signals from 87Rband 85Rb(both transitions) nuclei in a single-crystal sample of RbH,(SeO,), was determined from 120 to 190 K by means of a double-resonance technique.15 The increase in the number of chemically inequivalent Rb sites, from one in the higher-temperature paraelectric phase to four in the low-temperature ferroelectric phase, together with the observed T-dependence of the e2Qq/hand r ) values, agreed with the proposed soft-mode motion involving rotations of one type of SeO, group. The existence of an intermediate incommensurate phase between T , (the ferroelectric transition temperature, ca. 153 K) and T , 1- 4 K was confirmed. Group I11 (Boron-10 and -11, Aluminium-27, Gallium-69 and -71, and Indium-115). Four llB signals at 77 K were obtained by a double-resonance technique from l1 l2 l3

l4 l5

I. J. F. Poplett, J. Magn. Reson., 1982, 50, 397. T. Ito, J . Phys. SOC.Jpn., 1982, 51, 3623. R. Ramachandran and P. T. Narasimhan, J . Magn. Reson., 1983, 51, 67. R. Ramachandran and P. T. Narasimhan, J. Phys. E, 1983, 16, 643. J. Seliger, V. Zagar, R. Blinc, and L. A. Shuvalov, J . Phys., 1983, 44, 521.

Nuclear Quadrupole Resonance Spectroscopy

157

decaborane, BloH14.1sThe lines were assigned by recording the spectrum of the by a comparison of the deuteriated analogue, p-1,2,3,4,5,7,8,10-B10H2D12, signal intensities with theoretical calculations, and from transition frequencies calculated from SCF wavefunctions. Further lines at higher frequency obtained by using a different r.f. irradiation intensity were ascribed to loB signals, and a tentative fit was made, including some lower-frequency and/or overlapping signals. It was concluded that the description of the bonding in decaborane given by Lipscomb et al. was essentially correct. llB (and some l0B)and 14Nresonances at 77 K were similarly obtained from H,B.NH2CMe3.l7For llB e2Qq/h= 1510 f 30 kHz and y1 = 0.31 f 0.03, while for 14N e2Qq/h= 1567 f 24 kHz and 3 = 0.70 f 0.05. In deriving the coupling constants for boron, the loB spectrum was fitted with stick diagrams calculated from the analytical solution of the nuclear quadrupole spin Hamiltonian for I = 3, given in the paper. A preliminary analysis of the coupling data suggested that a transfer of 0.5 electrons from nitrogen to boron takes place on forming the compound from its BH, and NH2CMe, components. The line intensities in loBn.q.r. spectra obtained by d.r.1.c. could not be correctly predicted from the squares of the quantummechanical transition matrix elements, but they were calculated from the spin thermodynamics of the 42 level crossings during the field cycling.18 The calculations showed that the relative intensities should be little affected by variation of q. Experimental results for loBnuclei in borazine B3N3H6at 77 K confirmed the validity of the simple level-crossing theory. As expected, even quantum-mechanically forbidden transitions were excited in zero field, presumably because dipolar fields admix closely neighbouring states to those involved in the transition. Solid-state transitions of the quadrupolar nuclei and their adjacent hydrogens led to stronger lines than in pure n.q.r. spectra but did not change the relative signal intensities. Low-frequency lines could be enhanced in intensity by continuous coupling, however. Nuclear quadrupole double resonance was used to obtain the 27Aln.q.r. parameters for A121s at 77 K, using the Qt, 8 transition of the bridging iodine atoms for dete~ti0n.l~ The dependence of the signal amplitude on the duration of the r.f. pulse was shown. The values of e2Qq/hand y1 for 27AIwere compared with literature data for Al,Br,. sQGasignals, together with 36Clor 81Br resonances (as appropriate), - . ere recorded at 77 K from the compounds [Me4N],Ga,X6 and [Et4NI2Ga2X,(X = C1 or Br).2037Cl,79Br,and 'lGa resonances were also detected at the expected frequencies. The halogen frequencies were considerably lower than in gallium(m) compounds. [Me4N],Ga2C1,gave only one 3sCland one 69Garesonance, indicating crystallographic equivalence for both chlorine and gallium atoms in the unit cell, but the other complexes gave several resonance lines, showing a lower symmetry. Electron distributions on the gallium and halogen atoms were calculated according to Townes-Dailey theory. The results

*#

A. Lotz, J. Olliges, and J. Voitllnder, Chem. Phys. Lett., 1982, 93, 560. A. Lotz, E. Palangie, and J. Voitltinder, J . Magn. Reson., 1983, 50, 417. A. Lotz and J. Voitllinder, J. Magn. Reson., 1983, 54, 421. G. K. Semin, A. V. Parygin, I. Yu. Amiantov, and A. A. Boguslavskii, Khim. Fiz., 1983.

2o

(lo), 1441. T. Okuda, N. Yoshida, H. Ishihara, K. Yamada, and H. Negita, J . Mof. S t r u t . , 1982, 96.

l6

l7

169.

158


showed that these charges were independent of the cation but varied with the halogen. Some l151n,12’I and 121Sb,123Sbresonance frequencies (as appropriate) were measured for InSeI and SbSeI at 77 K21The quadrupole-coupling constants and asymmetry parameters were given. The results were compared with those for some Group V tri-iodides and sulphoiodides MI3 and MSI (M = As, Sb, or Bi). Possible structure models for the compounds were discussed. l151n, and 35Cl or 7eBr,81Br,n.q.r. frequencies were recorded for the compounds A21nX,.H,0 (A = K, NH4, Rb, or Cs, X = C1 or Br) at room temperature.22 The T-dependence of the bromine resonances in the range 77-380K and of the In signals from K,InBr,- H20, (NH,),InBr, - HzO, and Cs,InBr, .H20 was also determined. Phase transitions were found for K,InBr,-H,O at 145.5 K and for (NH,),TnBr,.H,O at 82 K. Values of ezQq/h for l151n depended markedly on the cation radius rA and on the temperature. The Br n.q.r. frequencies also increased with increasing rA. 7;(l151n)as a function of temperature went through the maximum value of 1.0. The covalent character in the In-X bonds was estimated on the basis of the Townes-Dailey model. It was deduced that the observed temperature effects were due to small changes in the bond character with rA and with temperature.

Group V (Nitrogen-14, Arsenic-75, Antimony-121 and -123, and Bi~muth-2W)~A T-dependence study of the 14N resonances from 1,Zdiphenylhydrazine from 4.2 to 370 K showed five lines (one broad and ascribed to a doublet), two for v+, two for v-, and a doublet for vA, below 115 K, but only three lines, one for each transition, above this t e m p e r a t ~ r e A . ~ second-order ~ structural phase transition was deduced to occur. T-Dependence measurements on the relaxation times T, and T2*suggested that the molecule has inversion symmetry, but below 115 K there are two crystallographically inequivalent positions of the molecule in the unit cell. The 14Nn.q.r. spectra at various temperatures between 1 and 77 K were recorded for dibromo-(4H-l,2,4-triazole)copper(11) (A), dibromo-(N-nitrosopiperidine)copper(rr) (B), and dibromo(dimethylnitrosamine)copper(II) (C).24 Only the resonances due to nitroso nitrogens could be observed from B. The n.q.r. lines attributable to the nitroso nitrogen atoms of C could not be seen below 29.5 & 0.5 K, whereas those from the amino nitrogens could be detected even at 1.7 K. Phase transitions were found at 6.5, 1.90, and 29.5 K for A, B, and C, respectively. Magnetic-susceptibility measurements indicated that A has weak ferromagnetism below the transition temperature, showing the appearance of a long-range ordered state. The magnetic properties of the complexes were discussed in comparison with those of their chloro analogues, 14N, 35C1,and 37Cln.q.r. spectra were obtained by a double-resonance method from n-decylammonium chloride as a function of temperature in the range 320-365 K.25 The 35Clfrequency of 1215 kHz at 320 K was determined by the S. K. Shcherbakova, A. A. Boguslavskii, and G. K. Semin, Khim. Fiz., 1983, (9), 1285. K. Yamada and A. Weiss, Ber. Bunsenges. Phys. Chem., 1983, 87, 932. 23 H. Matsuura, T. Matsuzaki, Y. Fukazawa, and Y. Abe, J . Phys. SOC.Jpn., 1982 51, 3755. 24 T. Asaji, H. Sakai, and D. Nakamura, Inorg. Chem., 1983,22,202. 25 J. Seliger, V. zagar, R. Blinc, H. Arend, and G. Chapuis, J. Chem. Phys., 1983, 78, 2661.

21


159

N-H * * - C1 hydrogen bonds and was described as the lowest yet reported. For the * .C1 14N nucleus e2Qq/h= 760 kHz and q = 0, showing that the C-N-H. backbone i6 practically rigid at this temperature. A phase transition was observed at 328 f 1.5 K (temperature hysteresis on cooling is at most 2 K) from an intercalated to a non-intercalated structure, causing a sharp fall in the 14Nand 36Cln.q.r. frequencies. A model to account for this effect was proposed. Two-frequency double n.q.r.-n.m.r. methods were used to obtain 14N n.q.r. data for various organic compounds, together with (CH,),N4. HNCS and (CH,),N,. HN03, due to proton transfer along the hydrogen b ~ n d . ~ ,Hydrogen ?~' bonding in these compounds was discussed on the basis of the results. 14Nsignals at 120 K were similarly obtained for various hydrogen-bonded complexes, including the two mentioned above, C(NH,),+CI- and H,TeO,.2H2O. 2(CH,),N4.28 The relative sensitivity of the double-resonance method with respect to NH3, NH,, and NH groups was discussed. The time and frequency characteristics of n.q.r. signals in a multi-pulse sequence called pulsed spin locking were investigated, using the upper 14Ntransition frequency of a single crystal of NaNO, at 77 K.29 The results were discussed and compared with those of multi-pulse experiments in n.m.r. spectroscopy. The rate equation describing the evolution of quasi-steady states to equilibrium with the lattice in 14N n.q.r. multi-pulse experiments has been obtained by using average Hamiltonian These states were generally characterized by a non-zero transverse magnetization. The experimental curves of spin-echo envelopes in the phase-alternated multi-pulse sequence were obtained from a monocrystalline sample of NaNO, at 77 K ; these confirmed the theory. A thermodynamic theory of multi-pulse n.q.r. has been developed for nuclei with I = 1 and for the simplest multi-pulse spin-locking sequence.31The influence of spin-lattice relaxation was taken into account. Good agreement with experimental data for 14N n.q.r. in NaNO, was obtained. The T-dependence of the 14Nn.q.r. parameters (v+, v-, ezQq/h, q, and the linewidths) in the range 7 7 - 4 1 0 K was determined for both single-crystal and polycrystalline samples of NaN02.32The directions of the principal axes of the e.f.g. tensor at the 14Nnucleus were found from the angular dependence of the signal intensity of the single-crystal sample; the X-,Y-, and Z-axes coincided with the crystallographic c-, a-, and b-axes, respectively. The results were analysed in terms of polarization deformation and the order-disorder model. Differences were found in the resonance frequencies for single-crystal and powder samples, possibly associated with spontaneous polarization of the ferroelectric NaNO,, and more investigations were being undertaken to try to clarify this anomaly. Other results for 14Nhave been described in the subsection on Group I11 (l0B, 11B).17 In a study of some molybdenum complexes with arsenic ligands, two close V. P. Anferov, S. V. Anferova, V. S. Grechishkin, and V. M. Mikhal'kov, Russ. J. Phys. Chem., 1982,56, 1387. 27 V. P. Anferov, S. V. Anferova, V. S. Grechishkin, and V. M. Mikhal'kov. Khim. Fir.. 1983. (ll), 1505. 28 S. V. Anferova, Russ. J. Phys. Chem., 1983, 57, 578. D. Ya. Osokin, Sov. Phys. JETP, 1983, 57, 69. 30 D. Ya. Osokin, MoZ. Phys., 1983, 48, 283. 31 G . E. Karnaukh, B. N. Provotorov, and A. K. Khitrin, Sov. Phys. JETP, 1983, 57, 93. 32 J. Lee and S. H. Choh, J. Korean Phys. SOC.,1982, 15, 126. 26

160

Spectroscopic Properties o j Inorganic and Organometallic Compounds

75A~ signals were detected at 77 K from Mo,(O,CCF,),(ASE~,),.~~It was concluded from this and other spectroscopic evidence that the arsines occupy axial positions on the Mo,,+ unit. The relationship reported previously between the lH n.m.r. chemical-shift difference between the CH2 and CH, protons of the ethyl groups and the 7 5 An.q.r. ~ frequency was again apparent. No 7 5 Asignals ~ could be obtained from MO~X,(ASE~,)~ (X = C1, Br, or NCS), attributed to poor bulk crystallinity. The previously reported second-order phase transition in proustite, Ag,AsS,, which occurs between 60 and 50 K, was studied by various ~ obtained physical techniques, including the T-dependence of the 7 5 Aresonance, by a spin-echo method, and the T-dependence of the spin-lattice relaxation At 60K the single resonance began to broaden sharply, and the broad line disappeared abruptly at 48.5 K, being replaced by a sharp well resolved multiplet. It was concluded that an incommensurate phase exists between 49 and 60 K, with a second-order phase transition at 60 k 0.5 K and a first-order phase transition at 49 k 0.5 K. A possible model for the incommensurate phase was ~ of PbHAsO, discussed. The T- and pressure ( p - ) dependences of the 7 5 Asignal from 77 to 255 K and at pressures up to 300 MPa were dete~mined.,~ Similar experiments were carried out for PbDAsO, from 77 K to the vanishing temperature of the signal (195 K) and at pressures up to 260 MPa. The results were analysed on the basis of the pseudo-spin model of Blinc. By comparison also with the results for KH,AsO, and KD,AsO,~~ it was deduced that the lowered effectiveness of tunnelling on deuteriation makes the structure more rigid, reducing the lattice dynamics and affecting the n.q.r. parameters, thus accounting for the large isotopic effect. Similar experiments were performed on KD2As0, from 77 to 170 K and at pressures from 0.1 to 3000 MPa. 36 The effect of pressure on the transition temperature T , (160.1 K at atmospheric pressure) was also determined. Calculations of the hydrogen-bond compressibility, tunnelling frequency, dipole interaction energy I, and dZ/dp were carried out by means of the Blinc-Kobayashi theory. Similar isotopic effects to those in the lead compounds were apparent. 121Sb, 12,Sb, and 35Cl n.q.r. measurements at 77 K on the 1 : 1 complex SbC1,-PhCHO showed the existence of three modifications of the After crystallization of the melt supercooled by liquid nitrogen, the spectrum corresponded to a metastable modification I. In the specimen left at room temperature a second set of signals began to appear almost immediately (form 11) and increased in intensity at the expense of I over a period of several days. When the signals of form I had disappeared, a third set of lines due to modification I11 was detected, and this form eventually became stabilized in the spectrum (3-5 weeks, depending on the specimen). The results showed that I has equivalent J. Ribas, G . Jugie, and R. Poilblanc, Transition Met. Chem., 1983, 2, 93. A. V. Bondar, V. S. Vikhnin, Z. M. Alekseeva, S. M. Ryabchenko, I. M. Tsivileva, and V. E. Yachmenev, Bull. Acad. Sci. USSR, Phys. Ser., 1983, 47, (4), 87. 35 E. Lipihki, M. MaCkowiak, M. Zdanowska-Fraczek, J. Stankowski, and B. Brezina, Bull. Acad. Pol. Sci., Ser. Sci. Chim., 1981, 29, 477. 36 E. Lipihki, J. Stankowski, M. Fraczek-Zdanowska, and P. Koziol, Acta Phys. Poi., 1983. A63, 823. 37 I. A. Kyuntsel’, J. Struct. Chem., 1983, 24, 137.

33

34


161

complex units in the unit cell whereas 11 and 111 both have two sets of crystallographically inequivalent complex molecules. 121Sb, 123Sb(where appropriate), and 35Cl n.q.r. studies of the complexes SnCI,.P,O,CI, and 2SbC15.P203C14, including the T-dependence of the chlorine signals between 77 and 330 K, have shown that P203C14acts as a bridging ligand in both cases.38A phase transition was detected at 148 K in the SbCI, complex. The SnCI, adduct was deduced to have an infinite chain structure, with SnCI, co-ordinated by two oxygens in cis positions from different P203C1, units, each of which co-ordinates to another SnCl, via its second phosphoryl oxygen; this structure was represented as cis-[SnC14~2(P20,C14)+],.The SbCl, complex had thestructure of a 2 : 1 molecular adduct, with one oxygen from P203CI,co-ordinating to each of the SbCl, moieties. The 35C1frequencies at 77 K were measured for octahedral complexes of SbCl, with the organic donor ligands PhCOCl, 3-MeC6H,COCI,4-MeC6H4COCl, PhCN, 2-CIC,H,CN, 3-CICgH4CN, 2-CIC,H4N, 3-ClC5H4N, PhCOCHy C1,4-ClC,H,COMe, CC13CH0,CICOCH2CH2COCI,and Et20.39Some 121Sband 123Sbresonance frequencieswere also determined, usually at higher temperatures, and T-dependence studies from 77 K to room temperature were carried out for some of the complexes. Assignment of 35CI resonances to axial or equatorial chlorines of the SbCI, fragment was possible in several instances, but no systematic differences were apparent between the equatorial and axial frequencies since these were masked by crystal-field effects of similar magnitude. The electric hexadecapole-coupling constant eMm of 12,Sb nuclei in SbCl, was determined from very accurate measurement of the three n.q.r. transition frequencies at room t e m p e r a t ~ r ePrecautions .~~ were taken to avoid errors from temperature changes or from slight asymmetry in the lineshapes. For v2 (Qt, 8 transition)= 67.732 MHz eMm was evaluated as 109.8 k 60.6 kHz. On the assumption of a common for 123Sband 121Sb,a value of 57.4 f 48.6 kHz was obtained for eMm of lZISbfrom the measured n.q.r. frequencies. Compounds of the formula M,Sb,F,SO,-H,O (M = Rb, Cs, or N H 3 were synthesized and their structures investigated by various techniques, including n.q.r.,l 121Sb and 123Sbsignals were recorded at 77 and 295 K for M = Cs or NH,, but resonances could only be obtained at 77 K for the rubidium compound. One line for each transition at 77 K was seen for the Rb and Cs salts, and for the Cs compound at 295 K, but the NH4+analogue showed two inequivalent Sb sites at 77 K and one Sb site only at 295 K, indicating a phase transition between these temperatures. The crystal structure of the rubidium compound was determined and was shown to consist of polymeric [Sb,F,S04],2n- anions, Rb cations, and H 2 0 molecules. The SOa group formed an asymmetric tetradentate bridge, linking four SbF, groups. Several physical methods were used to study phase transitions in (NH4)2SbF5,including the T-dependence of the 12"Sbn.q.r. frequencies for the +

E. A. Kravchenko, V. G. Morgunov, T. L. Novoderezhkina, B. N . Kulikovskii. 0.N. Gilyarov, and V. G. Lebedev, Russ. J . Inorg. Chem., 1983, 28, 664. 39 J. Rupp-Bensadon and E. A. C. Lucken, J . Chem. SOC.,Dalton Trans., 1983, 19. 40 H.Gotou, J. Magn. Reson., 1983, 54, 36. 41 R. L. Davidovich, L. A. Zemnukhova, N . I. Sigula, and A. A. Udovenko, Koord. Kliini. (Engl. Transl.), 1982, 8, 415. 38

162


*++Q and Q++ 8 transitions from 77 to 276 K, at which point the signals d i ~ a p p e a r e d .Various ~~ phase transitions were detected and were ascribed to reorientation movements of NH4+and SbFj2- groups. An anomalous increase in the n.q.r. frequencies was observed between 110 and 168 K (phase transition temperature), after which they decreased in accordance with the Bayer law; the reasons for this behaviour were discussed. Other results for Sb have been detailed in the subsection on Group 111 (1151n).21 To explain anomalies observed previously in T-dependence studies of longitudinal (T,) and transverse (T2)relaxation times for 200Binuclei in Bi,,GeO,, and Bi12Si020,a model was developed for the mechanism of relaxation that averages the inhomogeneous contributions to the line broadening as a result of the motion of the defects causing this b r ~ a d e n i n g It . ~was ~ suggested that there are several mechanisms of inhomogeneous broadening, the principal one being static. Satisfactory agreement was achieved between theoretical and experimental results. In work on BiF, and some of its complexes, 200Biand 35Cln.q.r. frequencies at 77 K were measured for C1F2+BiF,-.44(These results have been reported in more detail in an earlier volume in this series - Vol. 15, p. 148, ref. 46.)

Group VI (Oxygen-l7).--The T-dependence from ca. 160 to 323 K of the 1 7 0 n.q.r. spectra of O-He .O-bonded oxygens in PbHP04 was studied by means of a double-resonance technique.45The non-H-bonded oxygens were not observed. The compound showed a ferroelectric second-order phase transition at 310 K. Three lines only were found above T,, showing equivalent oxygens in the O-H. units. At T , each line split into two components, and the splitting gradually increased with decreasing temperature. The lower-frequency components were stronger and corresponded to 'close' 170-H - 0 sites. It was deduced that the protons move in a double-well potential above T,, as in KH2P04,and that below T , they freeze into one of the two possible equilibrium sites. 1 7 0 n.q.r. was observed at 77 K by a double-resonance technique from KH2P04,which exists in a ferroelectric phase below 123 K, and fine structure due to dipolar interaction with the protons was Good agreement of the n.q.r. parameters was found with those from a previous study. From the best fit between calculated and experimental spectra it was concluded that proton motion along the hydrogen bond occurs even at 77 K. Linewidth measurements on the 1 7 0 n.q.r. signal from "0-enriched CO in the a-phase between 35 and 65 K were used to derive the order-disorder reorientational frequencies OR of the CO dipoles.47 Remarkably good agreement was obtained with results from dielectric dispersion measurements, and the values of OR were extended by almost seven orders of magnitude. In view of the small values for OR near the order-dis+

e

.

0

*

42

43

*

L. M. Avkhutskii, R. L. Davidovich, L. A. Zemnukhova, P. S. Gordienko, V. Urbonavitius. and J. Grigas, Phys. Status Solidi B, 1983, 116, 483. A. Yu. Kudzin, S. M. Ryabchenko, and A. D. Skorbun, Sov. Phys. Solid State, 1982, 24, 1483.

44 45

46 47

V. F. Sukhovcrkhov and A. V. Sharabarin, Russ. J . Inorg. Chem., 1983, 28, 352. J. Seliger, V. Zagar, and R. Blinc, Phys. Lett., 1983, 93A, 149. S. D. Goren, M. Shporer, and Y . Margalit, Phys. Rev. B, 1983, 27, 5419. J. Walton, J. Brookeman, and A. Rigamonti, Phys. Rev. B, 1983, 28, 4050.


163

order transition, a metastable state was expected to occur on cooling, possibly accounting for an anomaly in the heat capacity around 18 K. Other 170results have been described in the subsection on 2H.10.11

Group VII (Chlorine35 and -37, Bromine79 and -81, and Iodine-l27).-The 35Cl n.q.r. spectra were measured as a function of T between 77 K and room temperature for various complexes SnCI, - L, (L = tetrahydrofuran, tetrahydrothiophen, hexamethylphosphoramide, or trimethyl phosphate) and for the 1 : I complex of SnCl, with 1,2-dimetho~yethane.~~ The significance of the n.q.r. data with relation to a cis or trans arrangement of the donor molecules was discussed, and it was concluded that the n.q.r. results must be interpreted with considerable caution, even when T-dependence studies were carried out, 35Cln.q.r. and vibrational spectroscopic studies of the componds [ACI,+][AuC14-] (A = S, Se, or Te) have shown that the AuC1,- ion in the sulphur and selenium compounds, which are isomorphous with form I of SC13+IC14-,is considerably distorted The tellurium compound had a different structure, with a from D& ~yrnmetry.~~ less severe distortion of the anion. A previous suggestion that the highestfrequency 35Cl signal from the anion arose from a bridging chlorine in these compounds was discounted, and the lowest-frequency line was attributed to a chlorine involved in secondary bonding to A. Crystalline VOCl, showed two 35Cln.q.r. signals in a 2 : 1 intensity ratio at all temperatures from 77 to 194 K, just below the melting point, where the signals di~appeared.~~ The crystal structure of the compound at 133 K was also determined, and it showed the presence of isolated tetrahedral VOCl, molecules lying on a mirror plane and stacked with their V-0 axis along [lo01 to form trigonal-prismatic columns. The crystals were orthorhombic, space group Pnma, in full agreement with the n.q.r. data. The relationship of the structure to gas-phase data and to the structures of other compounds such as AsBr,, NbOCl,, and MoOCl, was discussed. A 35Cln.q.r. investigation at 77 K of a titanium-magnesium catalyst (TMC), obtained by reduction of TiCl, by an organomagnesium compound and used for ethene polymerization, showed three signals of unequal intensity with an average frequency of 6.367 MHz.~'In contrast a titanium-aluminium catalyst (TAC) used for the commercial production of polypropene gave a very similar single-line spectrum to that of pure TiC1,. The significance of these results with regard to the structure of the TMC was considered. A fourth, low-frequency (17.190 MHz) 35Cl signal was detected at room The other three temperature for NH,ICI, - HzO, as predicted previo~sly.~~ signals agreed well in frequency with the literature values. Four signals were also observed at 195 K but either five or (probably) six resonances at 77 K, suggesting a phase transition between these temperatures. A structure was 48 40

J. Rupp-Bensadon and E. A. C. Lucken, J. Chem. SOC.,Dalton Trans., 1983,495. A. Finch, P. N. Gates, T. H. Page, and K. B. Dillon, J . Chem. SOC.,Dalton Trans., 1983. 1837.

J. Galy, R. Enjalbert, G. Jugie, and J. Striihle, J. Solid State Chem., 1983, 47, 143. 51 A. A. Baulin, Yu. K. Maksyutin, T. I. Burmistrova, V. M. Shepel. V. P. Nekhoroshev, and S. S. Ivanchev, React. Kinet. Catal. Lett., 1982, 21, 269. 52 K. B. Dillon and J. Lincoln, Polyhedron, 1983, 2, 1393. 50

164

Spectroscopic Properties of Inorganic and Organometallic Cqmpounds

proposed for the IC14- ion at room temperature from the n.q.r. results, similar to that in KICI4.H2O.The 35Cln.q.r. spectrum of crystalline P,03C1, at 77 K showed the existence of two crystalline modifications, a stable form with four equally intense signals and a metastable form with three signals in a 2 : 1 : I intensity ratio.53 7'-Dependence studies in the range 77-200 K were carried out for the stable form. P,OS,CI, when crystallized gave two relatively broad signals at 77 K. The results were compared with published data for POCI,, and possible x-bonding in the compounds was discussed. 35Cln.q.r. measurements at 77 K for 1 : 1 mixtures of SnCI, and RCOCl (R = Me, Pr", CI,C, or MeO) showed no evidence of c ~ m p l e x a t i o n1. ~: ~1 mixtures of SnCI, with PhCOCl or 4X-C,H4COC1 (X = F, CI, Br, Me, or MeO) gave spectra indicating the formation of five-co-ordinate tin complexes, with the acid chlorides connected through oxygen in an axial position of a trigonal bipyramid. A 2 : 1 mixture of PhCOCl and SnCI, showed only signals from the 1 : 1 complex and free PhCOCI, indicating that a 2 : 1 complex does not form, and there was no evidence of co-ordination by the Me0 group from a 2 : 1 mixture of SnCI, and 4-MeOC,H4COCl. When X = COCl or NO2, no complexation occurred with SnCI,; this was attributed to the electron-withdrawing properties of the substituent. From comparison of the changes in the C-Cl frequency on complexation in 1 : 1 complexes of SnCI,, AICI3, and SbCl, with PhCOCI, the electron-pair acceptor capacity of the Lewis acids was deduced to follow the sequence SnCI, c AICI, c SbCI,. R2

\

C-N

//

\\

\

/

N

C=N

PCl,

/

R'

35Cln.q.r. frequencies at 77 K were reported for a series of 1,3,5,2h5-triazaphosphorines (1) with various substituents R1and R2.55The results and related CND0/2 calculations were analysed in terms of the transmission capability of the P=NC moiety. 35Clspectra at 77 K were recorded for a series of phenylsilane derivatives YC6H4SiX3and, for comparison, some carbon compounds CIC,H,CX,.56 It was concluded that effects due to px-dx conjugation between electrons of the aromatic ring and unoccupied 3d-orbitals of silicon were either absent or very small. A correlation was found between the 35Cln.q.r. frequencies of analogous silicon and carbon compounds CIC,H,EX, (E = C or Si) for meta and para isomers, but not for ortho isomers, ascribed to the peculiar features E. A. Kravchenko, V. G . Morgunov, B. N. Kulikovskii, and T. L. Novoderezhkina, Z . Chem., 1983, 23, 143. 54 G. V. Dolgushin, I. M. Lazarev, V. P. Feshin, and M. G . Voronkov, Dokl. Akad. Nauk SSSR (Engl. Transl.), 1982, 265, 652. j5 E. A. Romanenko and P. P. Kornuta, Teor. Eksp. Khim. (Engl. Transl.), 1983, 19, 330. je V. P. Feshin, M. G. Voronkov, L. S. Romanenko, P. A. Nikitin, G. V. Motsarev, V. T. Inshakova, and V. R. Rozenberg, J. Gen. Chem. U.S.S.R.,1983, 53, 1167.


I65

of the interaction of ortho substituents in an aromatic nucleus. T-Dependence studies on the 35Cl signals from 4-chlorobenzene sulphonyl chloride in the range 100-240K showed the existence of two solid phases t h r o ~ g h o u t . ~ ~ Molecular motion in the compound was discussed. A fast Fourier-transform n.q.r. spectrometer was described and was used to obtain the 35Cl n.q.r. of K,OsCl, at 298 and 77 K.58 A satellite associated with the nearest-neighbour chlorines to H+ ion impurities located at vacant octahedral sites was found. Data were also reported for K2ReC1658~59 and PrC13.68~s0 35CI frequency and lineshape data from 130 to 85 K for K,ReCI, showed phase transitions at T,, 109.1 f 0.5 K and T,, 101.3 f 0.5 K, reducing the crystal symmetry from cubic to tetragonal to monoclinic on Measurements were also made at nine hydrostatic pressures from 1 bar to 2.64 kbar in this temperature range. Some unexpected results were found; in both the tetragonal and monoclinic phases an additional low-frequency line was detected, together with an intensity distribution that was not simply a superposition of Lorentzian lineshapes, a total intensity that deviated from Curie-law behaviour as a function of T, and an unconventional absorption response. An explanation of these results was given, based on recent discussions of non-linear phenomena at phase transitions in crystals exhibiting reduced effective dimensionality. Accurate T1measurements by spin-echo methods were reported for both C1 isotopes in PrCl, at 4.2 K, and T, measurements in the range 4.2-17.4 K, in an extension of work in the literature.60 The results were explained on the assumption of onedimensional XY spin dynamics for the Pr spins, with the chlorine nuclei being relaxed both by fluctuating magnetic fields due to the longitudinal Pr moments and by fluctuating electric-field gradients due to the transverse Pr moments. T I relaxation was deduced to be primarily magnetic throughout the temperature range of one-dimensional ordering, while T2relaxation was quadrupolar at lower temperatures and probably magnetic at higher temperatures. As a result Tl and T2had opposite T-dependences. The data were consistent with relaxation calculations. A group theoretical analysis of previously published 36Cln.q.r. data for PrC13 between 0.15 and 0.55 K restricted to two the possible space-group symmetries of the low-temperature (below 0.4 K) phase.B1 This result together with other experimental information allowed the phase transition to be identified as a Jahn-Teller Peierls dimerization. The T-dependences of 35Cl n.q.r. parameters, including the inverse linewidth T2*, have been determined for a variety of chlorine-containing compounds.s2 Contributions from magnetic, electric, and spin-lattice effects in crystalline compounds to the resonance linewidths were discussed, and a general theory describing the relationship of these effects on T2*was derived. n.q.r. frequency and Tl measurements as a function of temperature were made for Ba(CIO,),.H,O (I), NaClO, (11), and AgC103 (111) from 77 K until the A. H. Brunetti and D. J. Pusiol, J. Mol. Struct., 1983, 96, 293. M.D’Iorio, Diss. Abstr. Int. B, 1982, 43, 1890. 5s M. D’Iorio and R. L. Armstrong, Can.J . Phys., 1983,61, 1374. 6o M. D’Iorio, R. L. Armstrong, and D. R. Taylor, Phys. Rev. B, 1983, 27, 1664. 61 R. M. Morra, R. L. Armstrong, and D. R. Taylor, Phys. Rev. Lett., 1983, 51, 809. 62 S. J. Melnick, Diss.Abstr. Int. B, 1983, 44, 1468. 57

68

166


signals disappeared (ca. 390, 425, and 440 K for I, 11, and 111, res~ectively).~~ A single resonance was observed in each case. The motional processes responsible for averaging of the electric-field gradients and spin-lattice relaxation were identified as anharmonic torsional motions in the low-temperature range, hindered rotation of the ClO,- ion in the high-temperature range, and diffusion of water molecules in Ba(ClO,), H 2 0 . Activation energies for these processes were derived by analysis of the data. Torsional frequencies were in good agreement with the results from Raman studies. A phase transition was detected in AgC10, at 415 K. A Zeeman n.q.r. study has been carried out on a single crystal of Sr(ClO,), at 308 K.S4 The principal field-gradient directions were determined, and q was evaluated as 0.176 +_ 0.005. The crystal class and probable twinning were discussed. A super-regenerator with frequency pulling from an external source for the frequency range 20-70 MHz has been described and used in a spectrometer to obtain 35Cln.q.r. signals from powdered KClO, at 293 K.65It was also tested as a temperature transducer between 77 and 443 K and provided a base for a wide-range precision thermometer. Theoretical calculations have been made of Zeeman-perturbed nuclear quadrupole spin-echo envelope modulations (ZSEEM) for spin-8 nuclei in polycrystalline samples, using the density-matrix formalism.66A parallel orientation of the external r.f. and static Zeeman fields was assumed. Experimental ZSEEM patterns were obtained for 35Clnuclei in polycrystalline KClO,, Ba(ClO,), - H 2 0 , HgCI, (two sites), and SbCl, (two sites) at 298 K, and they were compared with computersimulated patterns derived from the theory. For HgCl, the experimental patterns were almost identical for the two sites and corresponded to a near-zero value of y. The difference in the 7 values (ca. 0.06 and 0.16) for the two sites in SbCl, was reflected in both the experimental and theoretical ZSEEM patterns, and it showed that evaluation of y from ZSEEM studies may be possible. The relationship between the 35Cln.q.r. frequencies at 77 K and crystal symmetry in some metal chlorates MClO, (M = Na, K, Rb, Ag, or Cs) has been discussed, but no new experimental data were rep~rted.~' A theory has been developed of dynamic librational relaxation of a quadrupolar nucleus, associating the fluctuations of thermal librations with fluctuations of the e.f.g. and based on a model of molecular harmonic oscillations.68Some experimental results for 35Cl nuclei showed significant deviations from the expected T-dependence of spin-lattice relaxation with a librational mechanism, and the observed anharmonic effects were associated with librational anharmonicity. The effect of varying the percentage of deuteriation on the transition temperature from the ferroelectric to the paraelectric phase of HCl-DCl mixed

J. Kasprzak and J. Pietrzak, Actu Phys. Pol., 1983, A63, 461. V. Rama Krishna, D. Krishna Rao, G. Satyanandam, and C. R. K. Murty, Acta Phys. Pol., 1983, A63, 833. 65 0. N. Bryukhanov and T. N. Rudakov, Prib. Tekh. Eksp. (Engf. Transl.), 1982, 947. R. Ramachandran and P. T. Narasimhan, Mol. Phys., 1983, 48, 267. " D. B. Balashov, Sov. Phys. Crystuffogr., 1983, 28, 487. 88 Yu. N. Gachegov and G. B. Soifer, Deposited Doc., 1981, VINITI 5785'81 (Chem. Abstr., 1983, 98, 26 661).


167

crystals was found by monitoring the intensity of the 36Cln.q.r. signal.6vSpinlattice relaxation times for 36Clnuclei from both HCl and DCl dipoles were also measured at 55 f 0.1 K. The results were analysed using a dynamic Ising model in a transverse field, taking damping into account. The behaviour of the correlation times for the DC1 dipoles as a function of deuteriation was consistent with theory, but it could not account for the behaviour of the correlation times for the HC1 dipoles in the limit of almost complete deuteriation. Instead the persistence of quantum tunnelling was observed, in spite of the interaction with DCI dipoles. This was attributed to the effect of local phonon modes on the tunnelling of the HCl dipoles. The effect of hydrostatic pressure in the range 0-4 kbar on the two phase transitions at T,, (2: 262 K) and Tc2(2: 255 K) in K,SnCl, was investigated by means of 36Cl n.q.r.'O The pressure coefficients were dT,,/dp = 1.35(10) K kbar-l and dT,,/dp = - 1.25(20) K kbar-l. The significance of these results was discussed with relation to perovskite structures. The influence of hydrostatic pressure up to 3 x lo2 MPa on the 35Cln.q.r. spectrum of NH4H(CICH2C00), was examined from 77 K to the phase-transition temperature T, (120K at atmospheric pressure), enabling dT,/dp to be evaluated.'l The results could not be interpreted in terms of the effects of lattice vibrations on the e.f.g. but reflected the proton dynamics in the hydrogen bonds between ClCH,COO groups. The energies of proton tunnelling and the dipole-dipole interaction as functions of pressure were determined on the basis of the Blinc pseudo-spin model, and the nature of the phase transition was discussed. 35Cln.q.r. spectra were recorded at various temperatures from 300 to 78 K for (Me3S),MC1, (M = Pt, Se, Te, or Sn).72No signals could be observed for the Se and Te compounds below 200 K. The complexes each gave a single line, indicating cubic symmetry. This was confirmed by X-ray powder patterns, which showed that the compounds were isomorphous and allowed the unit-cell dimensions to be evaluated. lH n.m.r. second moments were also determined at various temperatures between 77 and 370 K, and molecular motions of the Me3S+ions were discussed on the basis of the results. The n.q.r. frequencies were correlated with data for hexahalometallates of other cations. 3sCln.q.r. spectroscopy was mentioned as a means of distinguishing between undeformed SC13+cations, as in SC13+MoOC14-, with three identical S-Cl bonds, and deformed SCI,+ ions, with interactions to a chlorine ligand of the anion, as in SCI,+AUCI,-.~~ No experimental data were given, however, in this brief summary. n.q.r. signals from Cchloroanilinium cations in the The T-dependence of compounds (4-C1C,H4NH3),MnC14(I), (4-ClC6HdNH3)2CuCl, (11),and (CClC6H4NH,),CuBr4 (111) was studied from 4.2 to 400 K.74 The magnetic susceptibilities of the copper complexes were also measured below 20K. The lattice

3'

M. Crowley, J. Brookeman, and A. Rigamonti, Phys. Rev. B, 1983, 28, 5184. C. Dimitropoulos and J. Pelzl, Solid State Commun., 1982,44, 849. M. Zdanowska-Fraczek and E. Lipiiski, J . Magn. Reson., 1983, 55, 1. R. Ikeda, D. Nakamura, R. Kadel, and A. Weiss, Ber. Bunsenges. Phys. Chem., 1983, 87, 570. L. Kolditz, T. Moya, U. Calov, Yu. A. Buslaev, and E. A. Kravchenko, Proc. Corzfi Coord.

74

Chem., 1983,9, 177. J. Ishikawa, T. Asaji, and D. Nakamura, J . Mugn. Reson., 1983, 51, 95.

io 71

168


constants of these isomorphous complexes were determined from X-ray powder patterns and a knowledge of the crystal structure of the Mn complex. All three compounds showed magnetic phase transitions, at 40 f 1 , 8 f 1, and 13 f 1 K for I, 11, and 111, respectively, together with structural phase transitions at 343 (I), 275 and 277 (11), and 198 K (111). The structural phase transitions were also detected by DTA. Magnetic properties in the ordered state and the nature of both types of phase transitions were discussed. T-Dependence measurements on the 35Cln.q.r. spectrum of K2ZnC14from 580 to 77 K showed phase transitions at 553, 403, and 145 K.75 The sequence was high-temperature paraelectric (phase I) incommensurate (phase 11) improper ferroelectric (phase 111) polar (phase IV). The two lowest-temperature phases were analysed by means of n.q.r. combined with group theoretical considerations. The eigenvector of the frozen-in soft mode in phase 111, which consisted mainly of rotations of ZnC1, tetrahedra around the pseudo-hexagonal a-axis, was shown to be very large compared with that in Rb2ZnC14.In phase IV a quadrupling of the n.q.r. lines was observed, which could be explained by a zone-boundary transition leading to a monoclinic phase. The low-temperature (77 K) phase transition from phase I11 to phase IV in Rb2ZnC1, was similarly followed by monitoring the T-dependence of the three highest-frequency 35Cllines from phase 111 between 110 and 30 K.', At the phase transition the number of lines was quadrupled. Phase 111 has the symmetry Pn2,a (2 = 12), and since the transition was continuous and phase IV was commensurate two conditions had to be fulfilled. Phase IV had to have the symmetry of one of the irreducible representations of Pn2,a, and the antisymmetric square of this representation could not transform as a vector component, i.e. no Lifshits invariant was allowed in the thermodynamic potential. These conditions were satisfied by the space group Alla (2 = 24), which also agreed with Raman results. The low-temperature phase transition in CsPbC13 has been studied by various physical techniques, including X-ray and neutron diffraction, Raman scattering, and the T-dependence of the 35Cl and 37Cln.q.r. signals from 77 to 360K.77 At all temperatures below the known phase transitions (310, 315, and 320 K) two signals were observed for each isotope, in a 2 : 1 intensity ratio. The width of the lower-frequency lines (intensity 2) increased rapidly by about 20% near 200 K, while the higher-frequency lines remained constant in width. This broadening was attributed to very slight inequivalence of two of the chlorines, which were completely equivalent at higher temperatures. It was concluded from this and other evidence that a secondorder phase transition occurs at ca. 200 K ( T J . Structural analysis showed orthorhombic symmetry at room temperature and monoclinic symmetry below Tc4.The transition was not associated with condensation of the rotational modes of the PbCl, octahedra around any principal axis, but with the elastic soft mode. 3sCl or 7gBr,81Brn.q.r. frequencies, mainly at 77 K but including some roomtemperature measurements, have been reported for a series of adducts of Group VI tetrahalides ECl, (E = S, Se, or Te) or SeBr,, with other halides MX, from --f

75 78 77

-

F. Milia, R. Kind, and J. Slak, Phys. Rev. B, 1983, 27, 6662. P. Muralt, E. Voit, and R. Kind, Phys. Sfatus Solidi B, 1983, 119, K65. M. Hidaka, Y. Okamoto, and Y. Zikumaru, Phys. Status Solidi A , 1983,79, 263.

-


1 69

Group I11 (Al, Ga) to Group VIII (Fe).78In some cases not all the signals were detected, particularly from compounds where low-frequency M-C1 resonances would be expected. The compounds were usually found to have the ionic structures EX,+MX,+,- for 1 : 1 adducts or (EX3+)2MX,+22-for 2 : 1 adducts. lS1Tasignals were also obtained at 77 and 296 K from TaCl, - SeCl,. These showed the presence of two very different Ta atoms in the unit cell, ascribed to the presence of two crystallographically independent molecules with differently distorted TaCl, octahedra. Other 36Clresults have been detailed in the subsections on Groups I,12,14 11120,22 and V.25,37-9,44 The Zeeman effect on 81Br n.q.r. from a single crystal of PBr,-BBr, was studied at 293 K.'O The crystal has orthorhombic symmetry, and the bond angles were determined as 111.2 k 0.1" and 111.5 f 0.1" for BrBBr and 107.0 f 0.1" and 109.1 f 0.3" for BrPBr. The r ) values were relatively large for the BBr, group (0.151 f 0.004 and 0.170 +_ 0.007 for the double-intensity line) but small for PBr, (0.020 & 0.004 and 0.025 f 0.005 for the lines of intensity 1 and 2, respectively). The large values in the BBr, moiety were ascribed to Tc-bonding in the B-Br bonds, although the results suggested that this was reduced on complex formation from ca. 12 % to 5 %. The second-order phase transition in [Me,N],ZnBr, has been investigated by '@Brn.q.r., X-ray, and DSC methods.80The n.q.r. results gave T, as 287 K. Four lines were observed in the low-temperature phase, but three of these broadened as T, was approached and were unobservable above 260 K. The fourth resonance could be followed up to 325 K. The transition was deduced to occur between the space groups Pnma and P2,/,11 over a very wide temperature range. Broadening of the first three lines was attributed to fluctuations of the soft mode, whereas broadening of the fourth line above 300 K was ascribed to increasing thermal motion of the organic groups. The T-dependence of 79Brsignals from [NH,Me,],SnBr, from 77 to 300 K showed the occurrence of a phase transition at 253 f 1 K.81 Two signals in a 2 : 1 intensity ratio were found at most temperatures, in agreement with the room-temperature crystal structure, which showed that two Sn-Br bonds were slightly longer than the other four; the higher frequency corresponded to the shorter bond length. The results were interpreted in terms of stronger hydrogen bonding in the low-temperature phase. The T-dependence of the 81Br n.q.r. lines in pure Rb,ZnBr, was determined from 100 to 367 K.82 Three signals in a 1 : 2 : 1 ratio were observed, in agreement with the symmetry of the ZnBra2-group. No resonance was found for the free Br- ion down to 20 MHz. The lines showed a normal T-dependence,and no phase transitions were apparent. The results accounted for some impurity lines seen in the n.q.r. spectrum of RbeZnBr4. A previous bromine n.q.r. study of (NH,),SnBr, had revealed the existence 2. A. Fokina, S. I. Kuznetsov, N. I. Timoshchenko, and E. V. Bryukhova, Bull. Acad. Sci. U.S.S.R.,Div. Chem. Sci. (Engl. Transl.), 1982, 31, 1720. 79 H. Terao, M. Fukura, T. Okuda, and H. Negita, Bull. Chem. SOC.Jpn., 1983, 56, 1728. R. Perrey, Y.Beaucamps, G. Godefroy, P. Muralt, M. Ehrensperger, H. Arend, and D. Altermatt, J. Phys. SOC.Jpn., 1983, 52, 2523. K. B. Dillon, J. Halfpenny, and A. Marshall, J . Chem. SOC.,Dalton Trans., 1983, 1091. 82 J. Pirnat, J. Luznik, and Z. Trontelj, Phys. Sratus Solidi A , 1982, 74, K55. 78

170


of structural phase transitions at 157 and 144 K. These were further investigated by a more detailed interpretation of the n.q.r. data, together with a neutron powder diffraction It was deduced that the 157 K transition involved the anti-ferro-rotation of halide octahedra, accompanied by a relatively small distortion of the unit cell, whereas the 144 K transition involved a further ferro-rotation of the octahedra, with a larger distortion of the unit cell. Possible space groups in the tetragonal (intermediate) and monoclinic (low-temperature) phases were deduced. The T-dependence of the two equally intense 'OBr resonances from N4P4Br8was determined from 77 to 298 K, and the temperature coefficients were analysed using a Bayer-Kushida-Brown treatment.84 The data were used to calculate torsional frequencies in the range 10-15 cm-l that were only slightly temperature dependent. Four 81Br resonances were detected from N3P3Br6at 77 K only, two of double intensity. The results were correlated with the known electron-density distribution. Data for the bromo compounds were compared with results for their chloro analogues. Single 'OBr and 81Brn.q.r. frequencies were measured for both Sr(BrO,),. H 2 0 and Ba(BrO,),- H 2 0 at 77 and 305 K.85Zeeman studies on single-crystal samples were carried out for the 'OBr lines at room temperature, and the e.f.g. parameters were determined. These were compared with theoretical values. The point-charge model did not yield satisfactory results. In a second model, the total e.f.g. was obtained as the sum of the covalent contribution (from CND0/2 MO calculations) and the interionic contribution. Good agreement with experiment was obtained for the strontium compound but not for the barium salt, and it was suggested that structural data for the latter needed refinement. Similar experiments were carried out for Cd(Br03)2-2H20.8s Two bromine (79Bror 81Br) n.q.r. signals were found at 77 and 305 K, showing two chemically inequivalent sites. Singlecrystal Zeeman experiments for the 'OBr isotope at room temperature gave results for the e.f.g. parameters in good agreement with those from the second theoretical model above. The intraionic e.f.g. was found to comprise more than 95 % of the total e.f.g. at the Br sites. The T-dependence of the halogen resonances in the range 7 7 4 K was determined for a series of substituted anilinium halides 4F-C6H4NH3+X-,4F-C6H4ND3+X-,4Et-C6H4NH3+X-,PhN(Me)H,+X-, and PhN(Et)H,+X- (X = Br or I).s7 All the 4-substituted compounds experienced a phase transition of higher (probably second) order, which was likely to be a ferroelastic one, as in PhNH,+X-. The transition temperatures were lower in the iodides than the bromides, attributed to stronger hydrogen bonding in the latter. Replacement of H by D in the 4-fluorocompoundslowered the transition temperature and the n.q.r. frequencies but raised the value of 3 in the iodide. N-Substitution inhibited the phase transition in PhN(Me)H,+I- and the N-ethyl compounds, although a first-order phase transition was observed for PhN(Me)H2+Br- at 141.5 K. Other results for bromine nuclei have been described in the subsection on Group III.20*22 83

R. L. Armstrong, R. M. Morra, B. M. Powell, and W. J. L. Buyers, Can. J . Phys., 1983,61. 997.

K. R. Sridharan and J. Ramakrishna, Polyhedron, 1983, 2,427. R. Valli and K. V. S. Rama Rao, J . Mol. Srrucf., 1983, 102, 365. 86 R. Valli and K. V. S. Rama Rao, J . Chem. Phys., 1983,79,4113. 87 V. G. Krishnan and A. Weiss, Ber. Bunsenges. Phys. Chem., 1983,87,254. 84


171

The large positive (anomalous) 7'-coefficient observed for the lowest-frequency 1271resonance from a terminal iodine atom in NH41,has been interpreted in terms of a theory that relates the reorientation of the NH,+ ion to a concerted change in the relative weights of the resonance structures of the I,- anion, through formation and scission of hydrogen bonds.88Measurements of proton spin-lattice relaxation times were also made. The activation energy for ammonium-ion reorientation was derived as 7.53 kJ mol-l, the energy of a hydrogen bond as 5.20 kJ mol-l. The T-dependence of e2Qq/hand q for 1271nuclei in NH4103from 300 to 400 K showed the existence of a first-order structural phase transition at 367 f 0.5 K, with hysteresis of 3.5 5 0.5 K.89 The phase-transition mechanism and the appearance of ferroelectricity in the NH4103crystal, due to variations in the structure and lattice dynamics, were discussed. The effect of hydrostatic pressures between 0 and 5 kbar on the low-temperature phase transition (120 K at atmospheric pressure) in a single crystal of KIO, was followed by recording the 12'J resonance(s) for the Qe, # transition at various temperatures and pressure^.^" (Two signals were seen below the phase transition, ascribed to the introduction of impurity hydrogen atoms in place of potassium in the KIO, lattice.) The phase diagram was obtained for a KIO, crystal in the temperature range 4.2130 K and pressure range 0 - 5 kbar from the results. It was deduced that the main effect of applying pressure to a KIO, crystal was on the interionic distance, and the change in geometry of the 10,- anions could be neglected in this pressure range. Other results for 1271nuclei have been given in the subsection on Group 111.19~21

3 Transition Metals and Lanthanides Copper43 and -65.-83Cu and W u n.q.r. frequencies were measured at 77 and 273 K for copper(I)+hloride and -bromide complexes of imidazolidine-2-thione

(izt) and tetrahydro-1H-pyrimidine-Zthione (tpt). No phase changes were detected. The crystal structure of [Cu(tpt),CI] was also determined at room temperature and showed only one kind of Cu' atom, trigonally co-ordinated by two tpt molecules and a chlorine atom, in agreement with the observation of a single 63Cusignal. One 63Cusignal was also observed for each of the other complexes, although X-ray analysis of [Cu(izt),CI], has shown that it is binuclear, with two different types of Cu' atoms, one tetrahedrally and one trigonally co-ordinated. No lower-frequency signals for 83Cucould be detected down to 5 MHz, however. As part of a study of some bis(thiocyanat0)-cuprate(1) and -aurate(r) complexes, mainly by vibrational spectroscopy, the 63Cu and ssCu n.q.r. signals at 301 K of the compound IN(PPh,),][Cu(SCN),] were 88

Y. Yoshioka, N. Nakamura, and H. Chihara, J. Chem. SOC.,Faraday Trans. 2, 1983, 79, 497.

89

D. F. Baisa, A. I. Barabash, I. G. Vertegel, and V. 1. Pakhomov, Ukr. Fiz. Zh. (Russ. Ed.). 1982, 27, 1850. D. F. Baisa, A. I. Barabash, and I. G . Vertegel, Bull. Acad. Sci. U.S.S.R.,Phys. Ser. (Engl. Transl.), 1983, 47, (4), 112. J.-M. Bret, P. Castan, G. Jugie, A. Dubourg, and R. Roques, J . Chem. Soc., Dalton Trans..

g2

1983, 301. G. A. Bowmaker and D. A. Rogers, J. Chem. SOC.,Dalton Trans., 1982, 1873.

172


The single strong 63Cu resonance at 34.86 MHz was in the region expected for digonal or trigonal co-ordination of copper. The vibrational spectroscopic results indicated that the copper compounds did not contain discrete [Cu(SCN),]ions. The effects of distortions on the “Cu n.q.r. frequencies in trigonal c U o , 5 and C U S ~and ~ - tetrahedral CUS,~-were examined by calculating the resonance frequencies, using a Mulliken-Wolfsberg-Helmholz MO method.93 The e.f.g. was larger in the trigonal complex with 0 ligands than with S ligands. In the tetrahedral case, the calculated e.f.g. arising on distortion of the C,, form was comparable in order of magnitude with the experimental value. The highest e.f.g. resulted when the central atom was shifted along the C , axis in the plane of a face of the tetrahedron. Praseodymium-l41.-The optically detected n.q.r. spectrum of la1Pr3+ions doped into a single crystal of YAG was obtained at 1.6 K.94 The ground state of the Pr3+nucleus showed large pseudo-quadrupole splittings of 33.4 and 41.6 MHz. Optically detected n.q.r. at 5 K was observed for Pr3+ ions in a single crystal of LaF3.95 The magnitude and orientation of the enhanced nuclear Zeeman tensor were obtained from measurements in 100 G magnetic fields. The data showed that six Pr3+ magnetically inequivalent sites of symmetry C, (and not Cs)were present. The results were discussed with reference to previous studies by various physical methods on the system. Tantalum-l81.-Results on Group VII.78

for this nucleus have been described in the subsection

Rhenium-185 and -187.-A theoretical treatment has been given of two-frequency relaxation in pulsed n.q.r.9s Experimental results for ls5Re and la7Renuclei in KRe04 at 77 K were interpreted for three types of program of two-frequency spin-echo excitation.

R. S. Abdullin, N. B. Yunusov, and I. N. Pen’kov, Deposited Doc., 1981, VINITI 3553-81 (Chem. Abstr., 1983, 98, 45 630). O4 R. M. Shelby, A. C. Tropper, R. T. Harley, and R. M. Macfarlane, Opt. Lett., 1983,8, 304. 9s B. R. Reddy and L. E. Erickson, Phys. Rev. B, 1983,27, 5217. 96 V. S. Grechishkin, G. V. Mozzhukin, and A. V. Bodnya. Izv. Vyssh. Uchebn. Zaved., Fiz. (Engl. Transl.), 1983, 26. 484. 83

3 Rotational Spectroscopy BY S. CRADOCK

1 Introduction As in previous years, this chapter contains references to work that gives informa-

tion about rotational energies of molecules, in ground states and in vibrationally or electronically excited states. There seem to be rather fewer reports of such studies than in recent years, though this may simply reflect a lower efficiency in the literature search, which is intended to cover the calendar year 1983. The organization of the material is much as last year, but the general group of hydrogen-bonded complexes of organic molecules with proton acids has been summarized in tabular form, being of rather less relevance to inorganic chemistry than other species in the section but of increasing importance in the literature. 2 van der Waals and Hydrogen-bonded Complexes

Studies of the rare-gas-hydrogen halide complexes now seem to be continuing using only Fourier-transform microwave techniques, with the emphasis being on detection by the rotational Zeeman effect. This leads to extensive information on the magnetic properties of the complexes, which is suitable for extraction of time-averaged structures, vibrational potentials, and other structural data. Speciesreported this year are Ar complexes with DF,' HCP and HBr,2Kr. HCN,3 and Xe-HBr.4 Similar studies of Ar complexes with OCS,6 COF2,Band furan' have also been reported, and the Hg-HCI complex has been identified by the same technique.*The Hg- - - C1 distance i s reported as 409.7 pm, leading to a van der Waals' radius of 199 pm for Hg. The N2 HCl complex has been studied by molecular-beam electric resonance methods, including Stark-effect measurements giving structural information as well as dipole moment (1.24 D) and eqQ for the chlorine nucleus,s while the rotational Zeeman effect, the rotational Stark effect, and the pure rotation spectrum of 15N,.HF and 16N2.DFcomplexes have been studied by FourierE. J. Campbell and W. G. Read, J. Chem. Phys., 1983,78,6490. W. G . Read and E. J. Campbell, J. Chem. Phys., 1983,79, 1669. E. J. Campbell, L. W. Buxton, and A. C. Legon, J. Chem. Phys., 1983,78, 3483. S . G. Kukolich and E. J. Campbell, Chem. Phys. Lett., 1983, 94, 73. J. A. Shea, W. G. Read, and E. J. Campbell, J. Chem. Phys., 1983,79,2559. J. A. Shea and E. J. Campbell, J. Chem. Phys., 1983,79,4724. ' S. G. Kukolich, J. Am. Chem. SOC.,1983, 105, 2207. * E. J. Campbell and J. A. Shea, J. Chem. Phys., 1983,79,4082. R. S. Altman, M. D. Marshall, and W. Klemperer, J. Chem. Phys., 1983, 79, 57.

173

174


transform techniques,1° together with rotational Zeeman measurements on complexes of CO with HF, DF, and HCI. Molecular-beam methods were used to record microwave and r.f. spectra of the CO-HCl complex,ll the Stark effect giving a dipole moment of 1.5 D. The complex band associated with HF stretching (vl) in OC. HF has been studied in the infrared;12the spectrum is complicated by the low-frequency bending motion (vJ, which gives a manifold of hot-bands. A similar study on the H F dimer, using a tunable difference-frequency infrared laser ~pectrorneter,~~ gives improved rotation and distortion constants for the ground states as well as for the vibrationally excited states involved. The HCN. . .HF complex has also been studied in the i.r.;14 the N - - - F distance is found to be 3.4 pm shorter in the vibrationally excited state. A series of papers has appeared concerning rotational spectra of hydrogen-bonded complexes HCN.HBr,15 HzO-HX(X = F,16 Cl,17 or CN1*), and CO,.(H/D)F, COz-HCl, and OCS-HF.” Table 1 lists a series of studies of hydrogen-bonded complexes of organic molecules with hydrogen halides or HCN. Org-HX.

Table 1 Organic

HX

TechniquP

Ref.

HCCH HCCH H,CO CZH, CZH4 Cyclopropane Furan C6H6

HCl HCN

FT Z FT Z

20

HF HCI

m.b.e.r.s. FT Z

HCN HCN HCI HCI

FT Z FT Z FTZ FT Z

21 22 23 24 25

26 27

nFT Z = Fourier-transform microwave, Zeeman-effect detection, m.b.e.r.s. = molecular-beam electric-resonance spectroscopy

G. Read and E. J. Campbell, J. Chem. Phys., 1983,78,6515. R. S. Altman, M. D. Marshall, W. Klemperer, and A. Krupnov, J. Chem. Phys., 1983,79,

lo W.

l1

52.

E. K. Kyro, P. Shoja-Chaghervand, K. McMillan, M. Eliades, D. Danzeiser, and J. W. Bevan, J. Chem. Phys., 1983, 79, 78. l3 A. S. Pine and W. J. Lafferty, J. Chem. Phys., 1983, 78, 2154. l4 E. Kyro, R. Warren, K. McMillan, M. Eliades, D. Danzeiser, P. Shoja-Chaghervand, S. G. Lieb, and J. W. Bevan, J. Chem. Phys., 1983, 78, 5991. l5 E. J. Campbell, A. C. Legon, and W. H. Flygare, J. Chem. Phys., 1983, 78, 3494. Z. Kisiel A. C. Legon, and D. J. Millen, J. Chem. Phys., 1983, 78, 2910. A. C. Legon and L. C. Willoughby, Chem. Phys. Lett., 1983,95,449. l8 A. J. Fillery-Travis, A. C. Legon, and L. C. Willoughby, Chem. Phys., Lett., 1983, 98, 369. J. A. Shea, W. G. Read, and E. J. Campbell, J. Chem. Phys., 1983,79, 614. 8o S. G. Kukolich, W. G. Read, J. A. Shea, and E. J. Campbel1,J. Am. Chem. SOC.,1983,105, l2

6423. 21 23

P. D. Aldrich, S. G. Kukolich, and E. J. Campbell, J. Chem. Phys., 1983, 78, 3521. F. A. Baiocchi and W. Klemperer, J. Chem. Phys., 1983, 78, 3509. S. G. Kukolich, P. D. Aldrich, W. G. Read, and E. J. Campbell, J. Chem. Phys., 1983,79, 1105.

S . G. Kukolich, W. G. Read, and P. D. Aldrich, J. Chem. Phys., 1983, 78, 3552. 25 S. G. Kukolich, J. Chem. Phys., 1983, 78, 4832. 26 J. A. Shea and S. G. Kukolich, J. Chem. Phys., 1983,78, 3545. 27 W. G. Read, E. J. Campbell, and G. Henderson, J . Chem. Phys., 1983,78, 3501.

24

175

Rotational Spectroscopy

3 Diatomic Species

Table 2 Species

Ref.

Technique

Stare(s)

( a ) 2-Electron species KH a Laser-induced

6Li2

h

cs,

c

A'Z+ ?-. XlC+ fluorescence (1. i .f.) Collision-induced h31T,, fluorescence 1.r. 1.i.f. 'Il,

Information derived

Equilibrium constants including we, Be Equilibrium constants, re = 259.1 pm Equilibrium constants including a,, Be

(6) 3-Electron species BeH, d Emission spectra BeD

C2Z+,X 2 C s

EquilibriumconstantsforC including re = 230.1 pm

(c) 5-Electron species CH e Laser magnetic resonance (1.m.r.)

X

Microwave and far4.r. transitions calculated

(d) 7-Electron species SH f Molecular-beam 1.i.f. A2Z$ SH g 1.r.-laser absorption X2Jl

Constants for v = 0 level Constants for v = 0 and I levels, equilibrium constants including re = 134.0379(5) pm

(e) 8-Electron species ArD+

Pb,

h i

Millimetre-wave absorption L.i.f.

X'C+

F-X

(f)9-Electron species FeD j - Emission ( - 1 micron) 45-+ 4L

CO+

k

13C160+ I

Isotopic frequencies

J = 1t0

Millimetre-wave absorption

1c+

L.i.f.

A2rI -+ X'C+

v=OorI

Equilibrium constants for both states [re = 307.9(5), 293.0(5) pm] Constants for v = 0 levels of both states Equilibrium constants, including Be, re = 111.517 59(15) pm Constants for both states

a A. Pardo, J. M. L. Poyato, M. S. Guijarro, and J. I. Fernandez-Alonso,J. Mol. Spectrosc., 1983,97, 248. F. Engelke and H. Hage, Chem. fhys. Lett., 1983, 103, 98. C. Amiot, C. Crepin, and J. Verges, Chem. Phys. Lett., 1983,98, 608. R. Colin, C. Dreze, and M. Steinhauer, Can. J. Phys., 1983,61,641. J. M. Brown and K. M.Evenson, Astrophys. J., 1983,268,L51. W. Ubachs, J. J. Ter Meulen, and A. Dymanus, Chem. Phys. Lett., 1983, 101,1. P.F. Bernath, T. Amano, and M. Wong, J. Mol. Spectrosc., 1983,98,20. !IW. C. Bowman, G. M. Plummer, E. Herbst, and F. C. De Lucia, J. Chem. Phys., 1983,79, 2093. H. Sontag and R. Weber, J. Mol. Spectrosc., 1983, 100, 75. W. J. Balfour, B. Lindgren, and S . O'Connor, Chem. fhys. Lett., 1983,96, 251. M. Bogey, C. Demuynck, and J. L. Destombes, J. Chem. fhys., 1983,79,4704. R.D. Brown, R. G. Dittman, D. C. McGilvery, J. C. Hansen, C. H. Kuo, F. J. and P. D. Godfrey, J. Mol. Spectrosc., 1983, 101, 6.


176

Table 2 (continued) Species

Ref.

Technique

State(s)

Information derived

N2+

m

Absorption

X2C+ --f A211 v=o v=4

Upper-state constants

CN

n

14C14N SiN

o p

Millimetre-wave and X, v = 0-3 sub-m.m.w. Visible emission A211 -+ X2C+ Microwave X2C+

A10

r

Emission

40Ca7DBrs

C%-XZZ+

BaCl

t

Microwave and mw/ X 2 C + laser double resonance L.i.f. 2A 4

NaAr

ii

L.i.f.

Dunham constants, spin-rotation constants Constants for both states Rotation constants, re = 157.2066(41) pm Equilibrium constants including re = 281.4, 261.2 pm, respectively Equilibrium constants for C-state Dipole moment 4.36D Equilibrium constants including Be I-,= 500.8(5)pm

?

( g ) 10-Electron species

Nz

Y

Emission

B3ng A 3 C t

co

M'

-

X1C+

14Cls0

x

Emission

c3n-a311

--f

28Si34S

y

Emission

v=ov=3 A'n-X'C+

BCI

z

Microwave

X

Equilibrium constants for both states including Be Dunham coefficients for 7 isotopic species Constants for each level Constants for A, e3C-, d 3 A , CIC-,and DIA states by analysis of perturbations eQq for CI

(h) 11-Electron species B = 21 899.49 MHz, etc. PO aa Microwave and 1.m.r. X211 PO bb 1.r. (diode laser) X 2 n , v = 0 + 1 yo, re = 147.6370(15) pm Dipole moment, re = CF cc Microwave X 127.1972(13)pm Rotation and distortion SiF dd Microwave X2%l constants, etc. Grieman, and J. T. Moseley, J. Chem. Phys., 1983, 79, 1111. D. D. Skatrud, F. C. De Lucia, G. A. Blake, and K. V. Sastry, J. Mol. Spectrosc., 1983, 99, 35. O C. Amiot and J. Verges, Chem. Phys. Lett., 1983,95, 189. S . Saito, Y. Endo, and E. Hirota, J. Chem. Phys., 1983, 78, 6446. V. E. Bondybey and J. H. English, J . Chem. Phys., 1983, 79, 4746. M. Singh and M. D. Saksena, Can. J. Phys., 1983, 61, 1347. S. Kindt, W. E. Ernst, and T. Torring, Chem. Phys. Lett., 1983,103,241. H. Martin and P. Royen, Chem. Phys. Lett., 1983, 97, 127. R. Aepfelbach, A. Nunnemann, and D. Zimmermann, Chem. Phys. Lett,, 1983, 96, 31 1. * F. Roux, F. Michaud, and J. Verges, J. Mol. Spectrosc., 1983, 97, 253. G. Guelachvili, D. Devilleneuve, R. Farrenq, W. Urban, and J. Verges, J. Mol. Spectrosc.. 1983, 98, 64. T. Siwiec-Rytel, J. Mol. Spectrosc., 1983, 97, 234. G. Krishnamurty, S. Gopal, P. Saraswathy,and G. Lakshminarayana, Can. J . Phys., 1983, 61, 714. Y.Endo, S. Saito, and E. Hirota, Bull. Chem. SOC.Jpn., 1983, 56, 3410. aa K. Kawaguchi, S. Saito, and E. Hirota, J. Chem. Phys., 1983,79, 629. bb J. E. Butler, K. Kawaguchi, and E. Hirota, J. Mol. Spectrosc., 1983,101, 161. cc S. Saito, Y.Endo, M. Takami, and E. Hirota, J. Chem. Phys., 1983,78, 116. dd M.Tanimoto, S. Saito, Y. Endo, and E. Hirota, J. Mol. Spectrosc., 1983, 100, 205. ee T. G. Slanger and D. L. Huestis, J. Chem. Phys., 1983, 78, 2274. ff A.

177


Table 2 (continued) Species

Ref.

Technique

( i ) 12-Electron species 0 2 ee

Se,

fl

Absorption

NCI

gg

Microwave

( j ) 13-Electron species FO hh 1.r. (diode laser) FS ii 1.r. (diode laser)

Brz+

jj

L.i.f.

Re0

kk

Absorption, -404.5 nm

(k) 14-Electron species 12 I1 Polarization labelling ( I ) 15-Electron species XeF mm L.i.f.

Information derived

Rotation and vibration analysis Constants for substates of B including re = 243.81 -244.78 pm Rotation, distortion, and hyperfine constants including e Q q for N and CI yo, Bo, B1 Constants for v = 0, 1, and 2, re = 159.6244(22)pm Equilibrium constants for both pairs of states Equilibrium constants for upper and lower states

Equilibrium constants including re = 357.4 pm, w e = 104.18~111-l Constants for C-state

(m) 16-Electron species

CuF CuF

nn

Af31

pp

00

L.i.f. Intermodulated fluorescence spectroscopy Microwave

(n) 20-Electron species YbO qq Laser spectra

Nuclear hyperfine splittings Constants including B = 0.374740(6) cm-l Dipole moment = 5.10(15) D and eQq for I Equilibrium constants including Be and o,

Jenouvrier, Can. J. Phys., 1983, 61, 1531. gg C. Yamada, Y. Endo, and E. Hirota, J. Chem. Phys., 1983,79,4!59. A. R. W. McKellar, C. Yamada, and E. Hirota, J. Mol. Spectrosc., 1983, 97, 425. Y. Endo, K. Nagai, C. Yamada, and E. Hirota, J. Mol. Spectrosc., 1983, 97, 213. j J T. Harris, J. H. D. Eland, and R. P. Tuckett, J. Mol. Spectrosc., 1983, 98, 269. kk W. J. Balfour and R. S . Ram, J. Mol. Spectrosc., 1983, 100, 164. ' I J. C. D. Brand and A. R. Hoy,J. Mol. Spectrosc., 1983, 97, 379. mm H. Helm, D. L. Huestis, M. J. Dyer, and D. C. Lorents, J. Chem. Phys., 1983, 79, 3220. n n C .R. Brazier, J. M. Brown, and M. R. Pwnell, J . Mol. Spectrosc., 1983,99, 279. O0 C. R. Brazier, J. M.Brown, and T. C . Steimle, J. Mol. Spectrosc., 1983, 97, 453. p p J. Hoeft and K. P. R. Nair, J. Mol. Structure., 1983, 97, 347. qa C. Linton, S. McDonald, S. Rice,M. Dullick, Y. C. Liu, and R. W. Field, J. Mol. Spectrosc., 1983, 101, 332.

178

Spectroscopic Properties of Inorganic and Organometallic Compounds 4 Triatomic Molecules and Ions

The ground state (X2B1)of ND2 has been investigated using microwave/optical double-resonance28and i.r./optical double-resonan~e~~ methods, The microwave spectrum of PH2 has been observed and analysed to give rotation constants, spin-rotation constants, and hyperfine coupling constants.30HDO absorption at DF-laser line frequencies (22 lines in the 3 . 5 4 . 1 micron band) has been rneas~red,~' and the spectrum of T2180in the 1100-900 cm-l region has been reported;32 the ro structures for the vibrational ground state and the v2 = 1 excited state are tabulated in Chem. Abstr. Another study of v2 of H2Sis r e p ~ r t e d , ~ ~ and the pure rotation spectra of 32S, 33S,and 34Sisotopomers in the far i.r. have been analysed, together with microwave data for the normal species, to give precise rotation constant^.^^ Laser excitation spectra of CaOH(D) (A-X emission)35and SrOH(D) (B-X emission)36have been reported; both molecules are linear in both ground and electronically excited states, and in each case r,(MO) is smaller in the upper electronic state than in the ground state. CuOH(D) has been studied by laser excitation and by chemiluminescence spectros~opy;~~ it is bent in the ground state ( F A ' ) and in the lA" excited state, which has a rather longer CuO bond than the ground state. The v1 band of the ion HN2+has been observed using velocity-modulated i.r.-laser-absorption spectros~opy,~~ while HCO+ has been studied in the same region using difference-frequencyi.r.-laser spe~troscopy.~~ Both P- and R-branch lines were measured, and the excited-state B value was determined as 1.475699(11) cm-l, with the band centre at 3088.7395(3) cm-l. Several bands of DCP have been observed by Fourier-transform i.r. methods, and the results have been analysed with earlier data to give an extended set of rotation and vibration constants.40 Fourier-transform i.r. spectra of HNO and DNO have allowed the identification of v1 and v2 for both species and of v3 for HN0,41giving data for calculation of band centres and rotation constants. Laser-excitation spectra of HCC142have been analysed to give ground-state constants leading to rz structural parameters [r,(CH) = 111.88(71) pm, r(CC1) = 169.61(25) pm, LHCCl = 101.4(12)"],

J. M. Cook and G. W. Hills, J. Chem. Phys., 1983,78,2144. R. E. Muenchausen and G. W. Hills, Chem. Phys. Lett., 1983,99, 335. 30 Y.Endo, S. Saito, and E. Hirota, J. Mol. Spectrosc., 1983, 97, 204. 31 C. W. Bruce and A. V. Jelinek, Appl. Opt., 1982, 21, 4101. 32 I. Kanesaka, M. Tsuchida, K. Kawai, and T. Takeuchi, Kenkyu Hokoku- Toyama Daigaku Torichumu Kagaku Senta, 1982, 2, 27 (Chem. Abstr., 1983, 99, 45 569). 33 L. L.Strow, J. Mol. Spectrosc., 1983,97,9. 34 J.-M. Flaud, C. Camy-Peyret, and J. W. C. Johns, Can. J. Phys., 1983, 61, 1462. 36 R. C. Hilborn, Zhu Qingshi, and D. 0. Harris, J . Mol. Spectrosc., 1983, 97, 73. 36 J. Nakagawa, R. F. Wormsbecher, and D. 0. Harris, J. Mol. Spectrosc., 1983, 97, 37. 37 M. Trkula and D. 0. Harris, J. Chem. Phys., 1983, 79, 1138. 38 C. S. Gudeman, M. H. Begemann, J. Pfaff, and R. J. Saykally, J. Chem. Phys., 1983, 78, 28

2a

5837.

T. Amano, J. Chem. Phys., 1983, 79, 3595. J. Lavigne, C. Claude, and A. Cabana, J. Mol. Spectrosc., 1983, 99, 203. 41 J. W. C. Johns, A. R. W. McKellar, and E. Weinberger, Can. J. Phys., 1983, 61, 1106. 42 M. Kakimoto, S. Saito, and E. Hirota, J. Mol. Spectrosc., 1983, 97, 194.

179


and the v, band has been studied using an i.r. diode laser ~pecfrometer.~~ The v1 band of H 0 2 has been observed using a difference-frequency i.r. laser,44and the microwave spectrum of DO, has been A partial rotational analysis of a band assigned as the 0-0 band of the A2E+-X211itransition of CNO is reported briefly, with preliminary constant^.^^ The v, + v1 - v, hot-band of FCISN has been studied using i.r./microwave double re~onance,~’ and the microwave spectrum of BrCN has been analysed to give rotation, distortion, and N and Br quadrupole-coupling The i.r. spectrum of FCP is reported at high res01ution.~~ The bending bands of N20,50CO,,sl and OCS51 have been studied using Fourier-transform spectrometers, the 2 micron bands of COz, again studied by FT methods, have been analysed to give effective constants for several excited states,62and laser Stark spectra of CO, in a supersonic beam have been recorded using a tunable (F-centre) i.r.-laser exciting lines in the v1 v 3 band.53Diode laser spectra of OCS in the v1 region have allowed study of the 2v, - v 1 hot-band, giving upper- and lowerstate B values.64 The microwave spectrum of NO, in several vibrationally excited states has been analysed to give an re structure [r(NO) = 119.389(4) pm, LON0 = 133 51.4(2)’].s6A colour-centre laser spectrometer with magnetic-rotation sensitivity enhancement has been used to study the v1 v2 v 3 combination band of NO,; the magnetic-rotation spectrum enhances high-K transitions and leads to improved K-dependent rotation and distortion constants.66The 2B1(K’= 0)2A1(K” = 1) bands of NO, have been analysedS7to give B values for v’ = 6,7, and 10. The 22B2-X2A1band of PO, shows vibrational and K fine structure but no resolved J the result is claimed as the first spectroscopic identification of the species. The v1 -t- v, v 3 ternary combination band of ozone near 2800 cm-l has been studied,6gand the vl band of SaO, has been investigated by i.r./microwave double-resonance spectroscopy.6oMicrowave and laser Stark spectroscopy of FNO has given dipole moments in the vibrationally excited states;l while microwave spectra of more isotopic forms of ONCl in ground and

+

O

+ +

+

48

M. Tanimoto, K. Yamada, G. Winnewisser, and J. J. Christiansen, J. Mol. Spectrosc., 1983, 100, 151.

C. Yamada, Y. Endo, and E. Hirota, J. Chem. Phys., 1983,78,4379. 45 S . Saito, Y. Endo, and E. Hirota, J . Mol. Spectrosc., 1983, 98, 138. 48 D. Ramsay and M. Winnewisser, Chem. Phys. Lett., 1983,%, 502. 47 J. Sheridan and H. Jones, J . MoL Spectrosc., 1983, 98, 498. 48 C. D. Cogley-and S. G. Kukolich, J. Mol. Spectrosc., 1983, 97, 220. 4g K. Ohno, H. Matsuura, H. Murata, and H. W. Kroto, J . Mol. Spectrosc., 1983, 100, 403. K. Jolma, J. Kauppinen, and V.-M. Horneman, J. Mol. Spectrosc., 1983, 101, 278. t1 K. Jolma, J. Kauppinen, and V.-M. Horneman, J . Mol. Spectrosc.. 1983,101, 300. 5z P. Arcas, E. h i e , M. Cuisenier, and J. P. Maillard, Can. J. Phys., 1983, 61, 857. 53 T. E. Gough, B. J. Orr, and G . Scoles, J . Mol. Spectrosc., 1983, 99, 479. h4 W. Klebsch, K. Yamada, and G. Winnewisser, J. Mol. Spectrosc., 1983, 99, 479. A5 Y. Morino, M. Tanimoto, S. Saito, E. Hirota, R. Awata, andT. Tanaka, J. Mol. Spectrosc., 44

1093, 98, 331.

W. Dillenschneider and R. F. Curl, jun., J . Mol. Spectrosc., 1983, 99, 87. 57 S. Takezawa, N. Sugimoto, and N. Takeuchi, Chem. Phys. Lett., 1983,97, 77. ti8 R. D. Verma and C. F. McCarthy, Can. J . Phys., 1983, 61, 1149. A. Barbe, C. Secroun, A. Goldman, and J. R. Gillis, J . Mol. Spectrosc., 1983, 100, 377. J. Lindenmayer, H. Jones, and H. D. Rudolph, J . Mol. Spectrosc., 1983, 101, 221. G. Cazzoli, C. Degli Esposti, and P. G. Favero, Chem. Phys. Lett., 1983,96, 664.

180


vibrationally excited states have been used with existing data to define an re structure [r(NCI) = 197.453(25) pm, r(N0) = 113.357(25) pm, LONCl == 113.320(13)"]for the major isotopic species and an r, structure, which is similar but less well defined.62Laser Stark spectra of C10, in the v1 region have been reported.63Far4.r. laser magnetic resonance spectra of FSO and ClSO have been no assignmentsare yet possible for ClSO, but the transitions observed for FSO were identified with the help of microwave spectra. Microwave/optical double-resonance spectra of OF, have been in the region of the v1/2v, Fermi diad, giving rotation and distortion constants for both upper states. 5 Tetra-atomic Molecules As usual there is a plethora of paper^^^-^^ on various aspects of the spectra of ammonia and its isotopes. Laser Stark spectra of the v2 band of PH3 have been used to study the K = 3 doubling.72 Laser excitation spectra of CaNH, (C2A1--X2A1)have been reported;73the molecule is effectively planar in both states, and the CaN bond appears to be shorter in the excited state. The 3,' band of the a3A,-X1A1 transition of thioformaldehyde has been studied by laser-excitation spectroscopy and microwave/optical double resona n ~ eThe . ~ ~v4 band of HCNO has been at 0.006 cm-l resolution, and the necessary theory of the bending motion of a pseudo-linear molecule has been d e ~ e l o p e dThe . ~ ~ v2 band of HNCO has been investigated by 0.015 cm-l resolution grating i.r. technique^,^^ and millimetre-wave spectra of HCCI have been reported78[the dipole moment is only 0.02(1) D!]. The structure of the NO dimer has been deduced from Fourier-transform microwave the gas-phase molecule, formed in a supersonic expansion, is cis-planar, with a long NN bond and NO bonds barely lengthened from the monomer [r(NN) = 223.6(1) pm, r(N) = 116.1(4) pm, LNNO = 99.6(2)"]. The structure is very similar to that found in the crystal. The v3 band of SO3 has 6z

63 64 65 66

G. Cazzoli, C. Degli Esposti, P. Palmieri, and S. Simeone, J . Mol. Spectrosc., 1983,97, 165. K. Tanaka and T. Tanaka, J . Mol. Spectrosc., 1983, 98, 425. H. E. Radford, F. D. Wayne, and J. M. Brown, J . Mol. Spectrosc., 1983,99,209. G . Taubman, H. Jones, and H. D . Rudolph, J . Mol. Struct., 1983, 97, 285. P. Shoja-Chaghervand, E. Bjarnov, and R. H. Schwendeman, J . Mol. Spectrosc., 1983,97, 287.

67

P. Shoja-Chaghervand, E. Bjarnov, and R. H. Schwendeman, J. Mol. Spectrosc., 1983,97, 306.

68

S. Urban, D. Papousek, J. Kauppinen, K. Yamada, and G. Winnewisser, J. Mol. Spectrosc.,

1983, 101, 1. S. Urban, D. Papousek, S. P. Belov, A. F. Krupnov, M. Yu. Tret'yakov, K. Yamada. and G. Winnewisser, J . Mol. Spectrosc., 1983, 101, 16. 70 V. Spirko, J. Mol. Spectrosc., 1983, 101, 30. 71 V. A. Job, N. D. Patel, R. D'Cunha, and V. B. Kartha, J . Mol. Spectrosc., 1983, 101, 48. 72 M. Carlotti, G. Di Lonardo, and A. Trombetti, J . Chem. Phys., 1983, 78, 1670. 73 R. F. Wormsbecher, R. E. Penn, and D. 0. Harris, J. Mol. Spectrosc., 1983,97, 65. 74 T. Suzuki, S. Saito, and E. Hirota, J . Chern. Phys., 1983, 79, 1641. 75 B. P. Winnewisser and P. Jensen, J. Mol. Spectrosc., 1983, 79, 1641. 76 P. Jensen, J. Mol. Spectrosc., 1983, 101, 422. 77 D. A. Steiner, S. R. Polo, T. K. McCubbin, jun., and K. A. Wishaw, J . Mol. Spectrosc., 1983, 98, 453. 78 E. Schafer and J. J. Christiansen, J . Mol. Struct., 1983, 97, 101. 7g S. G. Kukolich, J . Mol. Spectrosc., 1983, 98, 80.


181

been studied by Fourier-transform i.r. spectroscopy.8o Microwave spectra of SOCI, have been analysed to give 'pseudo-substitution' structures, of which the preferred one has r ( S 0 ) = 142.78(5) pm, r(SC1) = 207.44(3) pm, LClSCl = 96.95", and LOSCl = 107.96(2)"; the variations among the structures calculated in different ways suggest that the error limits quoted are optimistic.81The species C 3 0 has been claimedeZas a short-lived linear molecule on the basis of a microwave spectrum; Bo is 4810.88(3) MHz and the dipole moment is found to be 2.39 D. 6 Penta-atomicMolecules

Two reports have appeared of the identification of lines in the NH stretching band of NH4+in the gas A rotational analysis of the Schuster band of ND4 has been the structure is much better defined than that in the corresponding band of NH,. The Raman spectrum of v, of CD,I, recorded at 0.28 cm-l resolution, allows A . to be defined;88analysis of the Raman data together with more precise line positions from the i.r. spectrum gives A, = 2.59608(10) cm-l. Combination of this result with previous values of aA for all fundamentals gives A, = 2.6200(8) cm-l and a very precise value for the distance of the D atoms from the three-fold axis. The millimetre-wave spectrum of SiH,F in the ground and vibrationally excited states has been and the results were used together with Fourier-transform i.r. spectra of the v2 and v5 bandsa8to define the upper-state constants for this pair of close-lying, strongly Coriolis-coupled levels. The Si-Br stretching band, v3, and some hot-bands in the same region have been analysed for SiH3Br,again at 0.05 cm-l r e s o l u t i ~ nThe . ~ ~ pure rotation spectrum of mono-isotopic '*GeH,F in the millimetre-wave region has been reported;OO the large B value ( 10 GHz) makes it impossible to define even B and DJ from the conventional microwave spectrum (up to 40 GHz). Fourier-transform i.r. spectra of the heavier germyl halides, again using mono-isotopic 74Ge,have been used to characterize the Ge-X stretching bands of H,GeX (X = C1, Br, or I).O1 The microwave spectrum of NH,SH has been studied in the gaseous products of a discharged mixture of N2 and H2S;02both cis and trans forms are N

N. F. Henfrey and B. A. Thrush, Chem. Phys. Lett., 1983, 102, 135. F. Mata and N. Carballo, J . Mol. Sfruct., 1983, 101, 233. az R. D. Brown, F. W. Eastwood, P. S. Elmes, and P. D. Godfrey, J . Am. Chem. SOC.,1983, 105, 6496. 84

M. W. Crofton and T. Oka, J. Chem. Phys., 1983, 79, 3157. E. Schiifer, M. H. Begemann, C. S. Gudeman, and R. J. Saykally, J . Chem. Phys., 1983,

79, 3159. G. Herzberg and J. T. Hougen, J . Mol. Spectrosc., 1983, 97, 430. C. Poulsen and S. Brodersen, J. Raman Spectrosc., 1983, 14, 77. R. J. Butcher and J. H. Carpenter, J. Mol. Spectrosc., 1983, 99, 476. R. Escribano and R. J. Butcher, J. Mol. Spectrosc., 1983, 99, 450. 8B H. Burger and G. Schippel, J . Mol. Spectrosc., 1983, 98, 199. S. Cradock and J. G. Smith, J. Mol. Spectrosc., 1983, 98, 502. O1 H. Burger, K. Burczyk, R. Eujem, A. Rahner, and S. Cradock, J. Mol. Spectrosc., 1983,97, 266. s2 F. J. Lovas, R. D. Suenram, and W. J. Stevens, J . Mul. Spectrosc., 1983, 100, 316.

182


observed, and the structures have been deduced from the rotation constants with some help from ab initio calculations. The nitrogen atoms are distinctly non-planar in both forms. The v3 band of SiF4 has been studied using i.r./microwave double-resonance technique^.^, The millimetre-wave spectrum of OP35C1,37C1 has been reported;94 the authors find it impossible to define the structure of OPCl, fully using the resulting rotation constants with B for OP35C1,. 7 Molecules with Six or More Atoms High-resolution Fourier-transform i.r. spectra of 11B2H6and the D, form have been reported;95 ground-state combination differences were analysed to give accurate ground-state molecular rotation and distortion constants. The microwave spectra of various isotopic species of H3BNH3 have been r e p ~ r t e d , ~ ~ and a substitution structure has been defined [r,(BN) = 165.76(16) pm, r(BH) = 121.60(17) pm, r(NH) = 101.40(20) pm, LNBH = 104.69(11)", LBNH = 110.28(14)"]. The barrier to internal rotation is just over 2 kcal mole-l, and the molecular dipole moment is measured as 5.216(17) D. The microwave spectra of some isotopic species of Me2B2H4allow r,(BB) to be estimated as 176(2) pm, but no other structural information can be extracted; analysis of the internal rotation structure gives a V , barrier for the methyl torsion of 1.39(16)kcal rn01-l.~~ The dipole moment is 0.87(3) D. The microwave spectrum of SiD3NC0 has been analysedB8in terms of a very anharmonic bending potential, as for the SiH, molecule. Microwave spectra of a number of isotopic species of ally1 silane are shown to be consistent with a single skew isomer;99 a molecular structure is deduced from substitution coordinates for most atoms, but some assumptions are necessary as one carbon lies very close to the centre of mass. Both the equatorial and axial isomers of cyclobutyl silane are identified by their microwave spectra.lo0The microwave spectra of EtSn(H/D), have been reported (together with vibrational spectra)lol and analysed to give a partial structure [r(SnC) = 214.3(3) pm, r(CC) = 155.2(25) pm, LSnCC = 112.6(9)"];the molecular dipole moment is 0.99(2) D. I.r./microwave double-resonance spectra have assisted the assignment of some microwave lines of excited vibrational states of N2H4 involving the NHa deformation mode near 10 microns;lo2excited-state rotation constants and splittings due to internal rotation, inversion, and Coriolis couplings are given.

M. Takami and H. Kuze, J . Chem. Phys., 1983, 78, 2204. J. H. Carpenter, R. Crane, and J. G. Smith, J . Mol. Spectrosc., 1983, 101, 306. O6 J. Harper and J. L. Duncan, J . Mol. Spectrosc., 1983, 100, 343. L. R. Thorne, R. D. Suenram, and F. J. Lovas, J. Chem. Phys., 1983,78, 167. Q7 C. W. Chiu, A. B. Burg, and R. A. Beaudet, J . Chem. Phys., 1983,78, 3562. 98 L. Halonen and I. M. Mills, J. MoZ. Spectrosc., 1983, 98, 484. Oe M. Imachi, J. Nakagawa, and M. Hayashi, J . Mol. Struct., 1983, 102, 403. loo A. Wurstner-Ruck and H. D. Rudolph, J . Mol. Struct., 1983, 97, 327. lol J. R. Durig, Y.S. Li, J. F. Sullivan, J. S. Church, and C. B. Bradley, J . Chem. Phys., 1983, 78, 1046. lo2 H. Jones and M. Takami, J. Chem. Phys., 1983, 78, 1039. 93 94


183

Torsional potentials for methane thiols CH2DSH and CHD2SH have been derived from microwave spectra; the V, terms have opposite sign for the two isotopic forms, allowing the trans-gauche energy differences to be e~tab1ished.l~~ The gauche and trans forms of Me2CHSeHhave been identified by their microwave spectra;lWthe resulting partial structures are similar [r(SeC) = 193.9(3), 193.0(3) pm, respectively, LCSeH = 93" 42'(61), 93" 24'(61), respectively] and the SeH torsional potential has been characterized by V2 = -0.088(15) kcal mol-l, V3 = 1.543(29) kcal mol-l, assuming V , = 0. Microwave spectra of bromine and sulphur isotopic forms of SF,Br have been usedlo6 to define a structure with r(SF)(equatorial) more than 10 pm greater than r(SF)(axial), which seems most implausible.

lo3 Chun Fusu and C. R. Quade, J. Chem. Phys., 1983, 79, 5828. lo4 J. Nakagawa, A. Nagayama, and M. Hayashi, J. Mol. Spectrosc., lo6

1983, 99, 415.

R.Jurek. P.Goulet, C. Verry, and A. Poinsot. Can.J . Phys., 1983.61.1405.

Characteristic Vibrations of Compounds of Main-group Elements BY S. CRADOCK

1 Group I

Low-frequency i.r. and Raman spectra have been reported' for lithium formate monohydrate and its aqueous solutions; bands due to formate ligand librations and to solvent structure were identified. Raman spectra of solid lithium hydrogen oxalate monohydrates (lithium-6 and -7, H and D isotopes) have been reported2 and interpreted using a factor-group analysis. The effects of lithium chloride and lithium perchlorate solutes on the Raman spectra of liquid water have been interpreted3 in terms of the effects of the solutes on Darling-Dennison and Fermi resonances in the OH stretching-mode bands. Low-frequency Raman spectra of glassy solid solutions of lithium and calcium halides in water show4 the importance of charge-transfer states of the hydrogen bonds in determining the intensities of the various bands. 1.r. and Raman spectra of sodium hydrogen formate have been reported,6 and the vibrational spectra of sodium hydroxide solutions at room temperature and at 77 K have been analysed." 2 Group11

Lr. spectra of monomeric Be(NR,), (R = SiMe,, Pri, or piperidino) and BeW(SiMe,)CMe,], all show7 a strong i.r. band between 1200 and 1300 cm-l assigned to v,,(BeN,). 1.r. data are used to show the presence of bridging hydrazine groups in Mg(N,)2(N2H4)2,formed by reaction of Mg with ammonium azide in hydrazine hydrate solution;* this decomposes on heating to give what is claimed to be a dinitrogen complex of magnesium, Mg(NH,),(N,), characterized by i.r. spectra. 1.r. spectra are reported for some hydrates and methanolates of magnesium acetate0 and some perchlorate complexes of magnesium, M[Mg(ClO,),] (M = Cs or Bu,N), which are said to contain bidentate perchlorate.1° Several studies of i.r. or Raman spectra of hydrates of strontium

' A. Agarwal, D. P. Khandelwal, and H. D. Bist, Can. J . Chem., 1983, 61. 2282. Y.Hase, Monatsh. Chem., 1983,114,541. A. Sokolowska and Z. Kecki, J. Mol. Struct., 1983, 101, 113. H. Kanno and J. Hiraishi, J . Phys. Chem., 1983, 87, 3664. E. Spinner, J . Am. Chem. SOC.,1983, 105, 756. I. Kanesaka, M. Tsuchida, and K. Kawai, J. Raman Spectrosc., 1982, 13, 253. H. Noth and D. Schlosser, Znorg. Chem., 1983, 22, 2700. K. C. Patil, C. Nesamani, and V. R. P. Verneker, Polyhedron, 1982, 1, 421. 1. Zlateva and M. Spasova, Z . Anorg. Allg. Chem., 1983, 497, 229. lo Z. K. Nikitina and V. Ya. Rosolovskii, Zh. Neorg. Khim., 1982, 27. 2224.

'

184

Characteristic Vibrations of Compounds of Main-group EIements

185

h a l i d e ~ , ~strontium14 l , ~ ~ $ ~ ~or barium15nitrites, and strontium formate16have been reported. 3 Group111

Boron.-1.r. spectra show the presence of exclusively tridentate borohydride T H F= groups in M(BH4),-nTHF (M = Lu or Gd) and L ~ L u ( B H ~ ) ~ . ~(THF tetrahydrofuran) so that the rare-earth metal is 12-co-ordinatein the Li c0mp1ex.l~ 1.r. spectra have been usedla to characterize the products of reaction of (NCS), with [BloHl,]2- as [2-BloHaNCSI2-and two isomers [1,2- and 1,6-BIOHa(NCS),I2-. Raman spectra have shown1, the existence of a low-temperature (near 165 K) phase transition in solid 1,7-dicarbaclosododecaborane. Decachlorodicarbaclosododecaboranes form hydrogen-bonded complexes with 0 and N organic basesY2O with the C-H groups acting as proton donors. Some new tris(norborny1)boranes have been characterized by Lr., n.m.r., and mass spectroscopy.21 1.r. spectra of matrix-isolated B203molecules have been studied and assignments discussed in the light of plausible structures.22Low-frequency Raman bands of vitreous and molten Ba03have been studied as a function of temperature and the results were interpreted in terms of boroxol ring rupture on melting.23 The state of boron in concentrated aqueous solutions has been studied using i.r. and Raman spectra; in alkaline solutions both B(OH)3and [B(OH),]- can be identified.24Three reports have appeared on vibrational spectra of borates, with suggested assignments for a diethylammonium borate,26 for BO, modes in B,03.S03,2a and for Mg,B206;,’ the last of these reports includes a normalco-ordinate analysis of the B2054-ion based on spectra of 1°B- and llB-enriched samples. A helical conformation is claimed for the new stable bisborate B(OCH2C3H4CH20),B,where -C3H4- is a cyclopropyl ring;28 i.r., Raman, T. C. Donnelly and C. P. Nash, Appl. Spectrosc., 1982, 36, 698. H. D. Lutz and H. Christian, J. Mol. Strut., 1983, 101, 199. l 3 H. D. Lutz, Spectrochim. Acfa, Part A , 1982, 38, 921. l4 0. P. Lamba, H. D. Bist, and D. P. Khandelwal, J. Mol. Strut., 1983, 101, 223. l5 0. P. Lamba and H. D. Bist, J. Phys. Chem. Solids, 1983,44,445. l6 A. C. Prieto, A. Gonzalez, E. Hernandez, F. Rull, and J. A. De Saya, Cryst. Res. Techno/.. l1

l2

1983, 18, 1093. l7

U. Mirsaidov, A. Rhakimova, and T. N. Dymova, Dokl. Akad. Nu& Tadzh. SSR, 1982.

l9

H. Mongeot and J. Atchekzai, Bull. SOC.Chim. Fr., 1983, 70. S. S. Bukalov, L. A. Leites, A. L. Blumenfeld, and E. I. Fedin, J. Raman Spectrosc., 1983,

25,407.

14, 210.

L. A. Leites, L. E. Vinogradova, J. Belloc, and A. Novak, J. Mol. Struct., 1983, 100, 37, 9. V. Dmitrov, K. H. Thiele, and A. Zschunke, Z. Anorg. Allg. Chem., 1982, 494, 144. 2a L. V. Serebrennikov, Yu. N. Sekachev, and A. A. Maltsev, High Temp. Sci., 1983, 16, 23. 23 G. E. Walrafen, M. S. Hokmabadi, P. N. Krishnan, S. Guha, and R. G. Munro, J. Chem. Phys., 1983, 79, 3609. 24 E. A. Kopylova, L. P. Ni, B. K. Nauryzbaeva, and L. A. Chernenko, Kompleksn. Ispol’z. Mier. Syr’ya, 1983, 24. 25 V. G. Skvortsov, R. S. Tsekhanskii, A. K. Molodkin, V. M. Akimov, 0.V. Petrova, and V. P. Dolganev, Russ. J. Inorg. Chem., 1983, 28, 741. 26 A. M. Bondar’, S. N. Kondrat’ev, and S . I. Mel’nikova, Russ. J. Znorg. Chem., 1983, 28, 2o 21

483. 28

Yu. N. Il’in, V. V. Kravchenko, and K. I. Petrov, Russ. J . Znorg. Chem., 1983, 28, 909. V. J. Heintz, W.A. Freeman, and T. A. Keiderling, Inorg. Chem., 1983, 22, 2319.

186

Spectroscopic Properties of Inorganic and Qrganometallic Compounds

and vibrational circular-dichroism spectra are reported. Boron is four-coordinate by oxygen in the 4chlorosalicylate complexes ML2B, for which i.r. spectra are reportedzD(M = Na, n-hydrate; M = K, monohydrate). Raman spectra of vitreous BZS3 and polycrystalline thioboric acid (HBS2)3 have been studied30 and interpreted in terms of planar B3S3rings, SB(pS),BS rings, and ring-bridging S groups. BC13 has been used to demonstrate the superior i.r. spectra that can be obtained from samples dissolved in liquid xenon, krypton, argon, or methane.31Ammonia adducts of the boron trihalides isolated in argon matrices have been studied using i.r. for the trichloride and tribromide the initial complexes are unstable to elimination of HX at higher temperatures. Aluminium.-THF adducts of calcium bis(tetrahydroa1uminate) have been prepared and characterized by i.r. spectros~opy.~~ The structures of complexes AlH3 with Cp,YX (Cp = cyclopentadienyl, X = Cl or H) have been using i.r. spectra of normal and deuterium-substitutedmaterials. 1.r. spectra show that co-condensation of methane with A1 atoms leads to reaction even at 10 K, whereas many other metal atoms fail to The new compound RzAIPPha (R = Me,SiCH,-) exists as a dimer-monomer equilibrium mixture in benzene solution;36its i.r. spectrum is described. 1.r. and Raman spectra of (Me,M),(NMeCS), (M = Al, Ga, or In) (1) have been analy~ed;~’ two isomeric forms are suggested. Some i.r. bands of RBui3Al,0 (R = H or Bu’) are reported,38 750-800 including v(A1-H) 1 6 0 0 - 1 9 0 0 cm-l (very broad) and v(A1-0-Al) cm-l (very strong, broad). Raman and i.r. spectra have been used to characterize iodine-doped phthalocyanines of Al, Ga, and Cr, (MPCFI,),.~~ 1.r. and Raman spectra of [MeN(SiMe,NMe),AlCl], are consistent with the centrosymmetric structure found in the A review of i.r. and Raman spectral data on @-aluminaand the gallium analogue has appeared.41Components of hydrolysed dilute aqueous solutions of aluminium salts have been characterized using i.r. spectra, showing the presence of polynuclear hydroxyaluminium species4, 1.r. spectra of aluminium hydroxy2s

A. Terauda, I. Vitola, I. Lange, and E. Svarc, Latv. PSR Zinat. Akad. Vestis, Kim. Ser.,

1983, 142. A. E. Geissberger and F. L. Galeener, Struct. Non-cryst. Muter., Proc. Int. Con$, 2nd. 1982, 1983, 381. 31 R. Holland, W. B. Maier, jun., S. M. Freund, and W. H. Beattie, J . Chern. Phys., 1983,78. 640,5. 32 R. L. Hunt and B. S. Ault, Spectrosc.: Int. J., 1982, 1, 31. 33 B. M. Bulychev, V. K. Bel’skii, A. V. Golubeva, P. A. Storozhenko, and V. B. Polyakova. Zh. Neorg. Khim., 1983, 28, 1131. 34 A. B. Erofeev, G. L. Soloveichik, B. M. Bulychev, and V. B. Polyakova, Koord. Khim.. 1983, 9, 190. 35 K. J. Klabunde and Y.Tanaka, J . Am. Chem. SOC.,1983, 105, 3544. 36 0. T. Beachley, jun. and C. Tessier-Youngs, Organometullics, 1983, 2, 796. 37 T. Halder, W. Schwarz, J. Weidlein, and P. Fischer, J. Organomet. Chem. 1983, 246, 29. 38 M. Bolestawski and J. Serwatowski, J . Organomet. Chem., 1983, 254, 159. 39 K. J. Wynne and R. S. Nohr, Mol. Cryst. Liq. Cryst., 1982, 81, 243. 40 U. Wannagat, T. Blumenthal, D. Brauer, and H. Burger, J . Organomet. Chem.. 1983.249. 33. 41 G. Lucazeau, Solid State Ionics, 1983, 8, 1. 42 S. S. Singh, Can. J. Soil Sci., 1982, 62, 559. 30

Characteristic Vibrations of Compounds of Main-group Elements

187

chloride suggest a spherical [Al1304(0H)24(H20)12]7+ cation, in which the central aluminium is tetrahedrally co-ordinated and the twelve equivalent peripheral aluminium atoms are octahedrally ~ o - o r d i n a t e d .Aluminium ~~~~~ atoms react with molecular oxygen or ozone in argon or N2 matrices giving initially asymmetric A100 in nitrogen but mainly ozonides in argon;46superoxide species such as those found for Ga, In, and TI were not observed. Aluminium is co-ordinated only by oxygen in thiocarboxylate complexes (R10)3-nAl(O,CRBSH), (R1 = Et, Pr'. or But; R2 = CH, or CHBCH2).u

1.r. spectra indicate the presence of the [A1F,I3- ion in K2HAIF6 formed in the reaction of KF with Al(OH), in 40% HF.47Reaction of chlorine with mixtures of AICI, or GaCl, with AsCI, gives only [AsC14]+[MC14]-(M = A1 or Ga) ;48 thermal decomposition gives the starting materials. A vibrational analysis based on experimental frequencies and ab initio calculations for ammonia complexes NH3.AlX3(X = F, C1, or Br) suggests that the trifluoride complex is thermodynamically unstable at high temperatures, which may explain why it has not been reported.4B Gallium and Indium.-Raman spectra of M, (M = Ga, In, or TI) matrix-isolated in argon show resonance-enhanced progressions,6O so that the equilibrium bondstretchingfrequenciescan be deduced ;they are 180,118, and 80 m-l,respectively. The i.r. spectrum of K[HGa(CH,SiMe,),] and the Ga-d, isotopomer have been reported;61the v(GaH) band is not identified, but v(GaD) at 1075 cm-l implies an unusually low GaH near 1510 cm-l. The i.r. and Raman spectra of [Me,As]+ salts of the deuteromethylhaloanions [(CDa),MCI,-,]- have been reported62 and combined with data for the light species to define simple valence force fields. The changes in M - C l and M-C force constants as n changes are rationalized in terms of a combination of inductive and resonance effects. 1.r. spectra are used to characterize hydrazidocarbonates MLa (M = In or Ga, L = NoH8D. L. Teagarden, J. F. Kozlowski, J. L. White, J. F. Radavich, and S. L. Hem, Truv. Com. Znt. Etude Bauxites, Alumine Alum., 1982, 17, 267. 44 S. Schonherr and R. Bertram, Z . Chem., 1983,23, 105. 46 S. M. Sonchik, L. Andrews, and K. D. Carlson, J. Phys. Chem., 1983,87, 2004. R. Ahmad, G. Srivastava, and R. C. Mehrotra, Zndiun J. Chem., Sect. A, 1983, 22, 32. 47 L. Kolditz, U. Bentrup, and I. Titt, Z . Chem., 1983, 23, 231. 48 B. Demircan and W. Brockner, 2.Natwforsch., Ted A, 1983, 38, 811. 40 G. N. Papatheodoru, L. A. Curtiss, and V. A. Maroni, J. Chem. Phys., 1983, 78, 3303. F. W. Froben, W. Schulze, and U. Kloss, Chem. Phys. Lett., 1983,99, 500. R. B. Hallock, B. T. Beachley, Y.-J. Li, W. M. Sanders, M. R. Churchill, W. E. Hunter, and J. L. Atwood, Inorg. Chem., 1983, 22, 3683. 6s A. Haaland and J. Weidlein, Acta Chem. Scand., Ser. A, 1982, 36, 805. 4a

188

Spectroscopic Properties of Inorganic and Organornetallic Compounds

C03-).53 1.r. and Raman bands of alkali-metal gallates and indates MIMaO, (M1 = Li, Na, K, Rb, or Cs, M2 = Ga; M' = Li or Na, M = In) have been listed.54New calcium gallates of La and Nd are shown to have a structure based on the [Ga0,l5- t e t r a h e d r ~ n The . ~ ~ i.r. and Raman spectra of a-GaTe have been used to establish the space group as Czh3.56 The Raman spectrum of Cu(GaCl,), shows it to have isolated molecules in the crystal with Cu-Cl-Ga bridges,57as shown earlier in the vapour. Complexes (1 : 1 and 1 : 2) of 0-nitroaniline with GaCl, are said to have some double-bond character in the 0-Ga bond, on the basis of i.r. and U.V. Raman spectra have been used to identify phases in the In-C1 system: between the compositions InCl and InCl, only In,Cl,, In,Cl,, and In5Cl, were detected.59 Low-frequency Raman spectra of K,InX,. HzO (X = C1 or Br) show distinct differences, attributed to the formation of hydrogen bonds in the bromo complex.GoIndium is penta-co-ordinate in InCl,(HMPA), (HMPA = hexamethylphosphoramide); the i.r. and Raman spectra are reported and discussed.B1The i.r. spectra of complexes of InCl, and TnBr, with a variety of Nand P-donor ligands have been reported.62 Thallium.-1.r. and Raman spectra of Tl,C03 at high pressure have been studied; the results confirm the existence of two phase changes up to 40 kbar and show that the high-pressure phase is orthorh~mbic.~~ 1.r. spectra have been used to characterize rare-earth thallium(1) carbonates MT1(CO3), prepared under pre~sure.6~ Several studies of T1' carboxylates use i.r. and Raman spectra to show that the carboxylate groups are essentially ionic.65J'e~s7 Complexes of T1' with a variety of organic acids and their insertion products with CS, have been reported together with their i.r. spectra.s8 A range of organo-T1"' dithiocarbamates has been shownG0 to contain bidentate dtc groups by i.r. spectroscopy. Raman bands of MTlBr, (M = K, Rb, 53

54

55

J. Macek, A. Rahten, and J. Slivnik, Vestn. Slov. Kem. Drus., 1982, 29, 249. A. A. Zakharov and I. S. Shaplygin, Russ. J . Inorg. Chem., 1983, 28, 59. A. A. Ismatov, Sh. Yu. Azimov, and T. A. Ismatov, Izv. Akad. Nauk SSSR, Neorg. Muter., 1982, 18, 1863.

S. S. Babaev, V. G. Nekrashevich, E. Yu. Salaev, and M. M. Tagiev, Tr. Vses. Konf. Fiz. Poluprovodn., 1982, 1, 100. 57 C. Verries-Peylhard, C.R. Seances Acad. Sci., Ser. 2, 1982, 295, 171. 58 B. A. Suvorov, Zh. Obshch. Khim., 1983, 53, 1205. G. Meyer and R. Blachnik, Z.Anorg. Allg. Chem., 1983, 503, 126. 6o A. Lorriaux-Rubbens, S. Turrell, F. Wallart, and J. P. Wignacourt, Raman Spectrosc. Proc. Znf. Conf. 8th, 1982, 477. S . P. Sinha, T. T. Pakkanen, T. A. Pakkanen, and L. Niinisto, Polyhedron, 1982,1,355.54. 62 M. A. Wassef and M. Gaber, Egypt J. Chem., 1981, 24, 165. D. M. Adams, P. D. Hatton, and I. D. Taylor, J . Raman Spectrosc., 1983, 14, 144. 64 H. Schweer and H. Seidel, 2. Anorg. Allg. Chem., 1983, 498, 205. 65 Yu. Ya. Kharitonov, I. I. Oleinik, N. A. Knyazeva, and I. S. Kolomnikov, Koord. Khim., *s6

1982, 8, 1285. 66 13'

68 69

Yu. Ya. Kharitonov, I. I. Oleinik, and N . A. Knyazeva, Zh. Neorg. Khim., 1983,28:2228. T. V. Lysyak, S. L. Rusakov, I. S. Kolomnikov, and Yu. Ya. Kharitonov, Zh. Neorg. Khim., 1983, 28, 1339. H. B. Singh and R. K. Negi, Indian J. Chem., Sect. A , 1982, 21, 1107. B. Khera, A. K. Sharma, and N. K. Kaushik, Synth. React. Inorg. Met.-Org. Chem.. 1982, 12, 583.


189

Cs, or N H 3 have been reported;70the TlBr stretches are distinct (around 200 cm-l), but only one band assigned to bending modes is observed, near 70 cm-l. Complexes of Tl"' halides with Ph2PCH2CH2PPh;l and of simple halides and monophenyldihalides of Tl'I' with HMPA72and 2,2'-bipyridyl have been studied by i.r.71or i.r. and Raman s p e ~ t r o s c o p y . ~ ~ - ~ ~ 4 Group IV

Carbm-The 3017 cm-l peak in type4 diamond is shown to be associated with a vinylidene ( )C=CH2) group, while other peaks between 2750 and 3400 cm-l are more probably due to NH The i.r. bands due to monomer and to C 0 2 dimers in D2,76and to CO, dimer CO in argon and oxygen rnatrice~,~~ monomer in argon matrices77have been studied in detail. The reaction of matrixisolated CO, with Li atoms is to give a range of products including Li+[C02]- and Li+[C204]-; the former exhibits two different i.r. spectra, indicating two structures interconverting under the influence of i.r. irradiation. CO has been identified in the atmosphere of Titan by i.r. spectroscopy ( 3 4 band); its abundance is about 60 parts per million of The Raman spectra of CS2as liquid and solid have been studied over a range of pressures at room temperature;80the spectra suggest that the high-pressure solid is similar to the low-temperature, 1 atmosphere crystal. Raman and i.r. spectra of solid CSe, have been reporteds1 at temperatures between 20 and 200 K: the spectra are consistent with a structure similar to that of solid CS,. Silicon.-The i.r. spectra of Si,C and its 13C isotope matrix-isolated in argon have been studied;82the SiCSi chain is bent, with a minimum bond angle of 110 '. The i.r. spectra of R,Si=CD, (R = CH, or CD,) have been reporteds3 and combined with data for R2Si=CH2 and for Me,SiX, (X = H or C1) to allow calculation of frequencies for H2C=SiX2, which were compared with observed values.84 The Si-0 stretching frequency in Me,Si=O (in argon matrix) is reported at 1204 cm-l; the silicone monomer was formed by oxygen-atom H. W. Rotter and G. Thiele, Z . Anorg. Allg. Chem., 1983, 499, 175. M. V. Castano, M. R. Bermejo, M. Gayoso, and J. Sordo, An. Quim., Ser. B, 1982,78,384. 72 S. Blanco, J. S. Casas, A. Sanchez, J. Sordo, J. M. Fernandez Solis, and M. Gayoso, J . Chem. Res. ( S ) , 1982, 328. 73 S. Blanco, J. S. Casas, A. Sanchez, M. V. Castano, J. Sordo, and M. Gayoso, An. Quim., Ser. B, 1982, 78, 377. 74 G. S. Woods and A. T. Collins, J . Phys. Chem. Solids, 1983, 44, 471. 76 M. Diem, T. L. Tso, and E. K. C. Lee, Chem. Phys., 1982,73, 283. 78 M. J. Irvine, A. David, and E. Pullin, Aust. J. Chem., 1982,35, 1961. 'I7 M. J. Irvine, J. G. Mathieson, A. David, and E. Pullin, Aust. J . Chem., 1982, 35, 1971. 78 Z. H. Kafafi, R. H. Hauge, W. E. Billups, and J. L. Margrave, J. Am. Chem. SOC.,1983, 70

71

105, 3886. 7*

so

B. L. Lutz, C. De Bergh, and T. Owen, Science, 1983, 220, 1374. H. Shimizu and T. Ohnishi, Chem. Phys. Left., 1983, 99, 507. B. H. Torrie, B. Andrews, A. Anderson, and B. M. Powell, J . Raman Spectrosc., 1983, 14, 96.

2. H. Kafafi, R. H. Hauge, L. Fredin, and J. L. Margrave, J . Phys. Chem., 1983, 87, 797. R3 V. N. Khabashesku, E. G. Baskir, A. K. Mal'tsev, and 0. M. Nefedov, Zzv. Akad. Nauk 82

R4

SSSR, Ser. Khim., 1983, 238. E. G. Baskir. A. K . Mal'tsev, and 0. M. Nefedov, Izv. Akad. Nauk SSSR,Ser. Khim.. 1983, 1314.

190


transfer from N,O to Me,Si: or to MeSiH=CH, at 35 K.85The i.r. bands due to G(SiHa)modes of (H,SiO), (n = 4, 5 , or 6) are strong and sharp and allow the oligomers to be distinguishedss ( n = 4, 938 cm-l; n = 5 , 925 cm-l; n = 6, 915 cm-l). The large-amplitude anharmonic bending motion of disiloxane has been studied using a new vibration-torsion-rotation Hamiltonian the Raman spectrum reported earlier is reinterpreted. High-resolution i.r. studies are reported of the SiBr stretching fundamental of SiH,Br and its hot-bandss8 and of the SiH, deformation region of SiH3La9 Vibrational spectra of MeSiH,D and MeSiHD, have been reportedg0and the assignments discussed. The vibrational spectra of MeSiCl, and MeGeCI, are of the vibrational spectra of the dimethylhalosilanes also r e p ~ r t e d A . ~ study ~ Me,SiHX (X = F, C1, Br, or I) leads to a suggested reassignment of some fundamental^.^^ Vibrational spectra are used to study rotational isomers of Me,SiHCH,X (X = Me or halide), which have two forms of symmetries C, and C1 depending on the conditions.e 3 Vibrational spectra of Me,Si( pCH,),SiMe, suggest that it has a planar ring.e4The i.r. spectrum of SiH,C=CMe has been studied at high resolution; some of the perpendicular bands show fine structure consistent with free internal rotation of the two end groups, while in other bands more complex structure suggests that some barrier to the torsional motion is involved. The simple structures are analysedg5in terms of theories of Bunker and Hougen. The i.r. spectra of twelve ethynyl silanes are saidesto show evidence of the transmission of electronic effects through Si by a x-mechanism. The C=C bond-stretching bands of some 1,2-diethynyIdisilanes R=CSiMe,SiMe,C=CR [R = SiMe,, R2 = SiMe,, SiMe,SiMe,, or (SiMe,),, all cyclic] have been reported;e7they show an effect of ring size. 1.r. and Raman spectra of Me,SiHSiHMe, and the Si,Si-d, isotopomer have been reported in detail ;e8 there is some evidence that rotational isomers can be identified. 1.r. and Raman spectra of some new disilanes in the series Si2Phs-xCl,, Si,Phs-xHx, and SiBCl,-,H, have been reported.ee1.r. bands associated with hydrogen chemisorbed

C. A. Arrington, R. West, and J. Michl, J. Am. Chem. Soc., 1983, 105, 6176. D. Seyferth, C. Prud’homme, and G. H. Wisemnn, Inorg. Chem., 1983. 22, 2163. 87 J. Koput and A. Wierzbicki, J. Mol. Spectrosc., 1983, 99, 116. 8a H. Burger and G . Schippel, J . Mol. Spectrosc., 1983, 98, 199. F. Lattanzi, C. Di Lauro, H. Burger, and P. Schulz, Mol. Phys., 1983,48, 1209. S. V. Sin’ko, G. M. Kuramshina, A. I. L’vov, Yu. A. Pentin, and G . S. Gol’din, Vesfn. Mosk. Univ., Ser. 2: Khim., 1983, 24, 360. g1 M. S. Soliman, M. A. Khattab, and A. G. El-Kourashy, Spectrochim. Acfa, Part A, 86

88

1983, 39, 621. A. J. F. Clark, J. E. Drake, R. T. Hemmings, and Quang Shen, Spectrochim. Acfu, Part A , 1983, 39, 127. OS K. Ohno, K. Suehiro, and H. Murata, J. Mol. Struct., 1983, 98, 251. e4 V. F. Kalasinsky and S. Pechsiri, J . Phys. Chem., 1982, 86, 5110. 96 S. Cradock and J. Koprowski, J. Mol. Spectrosc., 1983,99, 167. 98 Yu. V. Kolodyazhnyi, N. I. Sizova, I. G. Lorents, L. I. Kuznetsova, A. P. Sadimenko, L. I. Ol’khovskaya, and N. V. Komarov, Zh. Obshch. Khim., 1982, 52, 1855. O7 H. Sakurai, Y. Nakadaira, A. Hosomi, Y. Eriyama, and C. Kabuto, J . Am. Chem. Soc.. 1983,105, 3359. 98 K. Ohno, M. Hayashi, and A. Murata, Spectrochim. Acta, 1983, 39, 373. O9 H. Soellradl and E. Hengge, J . Organomet. Chem., 1983,243,257. 92


191

on Si(lOO),looRaman spectra of SiO, films on Si,loland i.r. bands associated with hydrogen, oxygen, halogens, boron, and phosphorus in amorphous siliconlo2-Io5 have been reported. Two groups report vibrational spectra of ranges of ~ i l a t r a n e s ; ~the ~J~~ assignment of the Si- - . N stretching mode is discussed.lo7The influence of the ligands R and Ar (aromatic) on the NH stretching frequency in R,SiNHAr and on the hydrogen-bonding shift for complex-formation with THF has been studied.lo81.r. spectra are used to help elucidate the structures of the products of the thermal condensation reaction of (Me,SiNH),Si, which are based on four-membered Si2N, rings.lo@ 1.r. bands have been reported for some Group I V phthalocyanines PcMX, [M = Si, Ge, or Sn, X2 = Cl,, (OH),, or -O-].ll* 1.r. and Raman bands of P(SiMe,SiMe,),P have been reported with some suggested assignments.111 The symmetric ring-stretching mode gives a very strong Raman band at 320 cm-l, while the Sip mode of a," symmetry (in assumed Dghsymmetry) gives a very strong i.r. band at 409 cm-l. The Raman spectrum of vitreous 30Si0, has been studied112and used to establish a vibrational assignment, which suggests..that recent assignments of the low-frequency 'defect' lines to highly ordered planar rings are correct. Raman spectra of vitreous CaMgSiO, were compared with those of natural and synthetic crystalline silicates, and assignments were suggested.113 Monothiocarbamate derivatives of Si'", GelV,and Sn" have been studied by i.r. s p e c t r o ~ ~ o p yand , ~ ~their * stereochemistry was discussed. The i.r. spectrum of (Pr'S)3SiC104shows bands of ionic perchlorate,l15suggesting the presence of a cationic silicon group. High overtones of the Si-H stretching modes of SiHCl, and SiH2C12have been reported116and interpreted in terms of the local-mode theory. The product of photoreaction of SiHC13and O2in SiC14solution is identified117as C1,SiOH by i.r. spectroscopy; the hydroperoxide is not detected. Hyper-Raman spectra of loo

Y.J. Chabal, E. E. Chaban, and S. B. Christman, J. Electron Spectrosc. Relut. Phenom.,

lol

H. J. Fitting, J. Gabrusenok, and A. Lusis, Wiss. Z . , Wilhelm-Pieck-Univ. Rostok. Notrrr-

1983, 29, 35.

wiss. Reihe, 1982, 31, 1. G. Lucovsky and W. B. Pollard,J . Vuc. Sci. Technol., 1983,1,313. lo3E. Martinez and M. Cardona, Phys. Rev. B: Condens. Mutter, 1983, 28, 880. lo4J. Chevallier, S. Kalem, J. Bourneix, and M. Vandevyver, Physicu B C (Amsterdam), 1983,117-118, 874. lo6S. C. Shen and Q. L. Jue, Physicu B C (Amsterdam), 1983, 117-118, 868. P. Hencsei, L. Bihatai, L. Kovacs, E. Szalay, E. B. Karsai, A. Szollosy, and M. Gal, Acra Chim. Hung., 1983, 112, 261. lo' M. Imbenotte, G. Palavit, and P. Legrand, J . Raman Spectrosc., 1983, 14, 135. J. Pikies and W. Wojnowski, 2. Anorg. Allg. Chem., 1983, 503, 224. M. M. Win, H. S. Moskovkin, V. N. Talanov, I. V. Miroshnichenko, V. N. Bochkatev, and A. E. Chernyshev, Zh. Obshch. Khim., 1983. 53, 110. 110 C. W. Dirk, T. Inabe, K. F. Schoch, and T. J. Marks, J. Am. Chem. SOC.,1983,105, 1539. ll1 K. Hassler, J. Orgunomet. Chem., 1983, 246, C111. 118 F. L. Galeener and A. E. Geissberger, Phys. Rev. B, 1983, 27, 6199. 11* B. Piriou and P. McMillan, Am. Mineral., 1983, 68, 426. 114 V. D. Gupta and V. K. Gupta, Indian J. Chem., Sect. A , 1983,22,250. 116 J. B. Lambert and W. J. Schulz, J. Am. Chem. Soc., 1983,105, 1671. 116 R. A. Bernheim, F. W. Lampe, J. F. O'Keefe, and J. R. Qualey, Chem. Phys. Lett., 1983, loo, 45. 11' R. Gooden, Inorg. Chem., 1983,22, 2212. lo8

+

+

192


SiC1, and other Group IV halides have been reportedl1*and compared with the normal Raman spectra. 1 : 1 molecular complexes of SiF, with H20, MeOH, and Me,O have been identified by i.r. spectroscopy in argon matrices;llg an intense Si-F stretching band below lo00 cm-* was shown to vary in frequency according to the basicity of the Lewis base. Germanium.-1.r. spectra of MeCOSGeH (germylmonothioacetate) are consistent with a structure with Ge bound exclusively to S,120 as found by electron diffraction. High-resolution i.r. spectra of the germyl rocking band of germyl iodide GeH31 and its overtone121and the GeX stretching bands of the germyl halides GeH,X (X = CI, Br, or I)122have been reported; monoisotopic 74Gewas used in these studies to reduce the complexity of the spectra arising from natural Ge with its five isotopes. 1.r. and Raman bands are listed for cyclo(Bu 'P),GeEt, without assignment.12 Vitreous GeO, has been studied by Raman spectroscopy; 0 and Ge isotopic samples were used and an assignment was suggested.12* The i.r. spectra of Ge(OH)(ZO,) (Z = P or As) that the compounds are isostructural. 1.r. and Raman spectra of vitreous and crystalline GeS, have been reported and discussed in terms of the presence of GeS, tetrahedra in both vitreous and hightemperature crystal samples.12, An analysis of the spectra of GeS, and GeSe, crystalline solids based on GeY, tetrahedra linked in various ways has been proposed. 127 The i.r. and Raman spectra of single-crystal PbGeS, have been studied12*and analysed using a factor-group treatment. Raman bands of Na,Ge,Se,- 16H20are reported;129the anion is similar in structure to Al,CI,. A characteristic i.r. band at 743 cm-l is proposed as identification for (GeCI,),O, formed by oxidation of GeCl, near loo0 OC.130 Tin.-1.r. spectra of R,Sn: monomers (R = CH, or CD3) matrix-isolated in argon have been reported and assigned.131The i.r. spectrum of CI,SnCH,CH,11*

T. J. Dines, M. J. French, R. J. B. Hall, and D. A. Long, J . Raman Spectrosc., 1983, 14.

225. B. S. Ault, J . Am. Chem. SOC., 1983, 105, 5742. E. A. V. Ebsworth, C. M. Huntley, and D. W. H. Rankin, J. Chem. SOC.,Dalton Trans., 1983, 835. I 2 l H . Burger, R. Eujen, A. Rahner, P. Schulz, J. E. Drake, and S. Cradock, 2. Nuturforsch.. Teil A, 1983, 38, 740. 123 H. Burger, K. Burczyk, R. Eujen, A. Rahner, and S. Cradock, J. MoI. Spectrosc., 1983, 97, 266. lZ3 M. Baudler and H. Suchomel, Z . Anorg. Allg. Chem., 1983, 503, 7. 124 F. L. Galeener, A. E. Geissberger, G . W. Ogar, and R. A. Loehman, Phys. Rev. B, 1983, 28, 4768. N. G. Chernorukov, I. A. Kershunov, and G . F. Sibrina, Russ. J. Inorg. Chem., 1983, 28, 816. Y. Kawamoto and C. Kawashima, Muter. Res. Bull. 1982, 17, I51 1. 12' 2. V. Popovic, Fizika (Zagreb), 1983, 15, 11. 12* Z. V. Popovic, Physica B C, 1983, 119, 283. 129 B. Krebs and H. Muller, Z . Anorg. Allg. Chern., 1983, 496, 47. lR0 P. Kleinert, D. Schmidt, and H. J. Laukner, 2. Anorg. Allg. Chem., 1982, 495, 157. I 3 l P. Bleckmann, H. Maly, R. Minkwitz, W. P. Neumann, and B. Watta, Tetrahedron Lerr., 1982, 23, 46. ll@ I2O

+


193

CH,CI has been and reported. Deuterium-substituted samples of Me,SnC=CH have been used in an i.r. and Raman study of the normal modes.133 Full vibrational spectra (except for the torsions) are reported for ethyl stannane and EtSnD, and assigned with the aid of a normal-co-ordinate ana1~sis.l~~ SnC stretching modes are assigned135in the range 531-535 cm-l for Me,SnR (2)-(5). Hydrated SnO, has been studied by Raman and i.r. s p e ~ t r o s c o p y a; ~ ~ ~ structure containing octahedrally co-ordinated tin is proposed. 1.r. spectra of gaseous SnO at diode-laser resolution allow the vibration frequency for lZ0Snl60 to be specified as 814.702 49 k 0.0oO 27 cm-l.lZ7 The antisymmetric SnOSii stretching mode of (R,SnO), (R = 2,6-diethylphenyl)is assigned at 710 cm-1.138

The vibrational spectra of Mg,Sn04 and Zn,SnO, have been assigned with the aid of Mg and Zn isotopic data;13gthe number of bands observed is too great for the highest possible space group (Oh7),and a lower symmetry structure is inferred. 1.r. and Raman spectra of (MeSn),S, are consistent with an adamantane skelewith a Sn-S bond-stretching force constant of 168 N m-l. Monothiophosphate esters of SnIV are reported,141 with i.r. and Raman spectra, and bidentate xanthate ligands are proposed for Ar,Sn(S,COR), (Ar = p-biphenyl, R = Me, Et, Pr, or Bu)14, on the basis of i.r. evidence. Raman spectra of single crystals of SnI, have been reported and d i s c u ~ s e d . l ~ ~ 3 ~ ~ Raman spectra have been used to study hexahalotin(1v) complexes in glassy aqueous acids;145the ions [SnF4X,I2-(X = CI or Br) are both trans. The vibrational spectra of a number of complexes of tin compounds with organic ligands are collected in the Table. V. I. Shirayev, T. G. Basanina, S. N. Gurkova, A. I. Gusev, G. V. Dolgushin, V. P. Feshin, V. P. Anosov, G. M. Apal'kova, and V. S. Nikitin, Koord. Khim., 1983, 9, 780. 133 A. V. Belyakov, E. T. Bogoradovskii, V. S. Zavgorodnii, G. M. Apal'kova, V. S. Nikitin, and L. S. Khaikin, J . Mol. Struct., 1983, 98, 27. 134 J. R. Durig, Y. S. Li, J. F. Sullivan, J. S. Church, and C. B. Bradley, J. Chem. Phvs., 1983, 78, 1046. 135 P. Jutzi and U. Gilge, J . Organomet. Chem., 1983, 246, 163. 136 L. M. Sharygin, S. M. Vouk, V. F. Gonchar, V. L. Barybin, and T. N. Perekhozheva. Zh. Neorg. Khim., 1983, 28, 576. 13' A. G. Maki and F. J. Lovas, J. Mol. Spectrosc., 1983, 98, 146. 13* S. Masamune, L. R. Sita, and D. J. Williams, J. Am. Chem. SOC.,1983, 105, 630. 130 N. V. Porotnikov, V. G. Savenko, and 0. V. Sidorova, Russ. J. Znorg. Chem., 1983,28,932. 140 A. Blecher, B. Matthiasch, and M. Drager, Z . Anorg. Allg. Chem., 1982, 488, 177. 141 F. A. K.Nasser and J. J. Zuckerman, J . Organomet. Chem., 1983,244, 17. 14* A. K. Garg, C. P. Sharma, and B. S. Garg, Indian J . Chem., Sect. A , 1982, 21, 1OOO. 143 A. V. Bobyr, R. V. Friezel, I. S. Gorban, V. A. Gubanov, G. I. Salievon, and T. N. Sushkevich, Solid State Commun., 1983, 47, 361. A. V. Bobyr, I. S. Gorban, V. A. Gubanov, G. L. Salievon. T. N. Sushkevich. and V. V . Friezel, Ukr. Fiz. Zh. (Russ. Ed.), 1983, 28, 1327. 145 M. Katada, H. Kanno, and H. Sano, Polyhedron, 1983, 2, 104. 132

194


Table Sn compound Ph,SnN, RL3SnOCONR2COMe (Me,X,-,Sn)2CHCH2CH,R [Sn]2+[SnC1,]2[R2SnI2+ R3SnX, RhSnX, Bu2SnC1, R,Sn R,Sn [Bu2SnI2+ SnCI, SnX,

Ligand(s)

Ref.

N, 0, S donors Internal COMe Internal R ( e . g . COOH, OCOMe, etc.) Schiff base [ MeCOCHCOCHCOMeI2Crown ethers Quinazoline A r c ( O+NN=CHFc N,N-Disubst. hydroxylamines [ArCR =N-N=C(SMe)SI2(Ar o-hydroxyphenyl) Esters

146 147 148 1 49 150 151 152 153 154 155

+

2-Amino-l,3,4-thiadiazoles

156 157

Lead.-A normal-co-ordinate analysis of a- and 9-PbO based on Raman and i.r. spectra allows an assignment to be proposed for both forms;15*the attractive force between layers, attributed to the Pb lone-pair electrons, is very much weaker than the within-layer forces, as expected. The i.r. and Raman spectra of some basic lead(@ carbonates are reported and interpreted in terms of oxygenbridged lead s u b l a t t i ~ e s Complexes .~~~ of PbC14 are prepared by reaction of chlorine with PbClz suspended in donor solvents HMPA, dimethylformamide, or formamide;ls0a 1 : 2 complex is formed in each case, the i.r. spectra suggesting octahedral co-ordination of lead(1v) with trans geometry. Complexes of Ph,PbSeCN with O-donor ligands may be Pb-Se bonded (py0, pic0) or Pb-N bonded (HMPA), but all N-donor ligands investigated gave Pb-Sebonded complexes.161This contrasts with the behaviour of Ph,PbNCS with 0and N-donor ligands, which give Pb-N-bonded NCS or ionic [NCSI- in the complexes.

146 147

T. N. Srivastava and P. C. Kamboj, J. Indian Chem. SOC.,1983, 60,396. G. Roge, F. Huber, H. Preut, A. Silvestri, and R. Barbieri, J . Chem. Soc., Dalton Trans.. 1983, 595.

H. G. Kuivila, T. J. Karol, and K. Swami, Organometalfics, 1983, 2, 909. 148 F. A. Bottino, P. Finocchiaro, E. Libertini, and A. Recca, J. Coord. Chem., 1983, 12, 303. 150 B. P. Bachlas, A. Kumar, H. Sharma, and J. C. Maire, Buff. SOC.Chim.. Fr., 1983, 2, 46. 151 P. J. Smith and P. N. Patel, J . Organornet. Chem., 1983, 243, C73. lj2 C. Pelizzi, G. Pelizzi. and P. Tarasconi, Polyhedron, 1983, 2, 145. lj3 S. R. Patil, U. N. Kantak, and D. N. Sen, Znorg. Chim. Acta, 1983, 68, 1. lZ4 M. K. Das, M. Nath, and J. J. Zuckerman, Znorg. Chim. Acta, 1983.71,49. 156 A. Saxena and J. P. Tandon, Pol.vhedron, 1983, 2, 443. Yu. A. Lysenko and E. A. Toshina, Zh. Obshch. Khim., 1983, 53, 895. 167 A. Benedetti, A. C. Fabretti, G. Peyronel, and A. F. Zanoli, Spectrochim. Acta, Part A, 1983, 39, 53. 15* J. P. Vigouroux, G. Calvarin, and E. Husson, J. Solid State Chem., 1982, 45, 343. lS8 M. H. Brooker. S. Sunder, P. Taylor, and V. J. Lopata, Can. J. Chem., 1983, 61, 494. 160 F. Carrera, E. Gayoso, M. R. B e k e j o , and M. Gayoso, Actu Cienr. Compostelana, 1981, 14*

161

18, 3. R. Wojtowski, I. Wharf, and M. Onyszchuk, Can. J. Chem., 1983, 61, 743.


195

5 Group V

Nitrogen.-Raman spectra of liquid ammonia (NH, and ND2H)are interpretedle2 in terms of hydrogen-bonded cyclic species, probably dimers; this accounts for the low viscosity and low boiling point. Interactions of ammonia are studied by i.r. spectroscopy in CO matrices at 10 K ; again dimers are suggested.lB3The i.r. spectra of cold deposits of ammonia with water, HCl, or HNO, have been reported,16, and i.r. spectra of RSN.HI complexes (R = H or Me) have been studied in argon, N,, O,, or ethene matrices.lBSSeveral species have been identified by i.r. spectroscopy in samples of NH, adsorbed on MO surfaces (M = Mg, Ca, or Sr).166Hydrogen bonding in ammonium salts and alkylammonium salts has been studied by i.r. s p e ~ t r o s c o p y . ~The ~ ~ Jspecies ~~ present in aqueous nitric acid have been studied by Raman methods,16ewhich indicated the presence of both covalent complexes HNOs-nH20(n = 0, 1, or 2) and ionic dissociation products such as [H30]+, [NO,]+, and [NO,(HNO,),]- and [NO,]-. The i.r. and Raman spectra of (MeSO,),N, and its perdeuterium-substituted analogue have been reported and assigned.170 Raman spectra of [NO]+ in (3-alumina have been studied in detail;171the vibrational spectra of crown-ether complexes of [NO]+ and [NO,]+ tetrafluoroborates have been and suggest that the crown ether (18-crown-6) has a very symmetrical Dsd structure in the complex. Raman spectroscopy has been used to determine the [NO,]+ concentration of HN0,-SO, and HN0,-H,S,O, mixtures.173Both symmetric (ONONO) and asymmetric ON-NO, isomers of and by both N203have been studied by i.r. spectroscopy in liquid xenon174$176 i.r. and Raman spectroscopy in NO Visible-laser irradiation causes conversion of either form to the other, depending on the frequency! Raman spectra of solid N,O, at high pressures show the existence of two new crystal forms;177one, like the normal-pressure crystal form, consists of planar covalent N-N-bonded molecules, while the other consists of ionic mO]+[NO,]-. High-resolution i.r. studies of cis- and trans-nitrous acid in the gas phase have been many of the fundamentals are resolved at 0.05 cm-l resolution. The vibrational spectra of solid trans-Na,N,O, and its aqueous solution are J. Fernandez Bertran, J . Mol. Struct., 1982, 95, 9. W. Hagen and A. G. G. M. Tielens, Spectrochim. Acta, Part A , 1982, 38, 1203. 184 T. Huston, I. C. Hisatsune, and J. Heicklen, Can. J. Chem., 1983, 61,2077. L. Schriver, A. Schriver, and J. P. Perchard, J . Am. Chem. Soc., 1983,105, 3843. l(M S. Coluccia, E. Garrone, and E. Borelli, J . Chem. Soc., Farahy Trans. I , 1983, 79, 607. lS7 M. Epple and W. Rudorf', 2. Anorg. Allg. Chem., 1982, 495, 200. 0. b o p , T. S. Cameron, M. A. James, and M. Falk, Can. J. Chem., 1983, 61, 1620. lee A. Potier, J. Potier, M. H. Herzog-Cance, and M. P. Thi, Raman Spectrosc., Proc. Int. Conf., 8th, 1982, 621. 170 F. Sucker, G. Bliefert, K. Brink, and R. Mattes, Z . Anorg. Allg. Chem.. 1983, 496, 75. C. Myers and R. Frech, Solid State Ionics, 1983, 8, 49. 172 R. Savoie, M. Pigeon-Gosselin, A. Rodrigue, and R. Chenevert, Can. J. Chem.. 1983. 61. lea

loa

1248.

Y. Jiang, X. Wang, X. Fu, and H. Liu, Fenxi Huaxue, 1983, 11,241. 17' R. F. Holland and W. B. Maier, J. Chem. Phys., 1983, 78, 2928. 176 R. F. Holland and W. B. Maier, J. Chem. Phys., 1983,78, 7521. I76 E. M. Now, L. H. Chen, and J. Laane, J . Phys. Chem., 1983,87, 1113. S. F. Agnew, B. 1. Swanson, L. H. Jones, R. L. Mills, and D. Schiferl. J . Phys. Cheni.. 1983, 87, 5065.

C. M. Deeley and I. M. Mills, J . Mol. Struct., 1983, 100, 199.

li4

196


reported,179with a new assignment. 1.r. and Raman spectra of some salts of the [NH,F]+ cation are reported,laOandmany i.r. absorption bands of NF, dissolved in liquid argon have been measured; frequencies, halfwidths, and intensities are listed.lsl A normal-co-ordinate analysis of CF2=NF has been based on i.r., Raman, and microwave spectra.la2 Assignments have been proposedls3 for the vibrational spectra of CF,0NF2 and CF2(0F)ONF2.Strong bands in the i.r. spectra of FS020CF2NFX (X = CI, Br, or OS02F) are assignedla4 to v,,(S02) (ca. 1500 cm-l), vs(S02) (1250-1272 cm-l), and v(CF,) (1100-1220 cm-l, 2 bands). A ‘convincing’ assignment is proffered for the bands observed in the Raman spectrum of single-crystal KN, due to the high-frequency stretch and the overtone of the bend,la5 and the variation of the main Fermi resonance with temperature has been studied for several isotopic species. The Raman spectra of [NCOI- in alkali halide solids have been studied and compared with the i.r. spectra.’ 86 Phosphorus.-The i.r. and Raman spectra of EtPH,BH, and its P- and Bdeuterium-substituted analogues have been studied in a range of phases;lS7 a normal-co-ordinate analysis is proposed for both trans and gauche conformers, the former being the more stable. The rocking modes of trimethylphosphine have been definitively assigned,ls8 following a detailed study of the spectra of do-, d3-, and d,-forms. The i.r. spectrum of fluxional Me(CF,),PH has been reported;la9 the compound is unstable above room temperature. 1.r. and Raman studies of EtPXF, (X = 0, S, or Se) have shownfQ0that the trans conformer is the only one present in the crystal, but both gauche and trans forms are found in gas, liquid, and solution phases. The i.r. and Raman spectra of MeP(S)F, in gas and solid phases have been reported,lgl and an assignment has been suggested. Assignments are proposed for i.r. and Raman spectra of MezHPS.lg2 Conformational isomers of allenyl phosphine oxides XYPOR (e.g. X = OMe, Y = C1, R = MeCH=C=CH-) have been found using i.r. spectra.lgS Experimental i.r. and Raman spectra of OP(NCS), have been L. H. Chen and J. Laane, J. Raman Spectrosc., 1983, 14, 284. R. Minkwitz and R. Nass, Z . Naturforsch., Teil B, 1982, 37, 1558. Is* 0. V. Bogdanova, T. D . Kolomiitsova. L. F. Strelkova, and D . N. Shchepkin, Opt. Spektrosk., 1983, 54, 650. D. Christen, H. Oberhammer, R. M. Hanmaker. S. C. Chang, and D . D. DesMarteau. J. Am. Chem. SOC.,1983, 105, 6186. l d 3 W. Maya, D. Pilipovich, M. G . Warner, R. D . Wilson, and K. 0. Christie, Inorg. Chem.. 1983, 22, 810. S.-C. Chang and D. D . DesMarteau, Inorg. Chem., 1983.22, 805. IRL M. Y. Khilji, W. F. Sherman, and G. R. Wilkinson, J . Raman Spectrosc., 1983, 14, 4.5. IR6M. R. Mohammad and W. F. Sherman, J . Raman Spectrosc., 1983, 14, 215. J. D. Odom, P. A. Brletic, S. A. Johnston, and J. R. Durig, J . Mol. Struct., 1983,96, 247. D. C. McKean and G . P. McQuillan, Spectrochim. Acta, Part A , 1983, 39, 293. l a S L. V. Griend and R. G . Cavell, Inorg. Chem., 1983, 22, 1817. 190 R. R. Shagidullin, S. A. Katsyuba, I. I . Vandyukova, and 1. A. Nuretdinov, Zh. Obshch. Khim., 1983, 53, 84. l s 1 J. R. Durig, J. A. Meadows, Y. S. Li, and A. E. Stanley, Znorg. Chem., 1983, 22, 4134. lQ2 M. A. Sarukhanov, I . A. Popova, and Yu. Ya. Kharitonov, Russ. J . Inorg. Chem., 1983. 28, 31. 193 R. Mathis, F. Mathis, N. Ayed, B. Baccar, and C. Charrier, Spectrochim. Acta, Part A. 1983, 39, 233. lXo


197

found to agree quite well with the predictions of a normal-co-ordinate analysis wing force constants transferred from other 1.r. bands are reportedlg5for CF,P=CF,, including v(P=C) at 740 cm-'. The i.r. spectrum of a Pv-tetraphenylporphin (TPP) complex [(TPP)PC12]+Cl- is reportedlgs as part of the characterization of the novel compound, which is very easily reduced. Li,Pls*8THF, prepared from white phosphorus and LiPH, in boiling THF, has been identified by Raman Raman and i.r. bands have been listed without assignment for Et,P,, which has two fused fivemembered rings.198The i.r. spectra of P,(MMe,), (M -= Si, Ge, Sn, or Pb) showlggvery little change in the P7cage modes as M changes. MP02, MP03, and MN03 (M = alkali metal) have been identified by i.r. i n inert matrices,200and the co-ordination of the cation to Z 0 3 or Z 0 2 anions has been discussed. Vibrations of the dihydrogen phosphates of potassium201and caesium202have been studied by i.r. or Raman spectroscopy and discussed in terms of the proton tunnelling motion. A number of new --OTeF, derivatives of P (and As and Sb) have been with i.r. and Raman spectra. 1.r. and (L = -OPF,) Raman spectra of PL3 and PL,(OMe)204and OPL3and OPFL2206 have been reported, with suggested assignments. 1.r. and Raman spectra of P2S10in a range of phases are reported, and a new assignment of the fundamentals is proposed.2M1.r. spectra have been used to identify thiophosphates formed by reaction of red or white phosphorus with alkali polysulphide solut i o n ~ The . ~ ~spectra ~ of MsPSl (M = Ag or Cu) are interpreted208in terms of tetrahedral PS4l3- ions in crystal sites of less than Td symmetry. A number of reports have appeared concerning the vibrational spectra of hexathiodiphosphates containing the P2SJ4- i ~ n . Skeletal ~ ~ ~ modes - ~ ~of ~RZ(SCH2CH2S) (R = C1, OMe, SMe, Ph, or NMe,, Z = P or As) have been assigned213and shown to be surprisingly insensitive to the nature of Z. Conformational isomers

*g4

V. D. Khavryuchenko, A. Sinkevich, and A . 1. Brusilovets, Ukr. Khim, Zh. (Russ. Ed.), 1983, 49, 914.

A. B. Burg, Inorg. Chem., 1983, 22, 2573. lg6 C. A. Marrese and C. J. Carrano, Znorg. Chem., 1983, 22, 1858. 19' M. Baudler and 0. Exner, Chem. Ber., 1983, 116, 1268. lea M. Baudler and Y. Aktalay, 2. Anorg. Allg. Chem., 1983, 496, 29. leg G. Fritz, K. D. Hoppe, W. Honle, D. Weber, C. Mujica, V. Manriquez, and H. G. von Schnering, J. Organornet. Chem., 1983, 249, 63. ,O0 L. Bencivenni and K. A. Gingerich, J . Mol. Struct., 1983, 98, 195. 201 J. J. Kim and B. K. Choi, Raman Spectrosc., Proc. Znt. Conf., 8th. 1982. 465. 2oa B. Marchon and A. Novak, J. Chem. Phys., 1983, 78,2105. 203 D. Lentz and K. Seppelt, 2. Anorg. Allg. Chem., 1983, 502, 83. 204 E. A. V. Ebsworth, G . M. Hunter, and D. W. H. Rankin, J . Chem. Sac., Dalton Trans., lgS

1983, 1983. 208

E. A. V. Ebsworth, G. M. Hunter, and D. W. H. Rankin, J . Chem. SOC.,Dalton Trans., 1983, 245.

M. Somer, W. Bues, and W. Brockner, Z . Nutwforsch., Teil A , 1983, 38, 163. 207 W. Krause and H. Falius, 2. Anorg. Allg. Chem., 1983, 496, 80. 208 U. Piitzmann and W. Brockner, Z . Natwforsch., Teil A , 1983, 38, 27. 20g W. Brockner and U. Piitzmann, 2. Nutwforsch., Teil A , 1983, 38, 92. R. Becker, W. Brockner, and C. Wibbelmann, 2. Naturforsch., Teil A , 1983, 38, 555. R. Becker, W. Brockner, and H. Schafer, 2. Natwforsch., Teil A , 1983, 38, 874. 212 C. Sourisseau, J. P. Forgerit, and Y. Matthey, J . Solid State Chem., 1983, 49, 134. 213 G. Davidson and K. P. Ewer, Spectrochim. Acta, Part A , 1983, 39,419.

198


of (MeS),P have been studied by i.r. spectroscopy in gas and The force field of SPCl, has been defined after a careful study of chlorine and sulphur isotope shifts using gaseous and matrix-isolated samples.215O=PCl has been observed in a matrix, using i.r., and a force field has been deduced from the frequencies and istotope shifts.21sRaman spectra of OPCl, in the solid state show doubling of the non-degenerate fundamentals, which suggests a cubic unit cell with four molecules in a centrosymmetric array.2171.r. spectra suggest218the existence of at least three different forms of Ph4PF, i.e. the covalent molecular monomer and two different ionic forms, Ph4P+F- and Ph4P+Ph4PF,-. Some generalized vibrational assignments are suggested2l9for new phosphoranes such as F,PNMeCH,Ph and (CF,),PRNHMe (R = F or Me). Arsenic.-The vibrational spectra of As,O, and the isostructural AsSbO, have been studied, using i.r. and Raman techniques over the range 30-1000 cm-1,220 and some band assignments have been suggested. Alkali-metal arsenites and antimonites 221 and arsenites and arsenates222have been studied by i.r. spectroscopy in inert matrices. The vibrational spectra of solid and molten As4S4and of solid As,Se4 have been and assigned ; cradle-shaped molecules of DPdsymmetry are indicated. A normal-co-ordinate analysis of the [Me,AsS,]-ion has been and it is suggested that the As-S force constant of 263 N m-l is consistent with some x-bonding. Skeletal modes are assigned225 for Me,AsL, Ph,AsL, and LH [L = Ph,P(=S)S-] and for Me,Sn[SAs(=S)R,] (R = Me or Ph); v(AsS) is assigned near 420 cm-l, v(P=S) near 640 cm-l, and v(As=S) near 480 cm-l. 1.r. spectra of some new dithiophosphate complexes of As and Sb, LnZC13-n [L = (R0)2PS2, Z = As or Sb, n = 1 or 2, R = Et, Pr, or Bu], have been reported226and suggest chelated structures. Vibrational spectra of complexes of ammonia and methyl- and dimethyl-amines with trihalides of As, Sb, and Bi are reported;227in 1 : 1 complexes the N ligand appears to be axial, with an equatorial lone pair. The gas-phase i.r. spectrum of AsCl, has been simulated in a study designed to establish the vibration frequencies, Coriolis coupling constants, and relative intensities of the fundamentals,22N leading to an improved force field. AsFCI, has been identified in a matrix among the products of vaporization of [ A S C ~ . , ] + [ A S F ~ ] - . ~ ~ ~ E. N. Ofitserov, A. A. Karelov, F. S. Bilalov, A. B. Remizov, and I. S. Paninov, Zh. Obshch. Chem., 1983, 53, 51 1. 215 R. R. Filgueira, L. L. Fournier, and A. Miiller, Can. J. Spectrosc., 1983, 28, 125. '16 M. Binnewies, M. Lakenbrink, and H. Schnockel, Z . Anorg. Allg. Chem., 1983, 497, 7. '17 S. R. Gupta and A. N. R. Warrier, Spectrochim. Acta, Part A , 1983, 39, 529. S. J. Brown and J. H. Clark, J . Chem. SOC.,Chem. Commun., 1983, 1256. 'lB R. G. Cavell, S. Pirakitigoon, and L. V. Griend, Inorg. Chem., 1983, 22, 1378. "O H. Ehrhardt and M. Jansen, 2. Anorg. Allg. Chem., 1983, 504, 128. "l L. Bencivenni and K. A. Gingerich, J . Mol. Strucr., 1983, 99, 23. 222 J. S. Ogden, T. J. Sibley, and S. J. Williams, J . Chem. Soc., Dalton Trans., 1983, 851. 223 W. Bues, M. Somer, and W. Brockner, 2. Anorg. Allg. Chem., 1983,499,7. p24 I. Silaghi-Dumittescu, L. Silaghi-Dumitrescu, and I. Haiduc, Rev. Roum. Chim., 1982, 27, '14

911. 226 226 227 229

L. Silaghi-Dumitrescu and I. Haiduc, J . Organomet. Chem., 1983, 252, 295. H. P. S. Chauhan, G. Srivastava, and R. C. Mehrotra, Polyhedron, 1983, 2, 359. A. K. Biswas, J. R. Hall, and D. P. Schweinsberg, Inorg. Chim. Acta, 1983, 75, 57. B. Lunelli, G. Cazzoli, and F. Lattanzi, J. Mol. Spectrosc., 1983, 100, 174. F. Claus and R. Minkwitz, Z . Anorg. Allg. Chem., 1983, 501, 19.


199

Antimony.--Tri(cyclohexyl)antimony(v) compounds R,SbX(OH) (X = CI, Br, OAc, or NO,) have been to be formed by hydrolysis of (R3SbX)z0, which was monitored by i.r. spectroscopy. 1.r. and Raman spectra are reported for (MezSb)zCH2and (MezSbXz)zCH,(X = C1 or Br).2311.r. and Raman spectra of ‘distibanes’ RzSbSbR2(R = Me, Ph, or SiMe,) are interpretedz32in terms of long chains of antimony atoms in an essentially linear conformation. The i.r. and Raman spectra of hydrothermally produced Sb,O, are in accord with the results of a factor-group analysisz33showing no signs of OH and H,O groups as for samples studied earlier. Vibrational spectra of rare-earth antimonates Ln,SbO, that they do not have a pyrochlore structure, having more bands than expected for a high-symmetry structure; the sharpness of the Raman bands suggests a highly ordered structure, however. 1.r. spectra have been reported for antimony(m) methoxides SbCl.(OMe),-,, (n = 0, 1, or 2) and Sb0(OMe).2351.r. and Raman spectra are used to characterize sulphate-bridged SbV species analogous to the perchlorate noted last year (6) (R = HZ3@ or Me237).Some oxofluorohaloantimonates such as MSbzXF40 (M = K, Rb, or Cs, X = C1, Br, or I) have been characterized by i.r. spectroscopy and X-ray

diffraction.238 Phosphates containing the [SbF]+ cation, MSbFPO, - nH,O (M = Na, n = 2 4 ; M = NH4, n = l), have been reported and characterized by Raman spe~troscopy.~~* Vibrational spectra of some tetrachloroantimonates(111) are discussed in terms of discrete dimeric and tetrameric anionszQoor Ac is conformationis suggestedfor [SbCI,Br,-,lchlorinebridged chain anions.241 Spectra are ions (n = 2 or 4) on the basis of far4.r. and Raman reported for complexes of SbCl, with benzoyl chloride and benzoic anhydride,z43 Y. Kawasaki, Y. Yamamoto, and M. Wada, Bull. Chem. SOC.Jpn., 1983, 56, 145. W. Kolondra, W. Schwarz, and J. Weidlein, Z . Anorg. Allg. Chem., 1983,501, 137. H. Biirger, R. Eujen, G. Becker, 0. Mundt, M. Westerhausen, and C. Witthauer, J. Mot. Struct., 1983, 98, 265. M. Jansen, J. Pebler, and K. Dehnicke. Z . Anorg. Allg. Chem.. 1982. 495, 120. J. Preudhomme, Stud. Znorg. Chem., 1983, 3, 497. 8a6 G. Gattow and F. J. Klsberger, 2.Anorg. Allg. Chem., 1982, 495, 193. 280 S. Blosl, W. Schwarz, and A. Schmidt, 2. Anorg. Allg. Chem., 1982,495, 165. a87 S. Blosl, W. Schwarz, and A. Schmidt, 2. Anorg. Allg. Chem., 1982,495, 177. L. A. Zemnukhova and R. L. Davidovich, Koord. Khim., 1982, 8, 1572. 230 R. Mattes and K. Holz, Angew. Chern., 1983, 95, 898. 940 U. Ensinger, W. Schwarz, and A. Schmidt, 2.Natwforsch., Teil B, 1982, 37, 1584. 341 U. Ensinger, W. Schwarz, and A. Schmidt, Z . Natwforsch., Teil B, 1983, 38, 149. a4a G. J. Gotz-Grandmont and M. J. F. Leroy, 2. Anorg. Allg. Chem., 1983, 496, 40. z4aN.Yu. Vykhrest, T. N. Sumarokova, and R. A. Slavinskaya, Izv. Akad. Nauk Kai. SSR,Ser. Khim, 1982, 29. 230 231

200


of antimony trihalides with 2-aminoben~othiazole,~~~ and of SbCl, with SeOC1,24s and some other O-donor l i g a n d ~ . ,Skeletal ~~ modes are assignedz4?for the 1 : 1 complexes of o-phenanthroline with SbX, (X = F, C1, or Br). A novel antimony fluoride [Sb,F,] is formulated as [Sb,F,]+[SbF,]-, where the cation is an infinite polymer, on the basis of i.r. and Raman Bismuth.-Raman spectra are reported for some dibismuthines R,BiBiR, (R = Me, i-propenyl, Ph, e t ~ . ) .A~hexanuclear ,~ oxybismuth cation is present in the perchlorate Bi,,04(0H)4(~104)6* 7H@, and the i.r. and Raman spectra are saidzs0to be consistent with the crystal structure. The i.r. spectrum of crystalline Bi2(Se04),supports a structure based on SeO, tetrahedra, slightly distorted and with somewhat weaker bonds than in other selenatesZ5l1.r. and Raman spectra are reported for BiF,, ClF2BiF6,and RbBiF6, with other spectroscopic and thermal data.252BiX stretching modes are assigned2s3for Ph3BiXR (R = 2-Me-8quinolinolato, X = C1 or Br). 6 GroupVI Oxygen,-The hydronium ion [H,O]+ has been detected in the gas phase by high-resolution i.r. and the antisymmetric stretching band for both inversion states has been analysed. A polemic has appeared,255putting the case for the existence of hydronium ion as a significant constituent of concentrated sulphuric acid, A detailed study of the proton motions in KHCO, modelling of the i.r. and Raman band structures. Single-crystal CsOH.H,O is shown to contain [H,O,]- ions in layers,257although it is claimed that the i.r. spectra allow OH and H 2 0groups to be distinguished. 1.r. bands due to the internal motions of water dimers in inert and to the intermolecular motions of water monomers in rare-gas or nitrogen are reported, and it is claimed that H,O.HF is the major species formed by the interaction of H,O and HF in solid argon;260the low-frequency (libration) band A. Giusti, G. Peyronel, and E. Giliberti, Polyhedron, 1982, 1, 655. 0. L. Alves and Y . Hase, An. Acad. Bras. Cienc., 1983, 55, 27. 246 N. Bertazzi, G. Alonzo, and T. C. Gibb, Inorg. Chim. Acta, 1983,73, 121. 247 W. A. S. Nandana, J. Passmore, D. C. N. Swindells, P. Taylor, P. S. White, and J. E. Vekris, J. Chem. SOC.,Dalton Trans., 1983, 619. 248 Y. Gushikem and 0. L. Alves, An. Acad. Bras. Cienc., 1983, 55, 179. 249 A. J. Ashe, E. G. Ludwig, and J. Oleksyszyn. Organometallics, 1983, 2, 1859. 250 B. Sundvall, Inorg. Chem., 1983, 22, 1906. 251 N. Dishovskii and Z. Boncheva-Mladenova, God. Vissh. Khim. Tekhnol. Inst.. Sofia. 1982., 244

24s

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27, 123. 252

G. Faraglia, R. Graziani, L. Volponi, and U. Casellato, J . Organomet. Chem., 1983, 253, 317.

263 253

V. F. Sukhoverkov and A. V. Sharabarin, Zh. Neorg. Khim., 1983,28, 629. M. H. Begeman, C. S. Gudeman, J. Pfaff, and R . J. Saykally. Phys. Rev. Lett.. 1983, 51. 554.

P. A. Gigdre, Can. J . Chem., 1983, 61, 588. 258 F. Fillaux, Chem. Phys., 1983, 74, 405. 267 H. Jacobs, B. Harbrecht, P. Muller, and W. Brouger, Z . Anorg. Allg. Chem.. 1982, 491, 2ss

154. 258 25g 260

B. A. Zilles and W. B. Person, J . Chem. Phys., 1983, 79, 65. E. Knozinger and R. Wittenbeck, J . Am. Chem. SOC.,1983, 105, 2154. L. Andrews and G. L. Johnson, J . Chem. Phys., 1983, 79, 3670.


201

in the i.r. spectrum shows evidence of an inversion doubling. Several papers on amorphous or report work on the vibrational spectra of liquid and on anion solvation crystalline ice,285-287 on an ice clathrate THF. 1 7Hp0,268 in mixtures of protic and aprotic ~ o 1 v e n t sFinally, . ~ ~ ~ studies on i.r. and Raman spectra of solid oxygen at high pressures suggest that in the &-phaseabove about 10 GPa there is increasing interaction between pairs of O2 molecules, with concomitant weakening of the 0=0 bonds;270a strong i.r. band develops whose frequency is lower than that of the Raman-active fundamental and decreases with increasing pressure. A low-frequency mode around 130 cm-l also develops, and its frequency increases with increasing pressure. The superoxide ion gives a Raman band at 1123 cm-l [v(OO)] in the tetramethylammonium compared to 1145 cm-l in KO,.

Sulphur, Selenium, and Tellurium Ring and Chain Species.-Raman spectra of sulphur vapours show the presence of species S, with n = 8-2 depending on the temperature,272though S, is apparently not detected. The resonance Raman spectra of Se, in argon or nitrogen matrices have been studied, and it is concluded that the species is bent.273Raman spectra of solid Se allotropes under high pressures show some ‘bond-stretching’ modes to decrease in frequency with The increasing pressure, suggesting increasing inter-‘molecular’ anionic species [S2]-, [S3]-, and [S4]- (or perhaps the neutral S,) and [Se4]- are shown to be important chromophores in ultramarine pigments, using resonance Raman s p e c t r ~ s c o p yRaman . ~ ~ ~ ~and ~ ~ i.r. ~ spectra of a number of compounds containing the [TesI4+cation are reported ;277 the cluster has a trigonal-prismatic structure of Dsd symmetry. Sulphur-Nitrogen Compounds.-The i.r. spectrum of S2N2* 2AlC1, is reported,258 1.r. and Raman spectra and i.r. and Raman spectra of S4Nzhave been C. I. Ratcliffe and D. E. Irish, Raman Spectrosc., Proc. Int. Conf., 8rh, 1982. 369. V. Holba, Collect. Czech. Chem. Commun., 1982, 47, 2484. aos A. C. Belch and S. A. Rice, J. Chem. Phys., 1983,78,4817. a(11 J. Wiafe-Akenten and R. Bransil, J. Chem. Phys., 1983, 78, 7132. a66 G. Nielson and S. A. Rice, J . Chem. Phys., 1983, 78, 4824. aar S. A. Rice, M. S. Bergren, A. C. Belch, and G. Nielson, J . Phys. Chem., 1983, 87, 4295. V. I. Yashkichev, Zh. Fiz. Khim., 1983, 57, 650. G. P. Johari and H. A. M. Chew, Nature (London), 1983,303,604. a6e P. Bacelon, J. Corset, and C. de Loze, J . Solution Chem., 1983, 12, 13. D. T. Sawyer, T. S. Calderwood, K. Yamaguchi, and C. T. Angelis, Znorg. Chem., 1983, aol

22,2577.

B. I. Swanson, S. F. Agnew, L. H. Jones, R. L. Mills, and D. Schiferl, J. Phys. Chem., 1983, 87, 2463. a7a M. Schinazi, J. Corset, M. Delhaye, and J. L. Lesne, Raman Spectrosc., Proc. Int. ConJ, 8th, 1982, 659. H. Schnockel, H. J. Goecke, and R. Elsper, 2. Anorg. Allg. Chem., 1982, 494, 78. a74 K. Nagata, T. Ishikawa, and Y . Miyamoto, Jpn. J . Appl. Phys. I, 1983, 22, 1129. a76 R. J. H. Clark, T. J. Dines, and M. Kurmoo, Inorg. Chem., 1983, 22, 2766. a76 R. J. H. Clark, D. P. Fairclough, and M. Kurmoo, Tinre-Resolved Vib. Spectrosc., (Proc. Int. Con$ TRVS), 1982, 1983, 213. a77 R. C. Burns and R. J. Gillespie, Specrrochim. Acta, Part A, 1983, 39, 439. a78 H. W. Roesky and J. Anhaus, Chem. Ber., 1982, 115, 3682. a7e W. V. F. Brooks, G . K. MacLean, J. Passmore, P. S. White, and C.-M. Wong, J. Chem. Soc., Dalton Trans., 1983, 1961. 271

202


of N(SX2)2+(X = F, C1, or Br) are reported,280with suggested general assignments, supported by normal-co-ordinate analyses for X = C1 or Br. The i.r. spectra of various R1R2S=NR3 have been studied281to show the effects of substituents R1, R2, and R3 on the S-N bond strength. Raman spectra of sulphamic acid282and sodium ~ u l p h a m a t eand ~ ~infrared ~ and Raman spectra of calcium and barium ~ u l p h a m a t e shave ~ ~ ~been reported and discussed. Other Sulphur and Selenium Compounds.-Reactions of fluorine atoms with CH3SHin an argon matrix gives CH2SHand CH3S,both of which form hydrogenbonded complexes with HF.285Some assignments are suggested for MS,CCI (M = Na, K, Rb, or Cs), studied by i.r. spectroscopy.286Detailed i.r. studies of (CF,S),CS in gas, solid, and matrix phases are reported287as a prelude to photolysis studies. Vibrational spectra of (X,C),SO, (X = C1 or Br) are reported for solids, melts, and they can be interpreted in terms of slight distortions from strict C2, symmetry. Torsional motions of MMeSO, salts The i.r. (M = alkali metal) have been studied by inelastic neutron spectra of some new compounds SF,CFXCF3 (X = -COF, CONH2, CN, COOH, or COOMe) have been Vibrational spectra of SF6CHXCF3 (X = H or Ag) are also reported.291SO, dimers in solid nitrogen have been studied by i.r. spectroscopy, which shows the two component molecules to be ineq~ivalent.~~, The i.r. and Raman spectra of some single-crystal samples of anhydrous sulphites and selenites of Sr, Ba, Pb, Cd, and Mn have been reported,293 and the bands due to [SO3I2- and [Se0312- ions implanted into alkali-metal halide crystals have been studied as a function of envir~nrnent.,~~ Many inorganic sulphur compounds can be identified routinely by Raman Raman spectra of K2S04 at high temperature^,^^^ of LiKS04 near the 11-111

R. T. Oakley, M. Trsic, T. Chivers, P. W. Codding, W. G. Laidlaw, and S. W. Liblong, J. Am. Chem. SOC.,1983, 105, 1186. 281 T. G. Zobolotnaya, Yu. P. Egorov, E. S. Levchenko, and T. N. Dubinina, Teor. Eksp. Khim., 1983, 19, 36. 282 C . I. Ratcliffe, W. F. Sherman, and G. R. Wilkinson, J. Raman Spectrosc., 1983, 14, 245. 283 P. Muthusubramanian and A. S. Raj, Can. J . Chem., 1983, 61, 2048. 284 P. Muthusubramanian and A. S. Raj, J. Raman Spectrosc., 1983, 14, 221. 286 M. E. Jacox, Can. J. Chem., 1983, 61, 1036. 286 B. Sturm and G. Gattow, Z . Anorg. Allg. Chem., 1983, 502, 7 . 287 K. Schlosser and H. Willner, Z . Naturforsch., Teil B, 1983, 38, 161. 288 M. Hargittai, E. Vajda, C. J. Nielsen, P. Klaeboe, R. Seip, and J. Btunvoll, Acta Chem. Scand., Ser. A , 1983, 37, 341. C. I. Ratcliffe, T. C. Waddington, and J. Howard, J . Chem. SOC.,Furaday Trans. 2, 1982, 280

78, 1881. 2Bo

R. Debuhr, J. Howbert, J. M. Canich, H. F. White, and G. L. Gard, J . Fluorine Chem., 1982, 20, 515.

H. F. Efner, R. Kirk, R. E. Noftle, and M. Uhrig, Polyhedron, 1982, 1, 723. 292 L. Nord, J. Mol. Sfruct., 1982, 96, 19. 293 H. D. Lutz, W. Buchrneier, W. Eckers, and B. Engelen, Z . Anorg. Allg. Chem., 1983. 496, 2. 294 V. V. Boiko, I. Ya. Kushnirenko, and V. I. Vaidanich, Fiz. Tverd. Tela, 1983, 25, 667. 296 S. Sato, H. Hayano, and N. Hatcho, Kanzei Chuo Bunsekishi Ho, 1983, 23, 1 (Chem. Abstr., 1983, 99, 15 634). M. Ishigame and S. Yamashita, Phys. Status Solidi B, 1983, 116, 49.


203

transition temperature around 700 K,2g7and i.r. and Raman spectra of KHSO, at ambient and lower temperaturesz0*have been studied. Raman spectra of K2S20,-KHS04 melts have been analysed2ggin terms of the equilibrium 2HS04- + S2072- H,O. The anion S0,F- has been identified300 by i.r. spectroscopy following reaction of SO, with CsF in Ar matrices; isotopic data confirm that the two oxygen atoms are equivalent. Similar reactions of CsF with SOF, and SO,F, give spectra assigned to SOF3- anions, respectively. The Raman spectra of salts of the [SeO,Br]- ion have been and discussed in relation to those of the other haloselenites;normal-co-ordinateanalyses suggest very weak Se-halogen bonds. 1.r. and Raman bands of SeOX3- (X = F or Br, various cations) are assigned302in terms of trigonal-bipyramidal co-ordination. with the lone pair and the oxygen atom equatorial.

+

Tellurium.-1.r. spectra indicate covalent binding of the chlorosulphate group to Te in R,Te(OSO,Cl), (R = Me or Et).3031.r. spectra of (CF,),TeX, (X = NO3 or CF,COO) have been rep~rted.~"The i.r. spectrum of Te,O,-HNO, is reportedso6and assigned on the basis of the known crystal structure. 1.r. spectra of tellurites have been reported and d i ~ ~ u s s eThe d.~ i.r.~ spectra ~~~~ of MPTeF8(OHXSO,) (M = Na or NH,) are consistent with the presence of Te as TeF80H units (uncharged),as shown by X-ray structure determination.3o81.r. and Raman spectra of TeF,OF have been reported.3oaComplexes of TeIVwith some aromatic i m i n e ~ , some ~ l ~ hydra~ones,~ll and thiopicolinamide~~~~ have been reported.

M. L. Bansal, S. K. Deb, A. P. Roy, and V. C. Sahni, Pramana, 1983, 20, 183 (Ch~rn. Abstr., 1983, 99, 79 303). 498 R. Fehrmann, N. H. Hansen, and N. J. Bjerrum, Inorg. Chem., 1983,22,4009. K. Garber and B. S . Ault, Inorg. Chem., 1983, 22, 2509. 300 B. Dey, Y. S. Jain, and A. L. Verma, J. Raman Spectrosc., 1982, 13. 209. 301 J. Milne and P. Lahaie, Inorg. Chem., 1983, 22, 2425. 30a J. Milne and P . Lahaie, Spectrochim. Acta, Part A , 1983, 39, 555. 309 Z.A. Siddiqi, M. Shakir, M. Aslam, and S. A. A. Zaidi, Synth. React. Inorg. Met.-OrK. Chem., 1983, 13, 173. 304 S. Herberg and D. Naumann, Z. Anorg. Allg. Chem., 1982,494, 159. 306 I. L. Botto and E. J. Baran, 2.Anorg. Allg. Chem., 1982,494,219. 3w D. Cachau-Hereillat, A. Norbert, M. Maurin, R. Fourcade, and E. Philippot, Rev. Chim. Miner., 1983, 20, 129. 307 M. Arnaudov, V. Dimitrov, I. Dimitriev, and L. Markova, Muter. Res. Bull., 1982, 17, zs7

1121. 30s

310

Yu. E. Gorbunova, S. A. Linde, V. I. Pakhomov, Yu. V. Kokunov, M. P. Gustyakova, and Yu.A. Buslaev, Koord. Khim., 1983, 9, 524. C. J. Schack, U.S.Pat. Appl. U.S.478 581 (Sep. 1983). W. E. Rudzinski, T. M. Aminabhavi, N. S. Biradar, and C. S . Patil, Inorg. Chim. Acta,

1983, 69,83. T . M. Aminabhavi, N. S. Biradar, C. S. Patil, and W. E. Rudzinski, Znorg. Chim. Acta, 1983, 78, 107. 31a T . M. Aminabhavi, W. E. Rudzinski, N. S. Biradar, and C. S . Patil, Znorg. Chim., Acta. 1983, 78, 51. 811

204


7 Group VII The i.r. spectrum of H F dimer has been studied at high resolution in the gas phase313and in argon matrices at 12 K.314The structure of liquid H F has been probed using i.r. and Raman suggesting short chains of six or seven molecules on average at room temperature. 1.r. studies of complexes of hydrogen halides with various bases (ranging from N2316to HCN317)have been c o l l e ~ t e d and ~ ~ ~discussed - ~ ~ ~ in terms of the proton affinities of the bases and other factors, The far-i.r. spectra of solid HCI and HBr under high-pressure and low-temperature conditions have been Raman spectra of [C13]+ and [Br3]+at 12 K are all three fundamentals of [C13]+were observed (in solids condensed from mixtures of HX and NO,), but only resonanceenhanced v1 and v, were found for [Br3]+. Raman spectra of [IBr2]+[Sb2F11]are discussed in relation to the chains of anions and and [IBro.,5Cll.,,]+[sbC16]cations found by diffraction 1.r. spectra suggest that IN3 is covalently bound to ring nitrogen through the iodine atom in 2,2’-dipyridylbis(i0dinea ~ i d e ) . The ~ , ~ benzene-iodine atom complex has been studied by i.r. and visible spectroscopy in solid argon at 17 K.327The symmetric stretching modes of [py-X-py]+ (X = Br or I) are assigned328near 170 cm-l. 1.r. and Raman spectra of some trichlorides X+[C13]- (X = Bu4N, Ph4P, Ph4As, or pyridinium) have been studied for solid and solution samples;329the symmetric C13 stretch is at about 270 cm-l in the Raman spectrum. Raman bands of [I3]-, [12CI]-, and [IC12]- are reported in melts of I, in mixed alkali iodides or chlorides.330 Chlorine oxides ClO, and CI2O,,(n = 2, 3 , or 4) produced in the reaction of ozone with chlorine in the gas phase have been characterized by i.r. spectroS C O P Y . ~ONF ~ ~ has been observed, matrix-isolated in argon following the co-condensation of discharged fluorine and methyl nitrate-argon and bands due to the isomer FON were also observed. It is suggested that it is possible to observe two forms of chlorine nitrate (CIONO, and ClOONO) using matrix-

A. S. Pine and W. J. Lafferty, J . Chem. Phys., 1983, 78, 2154. L. Andrews and G. L. Johnson, Chem. Phys. Lett., 1983, 96, 133. 316 B. Desbat and P. V. Huong, J . Chem. Phys., 1983, 78, 6377. 316 L. Andrews, B. J. Kelsall, and R. T. Arlinghaus, J. Chem. Phys., 1983, 79, 2488. 317 G. L. Johnson and L. Andrews, J. Am. Chem. SOC.,1983, 105, 163. 318 L. Andrews, J. Mol. Struct., 1983, 100, 281. 310 A. J. Barnes, J. Mol. Struct., 1983, 100, 259. 320 J. P. Perchard, J. Cipriani, B. Silvi, and D. Maillard, J . Mol. Struct., 1983, 100, 317. 3a1 L. Andrews, R. T. Arlinghaus, and G. L. Johnson, J . Chem. Phys., 1983, 78, 6347. 32a L. Andrews, R. T. Arlinghaus, and G. L. Johnson, J . Chem. Phys., 1983,78, 6353. 323 J. Obriot, F. Fondere, P. Marteau, and M. Allavena, J. Chem. Phys., 1983, 79, 33. 324 L. H. Chen, E. M. No.ur, and J. Laane, J. Raman Spectrosc., 1983, 14, 232. 3a5 T. Birchall and R. D. Myers, Inorg. Chem., 1983, 22, 1751. 3a6 H. Dorner, K. Dehnicke, W. Massa, and R. Schmidt, 2. Naturforsch., Teil B, 1983, 38, 313

314

437. 327

A. Engdahl and B. Nelander, J . Chem. Phys., 1983, 78, 6563.

328

Yu. N. Kukushkin and V. N. Demidov, Russ. J. Inorg. Chem., 1982, 27, 1464.

M. de Meyer, J. M. Levert, and A. Vanclef, Bull. Soc. Chim. Belg., 1983, 92, 699. W. C. Child and G. N. Papatheodorou, J . Phys. Chem., 1983, 87. 271. 331 R. C. Loupec and J. Potier, J. Chim. Phys., 1983, 80, 449. 332 M. E. Jacox, J. Phys. Chem., 1983, 87, 4940. 830


205

isolation i.r. spectroscopy;333both forms are apparently present for previously synthesized samples and for samples made in situ by reaction of ClO and NO, during deposition. The Raman spectrum of KClO, at high pressures has been a high-pressure phase I1 shows spectra similar to those of rhombohedral RbC10,. Alkali-metal chlorates MCIO, isolated in matrices give l60/l8O substitution patterns consistent with C,, 1.r. and Raman spectra of single crystals of MCIO, (M = K, Rb, or Cs) over a range of temperature (-600 K) covering both orthorhombic low-temperature forms and hightemperature cubic forms have been full Td symmetry is effectively present for the anion in the high-temperature forms. Raman bands of H F solutions of HXO, (X = C1 or Br) are interpreted3,' in terms of undissociated monomers and X04- ions; the dissociation constant was estimated. 1.r. and Raman spectra of [C1F,]+[BF4]- have been reported,338as have vibrational spectra of [clF,]+[zF,]- (Z = As or Sb),339with an assignment of the internal modes of the cation. The i.r. spectrum of PhIO] has been reassessed340following the preparation of the l80isotopomer. No oxygen mass-sensitive bands are found above 600 cm-l, but only one specific assignment is proffered, of ~ ~ ~ ( 1at0 1590 ) cm-l. I 0 stretching modes are assigned341for M 2 0- (2Mo0, * 1205) - 2H20 with 4 1 0 , ) near 800 cm-l and v(1OMo) near 715 cm-l. 8 GroupVIIl Argon dimers have been observed by means of Raman spectroscopy in a supersonic expansion ;342 pure rotational and vibrational Raman transitions were recorded for the v = 0 and v = 1 states of the dimer. Raman spectra of [XeF, * XeF,] +[RuF,]- have been reported.343 Raman spectra of XeW(SO,F),], with a detailed assignment consistent with D2symmetry. are

S. C. Bhatia, M. George-Taylor, C. W. Merideth, and J. H. Hall, J . Phys. Chem., 1983, 87. 1091.

A. M. Heyns, Raman Spectrosc., Proc. Znt. Con$, 8th, 1982, 403. 936 I. R. Beattie and J. E. Parkinson, J. Chem. SOC.,Dalton Trans., 1983, 1185. 33s H. D. Lutz, R. A. Becker, W. Eckers, H. J. Holscher, and H. J. Berthold, Spectrochim. Acta, Part A , 1983, 39, 7. 337 L. Stein and E. H. Appelman, Inorg. Chem., 1983,22, 3017. K. 0. Christe and W. W. Wilson, Znorg. Chem., 1983, 22, 1950. 339 K. 0. Christe, W. W. Wilson, and E. C. Curtis, Znorg. Chem., 1983, 22, 3056. 910 B. C. Schardt and C. L. Hill, Inorg. Chem., 1983, 22, 1563. u1 T. G. Balicheva and N. 0. Sablina, Russ. J. Znorg. Chem., 1982,27, 1745. a4z H. P. Godfried and I. F. Silvera, Phys. Rev. A, 1983, 27, 3008. 343 B. Zemva, L. Golic, and J. Slivnik, Vestn. Slov. Kem. Drw., 1983, 30, 365. s14 G. A. Schumacher and G. J. Schrobilgen. Znorg. Chem., 1983.22. 2178. 3a4

5 Vibrational Spectra of Transition-element Compounds BY G. DAVIDSON

1 Introduction This chapter is arranged as in previous volumes, with detaikd vibrational assignments considered first. These mostly involve both i.r. and Raman spectra, with use of isotopic substitution. In many cases some form of normal-co-ordinate analysis was also performed. These are followed by resonance Raman studies, while the remaining papers are classified according to the familiar triads of transition metals, ending with a survey of actinoid complexes. 2 Detailed Studies

Several of the species for which detailed data are now available are listed in Table 1.l--19

Table 1 Detailed studies involving vibrational analyses or isotopic data Species

Isotopes

trans-[MX,(H20),](M = Ti''', V'", or Crl'', X = C1 or Br) MTiF6* 6H20 (M = Mn or Zn) Ln2Ti,0, (Ln = Sm, Gd,Yb, or Y) Li4Ti6012

Ref. i

2 3

4 5

v206

Rbz WOFdH2O)I NH4[VO(O2)NH31 MOFs2- (M = Nb or Ta) CrOaF, M(NHg)63+ (M = Cr or Co) T12Cr0,, Et,NMnO, Ln2(E04)3.4Ln(Re04)3 (Ln = Y or Dy, E = Mo or W) M(octaethy1porphinato) (M = Mn, Fe, Co, Ni, Cu, or Zn) ML2 (M = Fe, Co, Ni, or Cu, HL = aromatic hydroxyoximes) Ni(oxamate),2-, Ni(~xamate),~~is-[Zn(glycine)~] .H20 Diaqua(oxydiacetato)sulphatot horium( iv) U(OMe), U02[CF,C(0)CHC(O)CF,J L (L = THF, DMSO, etc.)

-

206

6 7 8 9 10 11 12 13 "CU,66CU

'80

'80

14 15 16 17 18 19

Vibrational Spectra of Transition-element Compounds

207

The lanthanoid(1v) fluoro complexes Cs,MF, (M = Ce, Tb, Pr, Dy, or Nd) have been prepared. Their vibrational spectra are consistent with Dshsymmetry, and a detailed assignment was given for PcF?~-,together with a normal-coordinate analysis.2o The i.r. spectrum of YbCl, in an argon matrix shows it to be non-linear. 3sCl/37Clshifts and the relative intensities of v1 and v3 suggested an angle of 126 f 5". The vibrational wavenumbers/cm-l were: v1 296.5 (Yb3SC12),294.4 (YbSSC137Cl), 290.3 (Yb3?C12);v 3 287.2 (YbWl,), 282.7 (Yb36C137Cl),279.8 (Yb3?CI2).,l The complexes Mo(N,),, (n = 1-3) were characterized in krypton matrices by means of 16Nsubstitution.22Precise measurements have been made of v1 for in aqueous solutions. Extrapolating to infinite dilution gave and W042wavenumbers of 986.1 k 0.1 cm-I for and 931.1 f 0.1 cm-l for ~ 0 ~ 2 - 2 3

1.r. stretching fundamentals have been assigned for W(=E)X4 (E = S or Se, = F, C1, or Br) isolated as monomers in nitrogen matrices. v(W=S) showed a 32S/s4Sisotopic splitting of ca. 14 cm-l, e.g. in W(=S)F4 577.3 (s2S) and 562.9 ( 34S) cm-l.,, The i.r. spectra of solid and matrix-isolated Mn207are consistent with a bridged structure and with an 0,Mn-O-MnO, angle of ca. 150-160". The

X

D. Michalska-Fong, P. J. McCarthy, and K. Nakamoto, Spectrochim. Acta, Part A, 1983, 39,835.

* P. Choudhury, B. Ghosh, G. S. Raghuvanshi, and H. D. Bist, J . Raman Spectrosc., 1983, 14, 99. :' M. T. Vandenborre, E. Husson, J. P. Chatry, and D. Michel, J. Raman Spectrosc., 1983. .I

14, 63. E. V. Proskuryakova, 0. I. Kondratov, N. V. Portnikov, and K . I. Petrov, Russ. J . Znorg. Chem., 1983,28, 791.

L. Abello, E. Husson, Y. Repelin, and G. Lucazeau, Spectrochim. Acta, Part A , 1983. 39, 641. (I M. Schabert and G. Pausewang, 2. Anorg. Allg. Chem., 1983,506, 169. P. Schwendt and M. Pisarcik, Collect. Czech. Chem. Commun., 1982,47, 1549. " L. Surendra, D. N. Sathyanarayana, and G. V. Jere, J. Fluorine Chem., 1983,28, 115. R. J. French, L. Hedberg, K. Hedberg, G. L. Gard. and B. M. Johnson, Innrg. Chetn.. 1983, 22, 892. lo C. l1

l2 l3

Tellez, Semina (Londrinu, Bruz.), 1982, 3, 185. H. Homborg, 2. Anorg. Allg. Chem., 1983, 498, 25. V. V. Fomichev and A. A. Makarov, Russ. J. Inorg. Chem., 1983,28,602. J. R. Kincaid, M. W. Urban, T. Watanabe, and K. Nakamoto, J. Phys. Chem., 1983, 87, 3096.

C. Zhou, X. Chen, and C. Yuan, Huaxue Xuebao, 1983,41,623. I 5 G. Schoeters, D. Deleersnijder, and H. 0. Desseyn, Spectrochim. Acta, Part A , 1983,39, 71. Y . Zhou, X.Wang, M. Liao, and Y . Ou, Qinghua D a m e Xuebao, 1982,22,99. R. Graziani, G. A. Battiston, U. Casellato, and G. Sbrignadello, J. Chem. SOC.,Dalton Trans., 1983, 1. E.A. Cuellar, S. S. Miller, T. J. Marks, and E. Weitz, J. Am. Chem. SOC.,1983,105,4580. I @ R. G. Bray, Spectrochim. Acta, Part A, 1983,39, 559. 2oYu. M. Kiselev, S. A. Goryachenko, and L. 1. Martynenko, Rum. J. Inorg. Chem., 1983. l4

28, 651.

I. R. Beattie, 3. S. Ogden, and R. S. Wyatt, J. Chem. SOC.,Dalton Trans., 1983, 2343. T. Foosnaes, M. J. Pellin, and D. M. Gruen, J . Chem. Phys., 1983,78,2889. a3 K. J. Dean and G. R. Wilkinson, J. Raman Spectrosc., 1983, 14, 180. *4 P. J. Jones, W. Levason, J. S. Ogden, J. W. Tuff, E. M. Page, and D. A. Rice, J. Chern. SOC.,Dalton Trans., 1983, 2625.

41

a2

208


following assignments/cm-l were given : v,,(Mn=O) 955, v,(Mn=O) 890, vas(MnO)775, v,(MnO) 560, 6(Mn03)370-320.25 A detailed vibrational assignment for Mn(CO),Me, using i.r., Raman, and inelastic neutron-scattering spectra, gave a revised value for v(MnMe) of 416 cm-1.26 Matrix-isolation i.r. and Raman spectra of MReO, (M = K or Cs), with l80substitution, showed that they had C,, symmetry and allowed a definite assignment for v(ReO).,' Matrix isolation was also used in characterizing FeCI,, FeCI,, CoCl, CoCI2, CoCI,, and NiCl, molecules. The dichlorides are all non-linear, with bond angles close to 160". FeCI, and CoCl, both gave spectra consistent with planar, Dsh,geometry, despite earlier claims that FeCl, may be pyramidal.29 Skeletal vibrations have been characterized in the complexes [Co(gly),(ox),(en)z](3-x-2y)+ (gly = glycinate, ox = oxalate, en = ethylenediamine, x y z = 3) by means of Raman spectroscopy. Depolarized bands (300--400 cm-l) were particularly helpful in differentiating C,-cis isomers of CoN402- and CoN,O,-type complexes.30 Detailed skeletal-mode assignments were also made for [Rh(NCS),(SCN),-,]3- (n = M). Values of v(RhN) were in the range 300-340 cm-l, v(RhS) 265-306 cm-l. For n = 2 or 4 the data were consistent with cis geometry, for n = 3 with mer ge~metry.~' Raman spectra of K4[Pt2(pop),X2] and K4[Pt2(pop),l (pop = P205H22-, X = C1, Br, or I, or X2= MeI) have been analysed. The first group gave Ptl"-Pt'll stretching wavenumbers 110-1 58 cm-l [there was strong coupling with v(PtX)], the last a Pt"-Pt" stretch at 116 ~ m - l . , ~ Metal-isotope effects were used to identify skeletal modes in cis- and transbis-(a-alaninato)copper(~~)~~ and in copper and zinc glutamate hydrates.34 p28

+ +

3 Resonance Raman Spectra Quite a wide range of compounds have given informative resonance Raman spectra, although many of them are primarily of biological interest. v(VN) gives a resonance-enhanced band at 256 cm-l in VO(phthal~cyanine).~~ Resonance Raman spectra of W(NMe,), suggest that vs(WNB)and vas(WN6) modes, of alg and eg symmetry, respectively, are accidentally degenerate (554 ~ m - 9 . ~ ~ 26

26

W. Levason, J. S. Ogden, and J. W. Turff, J. Chem. SOC.,Dalton Trans., 1983, 2699. M. A. Andrews, J. Eckert, J. A. Goldstone, L.Passell, and B. Swanson, J. Am. Chem. SOC.. 1983,105, 2262.

S . A. Arthers, I. R. Beattie, R. A. Gomme, P. J. Jones, and J. S. Ogden, J. Chem. SOC., Dalton Trans., 1983, 1461. 38 L. Bencivenni, H. M. Nagarathna, and K. A. Gingerich, Chem. Phys. Lett., 1983,99,258. D. W. Green, D. McDermott, and A. Bergman, J. Mol. Spectrosc., 1983,98, 111. 30T.F. Maruyama, K. Okamoto, J. Hidaka, and H. Einaga, Bull. G e m . SOC.Jpn., 1983. 56, 2610. 31 H.-H. Fricke and W. Preetz, Z. Anorg. Allg. Chem., 1983, 507, 12. 32 P. Stein, M. K. Dickson, and D. M. Roundhill, J . Am. Chem. SOC.,1983,105, 3489. 33 Y. Saito, J. Odo, M. Nishio, Y.Tanaka, and K. Machida, Chem. Pharm. Bull., 1983, 31, 27

2967.

J. Odo, M. Nishio, Y. Saito, and Y. Tanaka, Chem. Pharm. Bull., 1983, 30, 2661. 36 R. Aroca and R. 0. Loutfy, Specfrochim. Acta, Part A , 1983,39,847. 36 R. 5. H. Clark and T. J. Dines, Znorg. Chim. Acta, 1983,70, 35. 34


209

Several papers report work on species containing WS42- 37 or MoSd2- or WS42- bound to other transition e l e m e n t ~ . The ~ ~ tfree ~ ~ WS42- ion gives a long progression in v1 (6J1 = 490.5 f 0.5 cm-l, xI1 = -1.1 k 0.1 cm-1 for the NH4+salt). Resonance Raman and polarized i.r. spectra of K,[Mn,O(CN),,] - CN suggested that v,(MnOMn) was at 258.5 cm-l, with va,(MnOMn) at 895 ~m-l.~O Progressions of bands involving v(ReRe) dominate the resonance Raman spectra of ReaXs2-(X = F, CI, Br, or while v(FeX) is dominant in FeX42 (X= C1 or Br).43 Other conventional transition-element complexes studied by this technique are Fe(CO),(di-imine),44 OsC1,- (a detailed assignment, also using i.r.),45 IrClg2-,46 N,N'-bis(salicy1aldehyde)-o-diaminobenzene nickel(^),^' and Ma(dppm),X, (M = Pd or Pt, X = C1 or SnCI,, dppm = Ph2PCHpPPh2).48 Clark and co-workers have continued their studies of mixed-valence platinum complexes [Pt11(pn)2][Pt1V(pn)aX2]Y4 (pn = 1,Zdiaminopropane; X = C1, Br, or I for Y = C104, X = Br for Y = BF4)40and [Pt'l(dien)I][PtlV(dien)I,]I, (dien = dieth~lenetriamine).~~ The latter shows a long overtone progression in the symmetric Pt-I,, stretch. Matrix-isolated Cu3 gives a most unusual resonance Raman spectrum, which can best be interpreted on the basis of fluxional b e h a ~ i o u r . ~ ~ The ability to obtain time-resolved resonance Raman spectra has been used to elucidate the processes taking place on oxygen binding in haemoglobinS2and to observe the transient species formed on photolysis of haern~globin.~~ Other resonance Raman studies on derivatives of haemoglobin and myoglobin, other than time-resolved, have been reported in references 54-57. 1),41942

37

30 40

R. J. H. Clark, T. J. Dines, and G. P. Proud, J. Chem. SOC.,Dalton Trans., 1983,2019. J. W. McDonald, G. D. Friessen, W. E. Newton, A. Muller, W. Hellmann, U. Schimanski, A. Trautwein, and U. Bender, Znorg. Chim. Acta, 1983,76,L297. A. Miiller, W.Jaegermann, and W. Hellmann, J. Mol. Struct., 1983,100,559. A. H. Jubert, J. A. Espindola, E. L. Varetti, and P. J. Aymonino, J. Raman Spectrow..

1983,14,259. R. J. H. Clark and M. J. Stead, Am. Chem. SOC.,Symp. Ser., 1983,211,235. 42 R. J. H. Clark and M. J. Stead, Znorg. Chem., 1983,22,1214. 43 R. J. H. Clark and T. J. Dines, Chem. Phys., 1982,70,269. 44 M. W. Kokkes, D. J. Stuf'kens, and A. Oskam, J. Chem. SOC.,Dalton Trans., 1983,439. 45 W. Preetz and M. Bruns,Z. Narwforsch., Teil B, 1983,38, 680. 46 H.Hamaguchi and M. Tasumi, J. Chem. Phys., 1983,78,131. 47 M. Datta, D. H. Brown, and W. E. Smith, Spectrochim. Acta, Part A , 1983,39,37. 48 0.L. Alves, M. C. Vitorge, and C. Sourisseau, Nouv. J. Chim., 1983,7,231. 4B R. J. H. Clark and M. Kurmoo,J. Chem. SOC.,Dalton Trans., 1983,761. 5 0 R. J. H. Clark, M. Kurmoo, A. M. R. Galas, and M. B. Hursthouse, J. Chem. SOC.,Daltort Trans., 1983, 1583. 5 1 D. P. DiLella, K. Taylor, and M. Moskovits, J. Phys. Chem., 1983,87,524. s2 J. M. Friedman, T. W. Scott, R. A. Stepnoski, and M. Ikeda-Saito, J. Biol. Chem., 1983, 41

258, 10 564. 53

J. M. Friedman, D. L. Rousseau, M. R. Ondrias, and R. A. Stepnoski, Science (Washington,

54

D.C.), 1982,218, 1244. E. A. Kerr, H. C. Mackin, and N. T. Yu, Biochemistry, 1983,22,4573. M. A. Walters, T. G. Spiro, D. M. Scholler, and B. H. Hoffman, J. Raman Spectrosc.,

55

1983,14,162. 56 57

H. C. Mackin, B. Benko, N. T. Yu, and K. Gersonde, FEBSLett., 1982,158,199. M. A. Walters and T. G. Spiro, Biochemistry, 1982,21,6989.

210


Considerable attention has been paid to the Fe-S bonds in the following species: oxidized spinach ferredoxin, bovine adrenodoxin, etc.,68 rubredoxin, desulphoredoxin, and synthetic analogue^,^^ cytochrome P450cam,B0 electrontransfer flavoprotein dehydrogenase,B1and a variety of ferredoxins that showed marked differences in the wavenumbers of Fe-S(cysteine) stretching modes.g2 A normal-co-ordinate analysis of the skeletal wavenumbers from the resonance Raman spectrum of the blue copper protein azurin has been carried out. The most realistic fit of observed and calculated wavenumbers occurred for a trigonal CuN,S ~ n i t . 6 ~

4 Scandium, Yttrium, and the Lanthanoids v[LnC(of the cyclopentadienyl group)] is near 250 cm-l in Cp,M(C6H,Me-p) (M = Er, Yb, or Gd); it is possible that v[LnC (of the a-bonded group)] is near 390 crn-l.8, v(Sc0) in Sc(TcO,), is at 328 cm-l, with ~(SCO) thought to be at 270 cm-1.65 Other lanthanoid-oxygen stretching modes were assigned in lanthanoid aquoacetylacetonato complexeses and in [ML,]- (M = Tb, L = acetylacetonate, benzoylacetonate, or benzoyltrifluoroacetone; M = Dy, Sm, or Gd, L = benzoyltrifluoroacetone).67 1.r. and Raman spectra of single crystals of Tb,.,E U ~ . ~ ( M O O and , ) , ~ ~B ~ G ~ , ( M O O , )gave , ~ ~ quite detailed vibrational assignments. Several v(Eu0) modes were identified (176-241 cm-l) for E U ( N O ~ ) ~ ~ - . ~ * Evidence was found for metal-oxygen co-ordination in a series of lanthanoid crown-ether complexes, e.g. M(NO,),-L (M = La-Gd, L = 15-crown-5 or 1 8-cr0wn-6).~~ The lanthanoid complexes {Ln[(-)-bdtp],)- [Ln = Nd or Eu, (-)-bdtp = ( -))-O,O'-1R,2R-dimethylethylenedithiophosphate] gave v(LnS) as a strong i.r. band at 250 ~ r n - l . ~ , V. K. Yachandra, J. Hare, A. Gewirth, R. S. Czernuszewicz, T. Kimura, R. H. Holm, and T. G. Spiro, J. Am. Chem. SOC.,1983,105,6462. B B V. K. Yachandra, J. Hare, L. Moura, andT. G. Spiro, J. Am. Chem. SOC.,1983, 105,6455. 6o P. M. Champion, B. R. Stallard, G. C. Wagner, and I. C. Gunsalus, Dev. Biochem., 1982. j8

23, 547.

62

J. Schmidt, J. Beckmann, F. Frerman, and J. T. McFarland, Biochem. Biophys. Res. Commun., 1983, 113,784. Y . Ozaki, K. Nagayama, Y. Kyogoku, T. Hase, and H. Matsubara, FEBS Lett., 1983,

13,

T. J. Thamann, P. Frank, L. J. Willis, and T. M. Loehr, Proc. Natl. Acad. Sci. U.S.A.,

64

C. Qian, C. Ye, H. Lu, Y. Li, J. Zhou, Y. Ge, and M. Tsutsui, J . Organomet. Chem., 1983.

61

152, 236. 1982,79, 6396. 247, 161. 66

L. L. Zaitseva, A. V. Velichko, A. V. Demin, and A. I. Soukhikh, Russ. J. Znorg. Chem., 1982, 27, 928.

C . Nie, P. Yao, Y. Li, C. Ye, and C. Qian, Huaxue Xuebao, 1983, 41, 616. 13' V. E. Karasev, N. I. Steblevskaya, E. T. Karaseva, and R. N. Shchelokov, Rus-. J. Inorq. Chem., 1983,28,492. 68 S . S . Saleem, G. Aruldhas, and H. D. Bist, J. Solid State Chem., 1983,48, 77. 68 V. V. Vakulyuk, V. V. Fomichev, and A. A. Evdokimov, Russ. J. Znorg. Chem., 1983, 28, 66

366.

J.-C. G. Bunzli, B. Klein, G.-0. Pradervand, and P. Porcher, Znorg. Chem., 1983, 22, 3763. i 1 Y. Liang, Y. Zhao, S. Zhang, F. Yu, and J. Ni, Huaxue Xuebao, 1983,41, 198. 72 P. Biscarini, Znorg. Chim. A m , 1983, 74, 65. 'O


21 1

Other vibrational assignments for Sc, Y, and lanthanoid complexes are given in the references summarized in Table 2.3912.2072*

Table 2 Some complexes of scandium, yttrium, and the lanthanoids in which metal-ligand modes are assigned Ref.

Specks

RbEu(NH2) ~H83010 Ln2Ti107(Ln = Sm,Gd, Yb, or Y ) LnaTia07(Ln = Sm-Lu) SrLa,Ti,O, 1 SrLniTiaOi (Ln = La-Nd) Sro.,LnTiOe LnV0,Cl (Ln = lanthanoid) Lng(E01)3.4Ln(Re04)3(Ln = Y or Dy, E = Mo or W) LnMO4C1(Ln = lanthanoid, M = Mo or W) Ln3WOeC13(Ln = lanthanoid) :j

}

KSm(WO& Lanthanoid crown-ether complexes Ln@PM), (Ln = lanthanoid, DPM = dipivaloylmethanato) Nda03 M1LnTiM207(M1= Ca or Sr, Ln = La, Pr, or Nd, M2 = Nb or Ta) LnL(HL)(H20) (Ln = lanthanoid, HL = peri-dihydroxynaphthindenone) MLnHP3010(M = Na, K, Rb, or Cs, Ln = lanthanoid) Cs3LnF7(Ln = Ce, Pr, Tb, Dy, or Nd) M3LnF7(M = K, Rb, or Cs, Ln = Ce, Tb, or Pr) YbCI, in Ar matrix

73 74 3 75

76 77

12 78

79 80 81

82 83

84 85 86

20 87

21

5 Titanium, Zirconium, and Hafnium

Reference has already been made to work on trans-[TiX,(H,O),]+ (X = C1 or Br),l MTiFB.6Hz0(M = Mn or Zn),2 Ln2Ti207(Ln = l a n t h a n ~ i d ) SrLa,,~~~~ TizOs and SrLn2Ti,01, (Ln = La-Nd),76 and Li,Ti,012.4 H. Jacobs, J. Kockelkorn, and J. Birkenbeul, J. Less-Common Met., 1982, 87, 215. Z. Kanepe and Z . Konstants, Zzv. Akad. Nauk SSSR,Neorg. Mater., 1983, 19,969. 75 L. L. Kochergina, N. V. Porotnikov, 0. I. Kondratov, and K. I. Petrov Rurs. J . Inorg. Chem., 1983, 28, 171. 76 N. V. Porotnikov, 0. V. Siderova, and L. N. Margolin, Russ. J. Znorg. Chem., 1983,28,163. 77 A. K. Molodkin, V. V. Kurilkin, Yu. E. Bogatov, V. I. Moskalenko, and A. 1. Ezhov, Russ. J. Znorg. Chem., 1982, 27, 1402. 78 L. H. Brixner, H. Y. Chen, and C. M. Foris, Mater. Res. Bull., 1982,17, 1545. 70 L. H. Brixner, H. Y. Chen, and C. M. Foris, J. Solid-State Chem., 1982,44,99. V. V. Fomichev, V. A. Gagarina, 0.I. Kondratov, L. A. Gribov, and K. I. Petrov, Russ. J. Znorg. Chem., 1983,28,61. W. Wang, B. Chen, Z. Jin, and A. Wang, J. Radioanal. Chem., 1983,76, 49. 82 V. P. Korsun and N. A. Kostromina, Ukr. Khim. Zh. (Russ. Ed.), 1983,49,577. 83 S. M.Klimova, Z. A. Uskova, and S . V . Koledova, Tr. Mosk. Energ. Inst., 1982,563,48. A. M.Sych and Yu. A. Titov, Ukr. Khim. Zh. ( R w s . Ed.),1983,49,572. S. S. M. Hassan, Mikrochim. Acta, 1983, 2, 23. N. V. Vinogradova and N. N. Chudinova, Zzv. Akad. Nauk SSSR, Neorg. Mater., 1983, 73 74

19, 116. 87

K. Feldner and R. Hoppe, Rev. Chim. Miner.,

1983,20, 351.

212


v(HfCp) ca. 450 cm-l, v(HfS) ca. 330 cm-l, and, where appropriate, v(HfC1) ca. 360 cm-l have been assigned for (q5-C5H5),Hf(S2CNR1R2)C1 and (qS-C5H5)Hf(S2CNR1R2)3.88 1.r. and Raman wavenumbers were reported for M2Ti,07 (M = La, Pr, or Nd),89 Sr,.,LnTi,O, (Ln = Nd, Pr, or La),g0TiNb207,g1TiTa207,92 and Ba7Nb,Ti,O,,. 93 v(Zr=O) modes were assigned and Zr=O stretching force constants were estimated in ZrOL, (HL = salicylic acid R-substituted salicylidene hydrazide, R = H, 5-C1, 5-Br, 5-NO2, 3-Et0, 5-Me0, 3,5-C1,, or 5,6-benz0).~~ The complexes (acac),Ti(OR), (R = CH,Ph, CH,CHMe,, CHMe,, or CMe,Ph) give v(Ti0) at 427-445 cm-l and v(Ti-OR) at 613-623 cm-l. In Ti(dpm),(OR), (dpm = Bu‘COCHCOBu‘) v(Ti0) bands were seen at ca. 500 cm-1 and v(TiOR) bands at 619-624 ~ r n - l . ~ , An intense i.r. band at 705cm-l in KTiOP04 was attributed to -Ti-0Ti-0chain stretching parallel to the crystal polar axis.gs The complex (1) gives v(Zr0) at 559 cm-l and v(ZrCl)/v(ZrS)(indistinguishable) at 333 ~ m - l . ~v(ZrS) ’ bands were found in the range 366-392cm-l in Zr(S2CNPriz)4.98

A normal-co-ordinate analysis was performed on the TiFa3- ion in (N,H,)ZnTiF, - 5H20.g9 Vibrational wavenumbers, etc., calculated from electrondiffraction data were compared with those from i.r. spectra for MF4 (M = Ti, Zr, or Hf).loORaman spectra were reported for MZrF, (M = Ba, Sr, or Pb”), showing that in vitreous samples the zirconium was predominantly eightco-ordinate.lol A microwave discharge through TiCI,/Ar mixtures gave TiCl, (n = 4, 3, 2, or possibly 1). Vibrational bands from TiCI, and TiCI, were seen at 497cm-1 and 489 cm-l, respectively.102 S. Kumar, G. S. Sodhi, and N. K. Kaushik, R w s . J . Inorg. Chem., 1983,28, 196. S . Yu. Stefanovich, N. A. Zakharov, F. Kh. Chibirova. and R. R. Shifrina, Fiz. Khim. Neorg. Mater., 1981, 23. @O 0. V. Sidorova, N. V. Porotnikov, and K. I. Petrov, Russ. J . Znorg. Chem., 1982, 27, 1107. B1 N. G. Eror and U. Balachandran, J. Solid State Chem., 1982,45,276. 92 N. G. Eror and U. Balachandran, Spectrochim. Acta, Part A , 1983,39, 261. B3 I. Lindner and S. Kemmler-Sack, Naturwissenschaften, 1982,69,445. 94 A. Syamal and D. Kumar, Pol. J . Chem., 1981,55, 1747. 96 R. C. Fay and A. F. Lindmark, J. Am. Chem. Soc., 1983, 105, 2118. 96 M. K. Rodionov, N. P. Evtushenko, and I. S. Rez, Ukr. Khim. Zh. (Russ. Ed.), 1983,49, 5 . @7 M. E. Silver and R. C. Fay, Organometallics, 1983, 2, 44. A. F. Lindmark and R. C. Fay. Znorg. Chem., 1983,22,2000. J. Slivnik, A. Rahten, J. Macek, S. Milicev, and B. Sedej, Vestn. Slov. Kem. Drus., 1983, 30, 313. looG. V. Girichev and N. 1. Giricheva, Zh. Strukt. Khim., 1983, 24, 14. lol Y. Kawamoto and F. Sakaguchi, Bull. Chem. SOC.Jpn., 1983,56,2138. lo2 T . C. DeVore and T. N. Gallaher, High Temp. Sci., 1983, 16, 83.


21 3

6 Vanadium, Niobium, and Tantalum

Skeletal-mode assignments were proposed for Cp,MX(CN) (M = V or Cr, X = CN, CI, Br, or I), i.e. v(MCp), v(M-CN), and v(MX). For w(M-CN) the values were Cr > V, paralleling the change in v(CN).lo3The same workers gave analogous data on C P ~ M ( N , )(M ~ = V or Cr). The v(MCp) stretches were at higher wavenumber than in the parent MCp, compounds.lo4 1.r. data gave evidence for a transannular V-N bond in l-oxovanadatrane and substituted analogues.lo6 The i.r. spectra of MVO, and MVO, (M = Na, K, Rb, or Cs) isolated in matrices could be interpreted in terms of C,, ring structures. Raman spectra of matrix-isolated CsVO, and CsVO, confirmed the bidentate co-ordination of V0,- and VO3-.lO6The Raman spectra of x- and $-forms of NaVO, show that the linear VO,- chains are formed by V 0 4 tetrahedra sharing two corners with each other.lo7 Bands in the range 490-660 cm-l for a wide range of Vv peroxo complexes are sensitive to the composition and geometry of the co-ordination polyhedron.loR v(V=O) in V202C14( p-2-hydro~y-6-methylpyridine)~ gives very complex i .r. bands. Hence both intra- and inter-molecular coupling takes place.loB v(V=O) is near 980cm-l in the heteropolyacids H,+,PMol,~,V,O,, (n =; 1-3). It was identified by its increasing intensity with increasing n.l10 In A12V10028~ 22H20, v(V=Oterminal) is found at 973 and 958 cm-l, v,,(VObridge) at 462 cm-l.ll1 v(V==O) bands are all at 831 and 715 cm-l, and ws(VObridpe) within a 25 cm-l range in Cs2V,011, K2VAO2,,and K2V,0,, x. v(V0V) bands are seen at 700-860 cm-l.l12 The bands due to v(V=O) in VO(L) (L is aquadridentate naphthaldimine ligand) are generally consistent w. 9 five-co-ordinatevanadium, i.e. the complexes are monomeric. Other work reporting v(V0) assignments is summarized in Table 3.196-7977r114-120 loSM.

Mordn and M. Gayoso, Z . Naturforsch., Teil B , 1983, 38, 177. MorAn and M. Gayoso, J. Organomet. Chem., 1983,243,423. E. E. Shestakov, M. G. Voronkov, Yu. L. Frolov, and V. P. Baryshok, Zh. Obshch. Khim.,

lo4M.

lo5

1983,53, 1298. l a t ~L. Bencivenni and K. A. Gingerich, J.

Mof. Struct., 1983, 96, 197. Seetharaman, H. L. Bhat, and P. S. Narayanan, J . Raman Spectrosc., 1983, 14,401. lo8P. Schwendt, Collect. Czech. Chem. Commun., 1983. 48, 248. lo@ F. A. Cotton, G . E. Lewis, and G. N. Mott, Znorg. Chem., 1983, 22, 378. 110 C. D. Ai, H. G. Jerschkewitz, P. Rcich, and E. Schreier, Z . Chem., 1982,22, 419. 111 G. Rigotti, A. E. Lavat, M. E. Escobar, and E. J. Baran, 2.Anorg. Allg. Chem., 1983, lo7S.

501, 184.

N. Krasil’nikov, M. P. Glazyrin, A. A. Ivakin, L. A. Perelyaeva, and A. P. Palkin. Rurs. J . Inorg. Chem., 1983, 28, 417. l1S K. S. Pate1 and G. A. Kolewole, J . Coord. Chem., 1982, 11, 231. 114 V. Dimitrov, Ya. Dimitriev, and V. Mihailova, Monatsh. Chem., 1983, 114 669. 116 M. A. Nabar and D. S. Phanasgaonkar, Spectrochim. Acta, Part A , 1983, 39, 777. 116 L. V. Kristallov, A. A. Fotiev, and M. P. Tsvetkova, RUSS. J . Inorg. Chem., 1982,27, 1714. 117 M. P. Glazyrin, V. N. Krasil’nikov, and A. A. Ivakin, Russ. J . Znorg. Chem., 1982,27, 1740. 118 A. A. Ivakin, I. G. Chufarova, A. P. Yatsenko, 0. V. Koryskova, N. 1. Petunina. and M. P. Glazyrin, RUSS.J . Znorg. Chem., 1983, 28, 519. 119 R. Mattes and H. Forster, J . Less-Common Met., 1982, 87, 237. 180P. Schwendt and D. Joniskova, Proc. ConL Coord. Chem., 1983, 9, 367. 1lSV.

214


Table 3 Some vanadium oxy complexes in which V-0

ligand modes are assigned

Species

Ref:

Crystalline V 2 0 6 Fe203/V106system Rb2[VOFdH,O)I

5 i14

NHI[VO(O2)NH31 trans-[VX2(H20),]+ LnV0,Cl (Ln = lanthanoid) TIM"Cr,(VO,), (M = Co, Ni, Cu, Mg, Ca, Sr, Ba, or Pb) a-,B-Mg2V20, MVOtdS04, M3VOz(S04)2, M4(V02)3(so4>2s2o, NaM2[(V02)3(H20),(S04)3] -(5-x)H,O (M = K, Rb, or Cs) [V,O4F61 3M3[HV202(02)aF41 (M = NH, or K)

6 7 1 77 115 116 117 118 119 t 20

VF, and V,Fz bands were seen in noble-gas matrices of VF3. Estimated bond angles were 113-120" (VF,) and 150-180" (VF,).lZ1 1.r. and Raman spectra were reported for MNb,O,F (M = Rb, Cs, or T1) and for RbTa,O,F, and Nb-0 and Nb-F force constants were calculated.lZ2 The bridging Nb-0-Nb group in [Nb,OCl,]- gives v(Nb0) at 838 cm-l, with seven bands (295-385 cm-l) due to ~(NbCl).l,~ 1.r. spectra of rapidly quenched glasses in the systems Li,O-MO-Nb,O, (M = Mg, Ca, or Ba) are interpreted in terms of both edge- and corner-shared Nb08 ~ c t a h e d r a . ~ ~ ~ ~ ~ Other Nb-0 systems studied are [MOF5lZ-(M = Nb or Ta),8 CrLaTiNbO, and SrMTiTaO, (M = La, Pr, or Nd),84A,B,O, (A = Ca or Sr, B = Nb or Ta), * TiNb207,91 and Ba7Nb4Ti20,1.B The complex NbS(S,CNEt,), has v(Nb=S) at 493 cm-1.128Tn CP,NbMe,[SC(=S)NEt,] a band due to v(NbS) is seen at 380 cm-l.12, Some calculations of (NbF,)3 vibrations were made from electron-diffraction data.loOv(NbC1) in Cp,NbCl(L) [L = PMe,Ph, P(OMe),, PhCECPh, PhCECH, HC=CH, CNPh, or CNCsHll] is ca. 250 crn-l.lz8 The unit Ta( p-H),Ta in [Ta(-q5-C5Me4Et)ClzH]z(CO) gives v(TaH) bands at ] .( Y ~ ~~- C~, H , ) ~ T ~ ( Bv(TaH) H ~ ) is 1590 and 1560 cm-l [v(TaD) 1140 ~ m - ~ In at 1820-1860cm-1. In (q5-C,H,),TaCKL) ( L = CO or a phosphine) v(TaCI) is always close to 300 cm-l.130 Ta-OR in Ta,Cl,(OBu'), is at 545 ~ m - l . 'Vibrational ~~ data were also given 0. V. Blinova, Yu. B. Predtechenskii, and L. D. Shcherba, Khim. Fiz.,1982, 1562. M. Vandenborre, E. Husson, and J. L. Fourquet, Muter. Res. Bull., 1982,17, 1359. 123 E. Hey, F. Weller, and K. Dehnicke, 2. Anorg. Allg. Chem., 1983, 502, 45. la4 M. Tatsumisago, A. Hamada. T. Minami. and M . Tanaka. J. Am. Ceram. SOC..1983, 66, 117. 125 M. Tatsumisago, A. Hamada, T. Minami, and M. Tanaka, J. Non-Cryst. Solids, 1983,56, 121

423.

Do, E. D. Simhon, and R. H. Holm, Znorg. Chem., 1983, 22, 3809. J. Sala-Pala, J.-L. Migot, J. E. Guerchais, L. Le Gall, and F. Grosjean, J. Orgunomet. Chem., 1983,248, 299. 128 R. Serrano and P. Royo, J . Organomet. Chem., 1983, 247, 33. lagP. A. Belmonte, F. G. N. Cloke, and R. R. Schrock, J. Am. Chem. SOC.,1983, 105,2643. A. Antiiiolo, M. Fajardo, A. Otero, and P. Royo,J. Orgunomet. Chem., 1983,246,269. 131 J.-L. Moransois, L. G. Hubert-Pfalzgraf, and P. Laurent, Znorg. Chim. Actu, 1983,71, 119.

la6Y. 127


215

for TiTa,07.ez1.r. and Raman data for KzTaF, cannot be assigned on the basis of a rigid, distorted, monocapped prismatic structure for the anion at ambient temperature, although a rigid structure appears to be present at low tempera(2) (R = H, Me, Et, Pr, etc.) give v(TaCltermin,,) t u r e ~ The . ~ ~ complexes ~ 350-365 cm-l and v(TaCl,,,,,,) 166 cm-1.1:33

7 Chromium, Molybdenum, and Tungsten

Fourier-transform far4.r. spectroscopy was used to study Cr, molecules in lowtemperature inert-gas matrices. The spectra were strongly dependent on the matrix material and the method of 1.r. and Raman data have been given for [Et,N][HM,(CO),,] (M = Cr, Mo, or W) and K[HCr2(CO)lo].136Another group reported that K[HCr2(CO)lo] gave spectra consistent with Dllh or Dad symmetry, while salts with Bu4N+, K(phen),+, and other related cations appeared to have bent anions with C,, 91

37

Previous reference has been made to work on Cp,CrX(CN) (X = CN, CI, Br, or I)lo3and CpzCr(N3)z.104 v(Cr=N) in CrN(tetra-p-tolylporphinato) has been identified, by 14N/16N substitution, as a weak band at 1015 cm-1.138339Detailed assignments were given for C T ( N H ~ ) ~v(CrP) ~+.~ is ~assigned to a band at 189 cm-l (R = PhCEC) or 186 cm-l (R = Ph) in the Raman spectra of Cr(CO)b(PR3).140 The following Cr-0 species have already been mentioned: trans-[CrX,(OH,),]+ (X = Cl or Br),l Cr02Fz,eCt-Opz-,eand TiM'1Cr2(V04)3(MI' = Co, Ni, Cu, Mg, Ca, Sr, Ba, or Pb).l16 An intense i.r. band at 590 cm-l is due to the skeletal Cr30 group in [(MeCp)CrI4O4 (3).141 The oxochromium(v) cation [O==Cr(salen)]+ [ d e n = N , N R. B. English, A. M. Heyns, and E. C. Reynhardt, J. Phys. C, 1983,16,829. B. Viard, A. Laarif, F. Theobald, and J. Amaudrut, J. Chem. Res. (S),1983,252. G . A. Ozin, M. D. Baker, S. A. Mitchell, and D. F. McIntosh, Angew. Chem., Int. Ed. Engl., 1983, 22, 166. 135 J. Rozibre and A. Potier, Bull. SOC.Chim. Fr., I, 1982, 339. - l W M. D. Grillone and B. B. Kedzia, Bull. Acad. Pol. Sci., Ser. Sci. Chim., 1981,29, 245. 137 M. D. Grillone and B. B. Kedzia, Bull. Acad. Pol. Sci., Ser. Sci. Chim., 1981,29,251. J. W. Buchler, C. Dreher, K.-L. Lay, A. Raap, and K. Gersonde, Inorg. Chem.. 1983.22. 13,

879. J. T. Groves, T. Takahashi, and W. M. Butler, Inorg. Chem., 1983,22,884. 140 A. Hengefeld, J. Kopf, and D. Rehder, Organometallics, 1983,2, 114. la8

A. A. Pasynskii, 1. L. Eremenko, Yu. V. Rakitin, V. M. Novotortsev, 0. G. Ellert, V. T. Kalinnikov, V. E. Shklover, Yu. Y. Struchkov, S. V. Lindeman, T. Kh. Kurbanov, and G. Sh. Gasanov, J . Organomet. Chem., 1983,248,309.

'I1

216


ethylenebis(salicylideneiminato)] gives v(C-0)

in the range 935-997 cm-l, dependent on the ~ a t i 0 n . lv(M=O) ~~ values lie in the expected regions for [MOX5Iz- (M = Cr, Mo, or W, X = C1 or Br).14, (C H Me)

\s4

Raman spectra of Cr042--Crz072-mixtures in aqueous solutions gave a value of log@,,(20 OC, KNO,, 0.8M) of 13.77 k 0.02 for the following reaction:144

2Cr042- t 2H+

+ C T ~ O , ~+- HzO

v(MoMo) was assigned as 424 crn--l in M0z(mhp)4 (mhpH = 6-methyl-2hydroxypyridine). Some tentative Mo-L mode assignments were made from the electronic spectral fine Mo-Mo stretching in [MO,(HASO~)~]~occurs at a lower wavenumber than in the phosphate analogue.14s Cp,Mo(H)SnCI,*DMF gives v(MoH) at 1840 cm-l; hence the hydrogen is essentially non-bridging. In [Cp,Mo(SnCl,)-H +,SnCl,, on the other hand, v(MoHSn) is at 1588 cm-l, shifting to 1173 cm-l on de~teriati0n.l~' v(MoHz) bands are at 1956and 1860 cm-l in [(Ph,MeP),MoH,( ~.-F),MOH~(PM~P~~),]+ A quite detailed vibrational assignment of [Mo(CN)J4- has been v(MoN) in [MO~(NO)~(S~),(S~)(OH)]~is at 608 cm-l, with v(Mo-0H-Mo) at 810 cm-l and v(MoS) at 341 and 315 crn-l.150 The i.r. and Raman spectra of ([Cl(PMezPh)4Re(Nz)]zMoC14} give v( MN), i.e. involving motion of both Re and Mo, at 682 cm-l (alq) and 675 cm-1 (azu),v(ReC1) at 285 cm-l (alq), v(MoC1) at 311 cm-l (al,) and 310 cm-l (a,"), and possibly v(ReP) at 347 cm-l (al9).l5l Work on MOW,),, in low-temperature matrices has been referred to above.2z MoCI,(NSCl), with the NSCl formally acting as a di-anionic ligand, has v,,(Mo=N=S) at 999 cm-l and v,(Mo=N=S) at 418/412 cm-l. [MoCl,value (962 ~ m - 9 . l A ~~ (NSCl)]- has a significantly lower v,,(Mo=N=S) T. L. Siddall, N. Miyaura, J. C. Huffman, and J. L. Kochi, J. Chem. SOC.,Chem. Commun.. 1983, 1185.

J. E. Ferguson, A. M. Greenaway, and B. R. Penfold, Inorg. Chim. Actn, 1983.71. 29. ll4 G. Michel and R. Machirow, J . Raman Spectrosc., 1983, 14, 22. 145 M. C. Manning and W. C. Trogler, J . Am. Chem. SOC.,1983,105, 531 1. 148 J. Ribas, R. Poilblanc, C. Sourisseau, X. Solans, J. L. Brianso, and C. Miravitlles. Trnnsition Met. Chem., 1983, 8, 244. A. N. Protsky, B. M. Bulychev, and G. L. Soloveichik, Znorg. Chim. Acta, 1983, 71, 3 5 . 148 R. H. Crabtree, G . G . Hlatky, and E. M. Holt, J. Am. Chem. SOC.,1983,105, 7302. 140 D. I. Zubritskaya, V. V. Dovgei, and L. I. Pavlenko, Koord. Khim., 1983,9, 1073. lS0 A. Muller, W. Eltzner, H. Bogge, and E. Krickemeyer, Angew. Chem., Int. Ed. Engl.. 143

1983, 22, 884. 151

lh2

J. R. Campbell, R. J. H. Clark, and M. J. Stead, J. Chern. SOC.,Dalton Trnns., 1983, 2005. U. Kynast and K. Dehnicke, 2. Anorg. Allg. Chem., 1983, 502, 29.


21 7

characteristic v(MoN) band is seen at 610 cm-l in the Raman spectra of monoand di-nitrosyl complexes of molybdenum with hydroxylamido, oximato, halogeno, and pseudo-halogeno ligands.ls3 Skeletal {v(Mo=O) and v[Mo(p-O),Mo]) modes in the cis and trans isomers (L = 1,4,7-triazacyclononane)are significantly different from of [Mo2O4L2I2+ one another.ls4 The i.r. band at 730 cm-l in p2-oxobischloro(tetra-p-tolylporphyrinato)molybdenum(Iv) is assigned to v(MoOMo), with v(MoC1) at 280 crn-l.ls6 Moz05L2(L = a tridentate monoanion with one thiolate donor, e.g. Me2NCH2CH2NHCH2CH2S-) gave bands due to (O=),Mo--O-Mo(=O), at 910 and 880 cm-l [v(Mo=O)] and 665-720 cm-l [v(Mo,O)]. These were confirmed by 180-labelling Raman spectra of MO,(O,CR)~(R = H or CF3) were reported; no resonance enhancement of skeletal modes Aqueous solutions of polynuclear molybdates gave Raman spectra showing the presence of MoOa2-, Mo,O,~'-, H~M07024~-, M O ~ O , ~Mo601Q2-, ~-, and M0120372-.158A characteristic shift of v(Mo=O) occurred on going from 12-molybdophosphoric acid (996 cm-l) to an 11-molybdometallophosphoricacid (986-980 cm-1).16D 1.r. and Raman spectra were reported and assigned for Mo2S2X3(SeX3) (X = C1 or Br).160 The symmetric Mo=S=Mo stretch in K6[Mo2(p2-S)(CN),,].4H20 is at 203 cm-l.lel Several groups of workers have reported vibrational assignments for polynuclear thio-anions containing molybdenum: [(P~S)CUS,MOS,CU(SP~)]~and [ ( P ~ S ) C U S ~ M O S , ][(PhS),FeS2MS2I2~-,~~~ (M = Mo or W),lS3 [(S5)FeS2MoS2I2-,le4and M3SD2-(M = Mo or W).le5 The i.r. spectra of MO,S~~(S,CNR~)~ (R = Me, Et, etc.) show that there are two terminal and two bridging Se atoms.166 Other Mo-0 and Mo-S species for which vibrational assignments have been given are listed in Table 4.12,23,68,69,78,110,167--180

A. Muller, W. Eltzner, S. Sarkar, H. Bogge, P. J. Aymonino, N. Mohan. U. Seyer, and P. Subramanian, Z. Anorg. Allg. Chem., 1983, 503, 22. 154 K. Wieghardt, M. Hahn. W. Swiridoff. and J. Weiss, Angew. Chem., Znt. Ed. Engl., 1983. 22, 491. J. Colin, B. Chevrier, A. De Cian, and R. Weiss, Angew. Chem.. Znt. Ed. Engl., 1983, 22, 247. lB8 C. P. Marabella, J. H. Enemark, K. F. Miller, A. E. Bruce, N. Pariyadath, J. L. Corbin, and E. I. Stiefer, Inorg. Chem., 1983, 22, 3456. 16' M. C. Manning, G. F. Holland, D. E. Ellis, and W. C. Trogler, J. Phys. Chem.. 1983. 87. 3083. 158 K. Murata and S . Ikeda, Spectrochim. Acta, Part A , 1983,39,787. l69 K. Murata and S . Ikeda, Anal. Chim. Acta, 1983, 151,29. 180 S. V. Volkov, V. L. Kolesnichenko, N. G. Timoshchenko, and N. G. Aleksandrova, Ukr. Khim. Zh. (Russ. Ed.), 1983, 49, 563. 161 C. Potvin, J. M. Manoli, and J. M. Bregeault, Znorg. Chim. Acta, 1983,72, 103. la* S. R. Acott, C. D. Garner, J. R. Nicholson, and W. Clegg, J. Chem. Soc., Dalton Trans., 1983, 713. R. J. H. Clark, T. J. Dines, and G. P. Proud, J. Chem. SOC.,Dalton Trans., 1983,2299. D. Coucouvanis, P. Stremple, E. D. Simhon, D. Swenson, N. C. Baenziger, M.Draganjac. L. T. Chan, A. Simopoulos, and V. Papaefthymiou, Znorg. Chem., 1983,22,293. W. H. Pau, M. Leonowicz, and E. I. Stiefel, Znorg. Chem., 1983, 22, 672. 188 K. S. Nagaraja and M. R. Udupa, Transition Met. Chem., 1983, 8, 191.

218


Table 4 Molybdenum-oxygen and -sulphur species for which vibrational assignments have been proposed Species

Ref.

WO,,23 167 M1M1"(MoO4),(MI = K, Rb, or Cs, MI" = Al or Sc) LiSc( MOO,), 168 78 LnM0,Cl (Ln = lanthanoid, M = Mo or W) GdTb(MOO,), I69 12 Ln,(E0,),-4Ln(Re04), (Ln = Y or Dy, E = Mo or W) Tbi&o.2(MoOd3 68 BaGd(MOO,), 69 170 ~ ~ S - [ M O O X ( C ~ H ~ ~(X N= O )0~ ]or S ) [MoO(OHz)(CN),l2I71 MoO,(RX), [RX = RN(O-)C(=O)C,H,X, R = H, Me, or Ph, X == OMe, 172 Me, H, C1, or NOz] CedMoO4)3, P-Ce2M04015, Y'Ce2M03013, Ce8MOl2O49 173 174 Mo,(fhp),(THF) (fhp = FCeHaN-O-) (R-Cp)Mo(=O)(y-0)( y-NAr)Mo(=O)(Cp-R) (R = H or Me, 175, 176 Ar = Ph, etc.) 177 [Mo,O a(SAr)doMe) 1Mo,04(glycinato),(H,0)2 178 (NH4)BMo7024 ' 4HZo 179 H,+n[PMo12-nVnO,OI (n = -3) 110 a- and P-[xM,2040]"- (X = BI", SiIV, GetV,Pv, or As", M = Mo or W) 180 p-9

v(WW) in W2(02CCF3),is seen in the Raman spectrum at 310 cm-l, consistent with quadruple W E W bonding.lS1 In the complex (OC),CoW(CO),(=CPh) v(W=C) is at 1372 cm-l.laz The complexes W(NR)C14 (R = Ph or Et) have

le7 16*

V. V. Fomichev, V. A. Efremov, D. D. Baldanova, 0. L. Kondratov, and K. I. Petrov, Russ. J. Inorg. Chem., 1983,28,669. N. V. Porotnikov, V. R. Safonov, N. G. Chaban, and K. I. Petrov, Rurs. J. Inorg. Chem.,

1982,27, 1128.

S. S. Saleem, G. Aruldhas, and H. D. Bist, Spectrochim. Acta, Part A , 1983,39,1049. S. Bristow, D. Collison, C. D. Garner, and W. Clegg, J. Chem. SOC.,Dalton Trans., 1983, 2495. 171 K. Wieghardt, G. Backes-Dahmann, W. Holzbach, W. J. Swiridoff. and J. Weiss, 2. Anorg. Allg. Chem., 1983,499,44. 17, P. Ghosh and A. Chakravorty, Znorg. Chem., 1983,22,1322. T . L. Barr, C. G. Fries, F. Cariati, J. C. J. Bart, and N. Giordano, J. Chem. SOC.,Dalton Trans., 1983, 1825. F.A. Cotton, L. R. Falvello, S. Han, and W. Wang, Inorg. Chem., 1983,22,4106. l 7 5 H. Alper, J.-F. Petrignani, F. W. B. Einstein, and A. C. Willis, J . Am. Chem. Soc., 1983, 105, 1701. 178 J.-F. Petrignani and H. Alper, Znorg. Chim. Acta, 1983,77,L243. 177 I. Buchanan, W. Clegg, C. D. Garner, and G. M. Sheldrick, Inorg. Chem., 1983,22,3657. 178 M.Chaudhury, J. Chem. SOC.,Dalton Trans., 1983,857. 170 M.E. Escobar and E. J. Baran, Afinidad, 1982,39,409. 180 C. Rocchccioli-Deltcheff, M. Fournier, R. Franck, and R. Thouvenot, Inorg. Chern., 1983,22, 207. lS1D. J. Santure, K. W. McLaughlin, J. C. Huffman, and A. P. Sattelberger, Znorg. Chem.. 1983,22, 1877. E. 0.Fischer, P. Friedrich, T. L. Lindner, D. Neugebauer, F. R. Kreissl, W. Uedelhoven, N. Q. Dao, and G. Huttner, J. Organomet. Chem., 1983,247,239. 170


219

v(W=N) at 1100 cm-l (R = Ph) or 1104 cm-l (R = Et) and v(WC1) at 350 cm-l (Ph) or 341 cm-l (Et).lE3 v(W=O) and v(WF) bands were assigned in WOF,.L (L = a phosphorylcontaining ligand); the L is trans to the oxygen. Increasing the basicity of L leads to decreases in both v(W==O) and v(WF).lE4w20&4, W204L2,W202S2L2, and W203SL2[HL = PhN(Et)CS,H or CyN(Me)CS,H] give v(W=Oterminal) 940-952 cm-l. The monoxo-, dioxo-, and oxo-sulphido-bridged species all give two bands in the range 815-440 cm-l due to v&-,s(WObridee)and v,(WObridge). V,,(WSbridgc) and v,(WSbridge) were ca. 470 cm-l and ca. 365 cm-l, respective1y.la6 Other W - 0 , W-S, and W-Se species investigated were CuLn(WO,), (Ln = lanthanoid),lss KSm(W0,),,80 Ln,WO,CI, (Ln = lanthan~id),'~[GaW,,04016- ,187 [PW12040]3-,188 W(=E)X4 (E = S or Se, X = F, CI, or Br),24and [Co(WS,)J- (n = 2 or 3).lE9 v(WC1) was identified at 258 cm-l in [WCI(PMe,Ph),( p3-N2)]2(AIC12)2.1go Normal-co-ordinate analyses for WC16, WOCI,, W02C12, and W 0 3 showed that the isolated-molecule approach could not give a satisfactory result .lgl 8 Manganese, Technetium, and Rhenium

The i.r. spectra of MnRl, and LiMnRl, [R1 = R22N(CH2)3-, R2 = Me or Et, Raa = (CH,),] contain bands due to v,,(MnC) near 550 cm-l and v(MnN) near 4 8 0 ~ m - l . lA ~ ~detailed assignment of the vibrational spectrum of Mn(CO),Me has been given.2s Mn'"(TPP)(N,), (TPP = 5,10,15,20-tetraphenylporphinato) has v(Mn-N,) at 418 cm-l, while v(Mn-NCS) in the analogous thiocyanato complex gives bands at 428 and 446 cm-l.lB3 v[MnN(NCS)] and v[MnN(bipy)] for Mn(bipy)(NCS), and the Co" complex are at 257 and 250 cm-l (Mn) or 269 and 250 cm-1 (Co), respectively. B4 (Iodosylbenzene)manganese(rv) porphyrin complexes give bands due to v(Mn0Mn) at 810 cm-l and to v(MnO1) at 575 cm-l, based on 180-labelling e x p e r i r n e n t ~ .Other ~ ~ ~ M n - 0 systems studied are Mn04-,11 Mn20,,26 Mn(octaethylp~rphinato),~~MnLCl (HL = thiosemicarbazone of a-hydroxyD. C. Bradley, M. B. Hursthouse, K. M. A. Malik, A. J. Nielson, and R. L. Short, J . Chem. SOC.,Dalton Trans., 1983, 2651. lE4 M. E. Ignatov, B. V. Golovanov, V. D. Butskii, and E. G. Il'in, Russ. J . Znorg. Chem., 183

1983,28,978.

R. Lozano, E. Alarcon, A. L. Doadrio, and A. Doadrio, Polyhedron, 1983,2,435. G. A. Arzumanyan, Koord. Khim., 1982, 8, 1464. M. V. Mokhosoev, L. G. Maksimova, L. V. Tumurova, and N. A. Suranova, Russ. J . Znorg. Chem., 1983, 28, 818. lS8S. S. Saleem and G. Aruldhas, Indian J. Pure Appl. Phys., 1983, 21, 112. 18B A. Muller, W. Hellmann, U. Schimanski, R. Jostes, and W. E. Newton. Z . Naturforsch., Teil B, 1983, 38, 528. l9O T. Takahashi, T. Kodana, A. Watanabe, Y . Uchida, and M. Hidai, J . Am. Chem. SOC., 186

1983,105, 1680. lQ1 E.

A. Pisarev, 0. I. Kondratov, D. V. Drobot, and V. V. Fomichev, Russ. J . Znorg. Chem.,

1982, 27, 1397.

A. Shakoor, K. Jacob, and K.-H. Thiele, 2. Anorg. Allg. Chem., 1983,498, 115. M. J. Camenzind, F. J. Hollander, and C. L. Hill, Inorg. Chem., 1983, 22, 3776. lg4 B. W. Dockum, G. A. Eisman, E. H. Witten, and W. M. Reiff, Znorg. Chem., 1983,22,150. lg5J. A. Smegal, B. C. Schardt, and C. L. Hill, J . Am. Chem. SOC.,1983,105, 3510. 1B8 lg3


220

@-naphthaldehyde),lgsand M(XCsH4Se02)2(M = Mn or Fe, X = H, p-C1, rn-CI, p-Br, m-Br, or p-Me).lg7 In addition to that of MnTiF,.6H202 the Raman spectrum of “Me,][MnCl,] has been analysed.lG8 Full vibrational assignments have been made for [TcOX,]- (X = C1, Br, or I), and these were backed up by a normal-co-ordinate analysis. This showed that k(T-0) was in the sequence C1 2 Br > I, and the k(TcX) values followed the same trend.lg9 Assignments have also been given for [M0X5l2- (M = Tc or Re, X = C1 or Br).14, v,,(Re=N=S) is at 948 cm-l in [(Cl,PO)ReCI,(NSCI),] and 930 cm-l in [(Cl,PO)ReCl,(NSCl)] ;v,(Re=N=S) was not observed.200v(ReN) and v(ReC1) modes were assigned in { [C1(PMe2Ph),Re(N2)]2MoCI,}.151 In addition to work on MReO, (M = K or Cs)27928 and on Ln2(EO,),.4Ln(ReOJ, (Ln = Dy or Y,E = Mo or W)12 assignments of v(Re0) modes were proposed for trans-[ReI,O(OR)(PPh,),] (R = Me or Et) (930-945 cm-l),,O1 Fe(Re0,)2.4H20,202and the apatites Balo(Re0,),X2 (X = F, C1, Br, I, Nor, or iC03).203*204 v(ReS,) modes in R,SnCS,Re(CO), (R = Me or Ph) are seen near 360cm-l and 380-390 cm-1.20K The complex Re2C14(DPPP)2[DPPP = Ph2P(CH2),PPh,] gives two v(ReC1) bands in the i.r. (307 and 270cm-l). This is consistent with CZhpoint-group symmetry for the 9 Iron, Ruthenium, and Osmium

v(FeH) in FeH(C,H,PPhCH,CH,PPh2)(Ph2PCH,CH,PPh,)is at 1890 The complex [Fe(NO),(CO)Ph2P],NH gives v(FeC) at 445 cm-l and v(FeN) at 562 cm-1.208 The resonance Raman spectrum of (TPPFe)2N (TPP = tetraphenylporphyrin) contains a band at 424 cm-l assigned as v,(FeNFe), which is shifted 6 cm-l on 64Fesubstitution. Bands of very low wavenumber were assigned to Fe(N,,,,,,,), out-of-plane deformations resonance-enhanced via a chargetransfer v(FeN) modes were assigned for FeBr,L, complexes (L = 4-aminobenzophenone, n = 1 4 or 6).210 lg6Y. 197 G.

K. Bhoon, Polyhedron, 1983,2, 365. Candrini, W. Malavasi, C. Preti, G. Tosi, and P. Zannini, Spectrochim. Actn. Part A ,

1983, 39, 635.

Y. Mlik and M. Couzi, J. Phys. C, 1982,15, 6891. E. J. Baran and C. I. Cabello, Z. Nuturforsch., Teil A , 1983, 38, 563. 200 U. Miiller, W. Kafitz, and K. Dehnicke, Z. Anorg. Allg. Chem., 1983, 501, 69. 801 G. F. Cianai, G. D’Alfonso, P. Romiti, A. Sironi, and M. Freni, Znorg. Chim. Actn, lg8 l99

1983, 72, 29. 202

L. L. Zaitseva, A. V. Velichko, and G. Yu. Kolomeitsev, Russ. J. Znorg. Chem., 1983, 28, 530.

E. J. Baran, M. Aneas, and J.-P. Besse, Z. Nuturforsch., Teil B, 1983, 38, 526. 204 E. J. Baran, G. Baud, and J.-P. Besse, Spectrochim. Actu, Part A , 1983, 39, 383. 205 T. Hattich and U. Kunze, 2. Nuturforsch., Teil B, 1983, 38, 655. N. F. Cole, F. A. Cotton, G. L. Powell, and T. J. Smith, Znorg. Chem.. 1983. 22, 2618. 207 H. Azizian and R. H. Morris, Znorg. Chem., 1983, 22, 6. 208 J. Ellermann and W. Wend, J . Organomet. Chem., 1983, 258, 21. 209 G. A. Schick and D. F. Bolian, J. Am. Chem. Soc., 1983, 105, 1830. alo I. M. Vezzosi, A. F. Zanoli, and G. Peyronel, Znorg. Chim. Actu, 1983, 72, 1. a03

22 I

Vibrational Spectra oj. Transition-elementCompounds

Earlier references to Fe-0 systems are Fe203/V205,114 Fe(octaethy1porand Fe(XC,H,SeOz)z phinato),13 FeL, (L = aromatic hydroxyo~imes),~~ (X = H, C1, Br, or Me).'@' v(Fe0) in Fe[C1C(COOEt)z]3is at 453 cm-l.zll The linear ion [C1,Fe=O=FeC13]2- gave the following vibrational wavenumbers: v,,(FeOFe) (az,) 875 cm-l, 8(FeOFe) (e,) 210 cm-l, and v(FeC1,) (e,) 359 cm-' and (a2,) 315 crn-l.,12 Oxygen reacts with (phthalocyaninato)iron(rI) to form two different species, both containing an Fe-0-Fe group. 180-Labelling experiments show that two bands, at 852 and 824 cm-l, are both due to an antisymmetric Fe-0-Fe stretch. Hence, two species are present, and they are believed to differ in their Fe-0-Fe bond angles and in the relative arrangements of the two phthalocyanine subunits Unambiguous assignments have been given for the iron-histidine stretching vibration in deoxymyoglobin, deoxyhaemoglobin, and ferrohorseradish peroxida~e.~l* Vibrational assignments have been reported for [(PhS),FeS2MSJ2- (M = Mo or W)163J64 and matrix-isolated FeCl, and FeCl,.,@

.

0 I /H H-RU I H ' PPh,

The Ru-Ru

stretches in the cluster HRU,(CO)~,(O--S~=) on a silica surface

are at 200 and 155 cm-1.216 The complex (4) has v(RuH) bands at 2040 and

1995 cm-l in the i.r., consistent with C,, local symmetry.21a For RuHCl(CS)(PPh,), v(RuH) is at 2027 cm-l and 8(RuH) at 787 cm-l. v(RuH) bands were also assigned in RU($-O,CR)H(CS)(PP~,),.~~~ v(RuC) modes in the cyclorut henapentadienyl complexes [(OC),RuC4(CHzOH),]Ru(CO) and [(OC),RUC~(CH~CH~OH)~E~~]RU(CO), are found in the range 540-560 cm-1.z18 The anion [Ru(NCS),]~- has the following v(RuN) wavenumbers: (al,) 340, (e,) 277, (tl,) 337 cm- J*9 A fairly detailed assignment of skeletal modes was proposed for RU(NO)(NH~)~(OH)~+, with various counter-ions.z20v(RuAs) is

,

211 Z12

W. Petz and S. Kremer, Z . Naturforsch., Teil B, 1983, 38, 30. K. Dehnicke, H. Prinz, W. Massa, J. Pebler, and R. Schmidt, 2. Anorg. Allg. Chem., 1983, 499,20.

213

C. Ercolani, M. Gardini, F. Monacelli, G . Pennesi, and G. Rossi, Inorg. Chem., 1983,22, 2584.

2l4

T. Kitagawa, Oxygenases Oxygen Metab. Symp. Honor Osamu Hayaishi, 1981, 1982, 451

(Chem. Abstr. 1983, 98, 103 453). A. Theolier, A. Choplin, L. D'Ornelas, and J. M. Basset, Polyhedron, 1983, 2, 119. S. G. Davies, S. D. Moon, and S. J. Simpson, J. Chem. Soc., Chem. Commun., 1983, 1278. 217 P. J. Brothers and W. R. Roper, J . Organomet. Chem., 1983,258, 73. A. Astier, J.-C. Daran, Y.Jeannin, and C. Rigault, J . Organomet. Chem., 1983, 241, 53. zlo H.-H. Fricke and W. Preetz, Z . Naturforsch., Teil B, 1983,38, 917. 220 N. M. Sinitsyn, G. G . Novitskii, I. A. Khartonik, V. V. Borisov, and A. B. Kovrikov, Russ. J . Inorg. Chem., 1982, 27, 1152. 215

222


said to be at 490cm-l in the complexes RuCl,(As-p-Tol,),L (L = MeOH, Me,CO, MeCN, or PhCN) and RuCl,(As-p-Tol,)(L-L) (L-L = bipy or phen) 221 v(RuS) is in the range 47-74 cm-l in the sulphido-bridged species Ru(N0)X2LzS(X = C1 or Br, L = PPh, or ASP^,).,^, The Ru-halogen stretches in RU(XC,&S~O,)~Y (X = H or halogen, Y = C1 or Br) are ca. 260 cm-1 (Y = Cl) or ca. 175 cm-l (Y = Br). Hence these are polymers, with bridging Y atoms.223The complex (Bu'DMP)Ru(C0)2C12 (Bu'DMP = l-t-butyl-3,4-dimethylphosphole)gives four v(RuC1) [and four v(CO)] bands, showing that it is a mixture of isomers (5a and 5b).224 The complexes RuX,L, [X = C1 or Br, L = ArN=NC(R)=NOH, R =Me or Ph, Ar = Ph or p-tolyl] give two v(RuX,) bands in the i.r., consistent with cis geometry.226

.

c1

c1

Bands due to v(0sH) were assigned in C~~-[OS(L-L)(CO)H]+.~~~ Skeletal modes associated with the Os,H group were assigned for Os,(CO),,(pH)(p+CH=CH,). A normal-co-ordinate analysis shows that there is extensive coupling between vs(Os3H) and an out-of-plane CH-CH2 deformation. v,,(Os,H) was at 1394 Osmium carbyne complexes such as OsCl(CPh)(CO)(PPh,), have v(Os=C) bands in the range 1355-1420 cm-1.228 ~[OS-N(NO)] (620 cm-l) and v[Os-N(N,)] (372 cm-l) bands were assigned in [OS(NO)(N,),]~-. [Os(NO)(N,),phen] gives similar v(0sN) is at 592 cm-l and v(OsC1,) at 318-340 cm-l in [OsC1,(NO)(SnCl,),]2-.230 Bands due to v[Os(NS),] and v(OsC1) were assigned for cis-[OsCl,(NS),] and compound (6).231 v(Os=O)

and v(Os0) features were identified in [OSO,(L-L),]~- (L-L = oxalato or malonato). The wavenumbers are lower for the malonato complex, showing that there is weaker x-bonding in the osmyl group in this case.,,, M. M. T. Khan and K. V. Reddy, Inorg. Chim. Acta, 1983,73,269. K. K.Pandey, Spectrochim. Acta, Part A , 1983,39, 925. 823 C. Preti, L. Tassi, and G. Tosi, Spectrochim. Acta, Part A , 1983, 39, 1. 224 L. M.Wilkes, J. H. Nelson, L. B. McCusker, K.Seff, and F. Mathey, Znorg. Chem., 1983, 22, 2476. 2z5 A. R. Chakravarty, A. Chakravorty, F. A. Cotton, L. R. Falvello, B. K. Ghosh, and M. Tomas, Inorg. Chem., 1983,22, 1892. 226 J. V. Caspar, B. P. Sullivan, and T. J. Meyer, Organometallics, 1983,2,551. a27 J. Evans and G. S. McNulty, J. Chem. SOC.,Dalton Trans., 1983, 639. 228 G. R. Clark, N. R. Edmonds, R. A. Pauptit, W. R. Roper, J. M. Waters, and A. H. Wright, J. Organomet. Chem., 1983,244,C57. 2z9 R. G. Bhattacharyya and A. M. Saha, Znorg. Chim. Acta, 1983,77, L81. 230 B. Czeska, F. Weller, and K. Dehnicke, 2. Anorg. Allg. Chern., 1983,498, 121. 231 R. Weber, U. Muller, and K. Dehnicke, Z . Anorg. Allg. Chem., 1983,504, 13. 232 W. Preetz and H. Schilz, 2. Naturforsch., Teil 8, 1983,38,183. 221

222


223

Deuteriation experiments showed that v(Os=O) bands in [OSO,(OH),]~-(with various cations) are in the range 730-870 cm-l, with 6(O=Os=O) and v(Os0) at 485-640 ~ m - The ~ characteristic . ~ ~ ~ v,,(O=Os=O) band in 0 ~ 0 ~ B r , ( P P h , ) ~ The i.r. spectrum of Na2[Os0,(OH),] suggests that the anion is at 847 is dimeric and linked by two bridging oxygens. v(Os,O,) was near 600 cm-1.235

1Skeletal modes have been assigned for a variety of complexes containing the units Os02S4, ass,, OsSe,, and OsS4Cl,. Likely assignments (approximate values only) are: v(0sS) 390 cm-l, 6(OsS) 140 cm-l, v(0sSe) 280 cm-l, G(0sSe) 100 ~ m - l . ~ ~ * vas(OsC12)in [ O S C I ~ L ~(L ] ~= N,N'-dimethyl- or IV,N'-diethyl-imidazoline2-thione) is at ca. 300 Four v(OsC1) bands were seen in the i.r. for solid [Os(NO)Cl,]-, showing that the symmetry is less than C4".This agrees with crystallographic results indicating a site symmetry of C, for the molecule in the (X = C1 or Br, R1 = Me The complexes OS~(~-O)(~-O~CR~)X~(PR~,)~ or Et, PRZ3= PPh, or PEt,Ph) give v(0sCI) at 340-350 cm-l and v(OsBr) at 225-240 cm-l. No band was assignable to V ( O S O O S ) . ~ ~ ~ +

10 Cobalt, Rhodium, and Iridium

A revised assignment of skeletal modes [v(CoC), S(CoCO)] has been given for ClHgCo(CO),, Hg[Co(CO),],, and Co2(CO),. These were based on analogous iron Skeletal (metal-ligand) modes have been assigned for [Co(NH3),X]X2 (X = Cl or Br).2411.r. spectra of mixed crystals Co,-,Ni,P,S, contained bands due to v(CoS) (152-159 cm-l) and v(NiS) (184-187 Other assignments involving cobalt compounds are summarized in Table 5 .10,13,14,2 9,30,9 8,194,24 3-26 3 B. N. Ivanov-Emin, N. A. Nevskaya, B. E. Zaitsev, N. N. Nevskii, and Yu. N. Medvedev. Russ. J . Znorg. Chem., 1983,28, 704. a3r J. E. Armstrong and R. A. Walton, Znorg. Chem., 1983,22, 1545. 236 I. V. Lin'ko, A. K. Molodkin, B. E. Zaitsev, V. P. Dolganev, and N. U . Venskovskii, Russ. J . Znorg. Chem., 1983, 28, 998. F. Cristiani, F. A. Devillanova, A. Diaz, and G. Verani, Spectrochim. Acta, Part A, 238

1983, 39, 955. 837

arl

L. Antolini, F. Cristiani, F. A. Devillanova, A. Diaz, and G. Verani, J . Chem. Soc.. Dalton Trans., 1983, 1261. B. Czeska, K. Dehnicke, and D. Fenske, Z . Naturforsch., Ted B, 1983, 38, 1031. J. E. Armstrong, W. R. Robinson, and R. A. Walton, Znorg. Chem., 1983,22, 1301. M. van Rentergem, E. G. Claeys, and G. P. van der Kelen, J . Mot. Srrucr., 1983, 99, 207. G. Diaz F. and C. A. Tellez S., Semina (Londrinu, Braz.), 1983, 3, 263. G. Klicke, 2.Naturforsch., Ted A , 1983, 38, 1133.


224

Table 5

Vibrational assignments in cobalt complexes

Species

Ref.

H 3Co(CN)8 K3[Co(CN)5N31 [C0(NH3)J3+ CoL2(N3),(L = 3- or 4-substituted pyridine) CoL, (L = valine) [CoL3I3+(L = several aminopropanols)

243 244

Ezzk2}(X

=

C1 or Br, L

=

10

245 246 247

2-acetyl- or 2-benzoyl-pyridinehydrazone)

CO(biPY)(NCS), Co(RIz),(sf),(H,O) ,, (RIz = alkylimidazole,sf = substituted phenolate anion, n=Oorl) CoLX, [X = C1, Br, I, or NCS, L = 1,2-bis-(2-benzothiazolyl)ethane] [C~(gly),(ox),(en),](~-~-~Y)+ (gly = glycinate. ox = oxalate, x v + z = 3) CoL, (L = aromatic hydroxyoxime) Co(octaethy1porphinato) Co(pyO)62f [Co(q-Cp)(X)(S,CNR',)] (X = halide, CN, NCS, efc., R1 = various, L = PR2,, py, H20, etc.) [CO(TCP)(L)(S2CNR'z) I Co(S,CNPri,), CoC1, (matrix-isolated, n = 1-3) Cs,CoCI 5

+

}

248 194 249 250 30

14 13

25 1 252

+

98 29 253

v(RhH) has been assigned in compound (7) (R = alkyl) and related species.264 Such modes are also reported for [Rh(~-C,H,)H(dppe)]+[dppe = Ph,P(CH,),PPh, J [v(RhH) 2032 cm-l] and [RhH(dppp)CI,], [dppp Ph2P(CH2),PPh21 [v(RhH) 2060 and 1988 cm-'1. The latter also has v(RhC1) at 320, 290, and 280 cm-1.266 5

PBut, @{,h-R PBut,

S. U. Qureshi and B. M. Chadwick, Pak. J. Sci. Znd. Res., 1982,25,95. J. L. Amalvy, E. L. Varetti, P. J. Aymonino, E. E. Castellano, 0. E. Piro, and G. Punte, J . Crystallogr. Spectrosc. Res., 1983, 13, 107. 245 N. A. S . Goher, Acta Chim. Hung., 1983,112,205. 246 C . W. Moszczenski and R. J. Hooper, Znorg. Chim. Acta, 1983,70, 71. 247 G. Nieuwpoort and J. Reedijk, Inorg. Chim. Acta, 1983,71, 125. 248 D. Demertzi and D. Nicholls, Znorg. Chim. Acta, 1983. 73, 37. 249 R. C. van Landschoot, J. A. M. van Hest, and J. Reedijk, Znorg. Chim. Acta, 1983, 72, 89. 250 G. C. Wellon, D. V. Bautista, L. K. Thompson, and F. W. Hartstock, Znorg. Chim. Acta, 243

244

1983, 75, 271.

J. F. Arenas, J. I. Marcos, and J. C. Otero, J. Raman Spectrosc., 1983, 14, 7. 252 J. Doherty and A. R. Manning, J. Organomet. Chem., 1983,253, 81. 253 M.Natarajan, J. Quinn, and E. A. Secco, J. Solid-State Chem., 1983, 49, 258. 254 S. Nemeh, C. Jensen, E. Binamila-Soriaga, and W. C. Kaska, Organometallics, 1983, 2, 251

1442. 256

F. Faraone, G. Bruno, S. Lo Schiavo, G. Tresoldi, and G. Bombieri, J. Chem. SOC., Dalton Trans., 1983,433.


225

Skeletal-mode assignments were given for [Rh(NCS),(SCN),-,]3- for n = M.31 v(RhC1) wavenumbers have been listed for RhCl(C0)L and trans[RhCI(CO)L2][L = Ph2P(CH2).SPh, n = 1 or 2].26s

Numerous assignments of v(1rH) modes have been proposed, e.g. for (8) (R = OMe or R2 = OCH2CMe2CH20or OCMezCMez0),257 (9) (P = P B U ~ ~ ) , ~ ~ * and other systems summarized in Table 6.259-2s3

Table 6 Iridium hydride complexes for which v(TrH) assignments have been made Species

Ref.

[IrH(SMe)(dppe)I+ [dppe = Ph2P(CH2)2PPh2] IrHCl,(CSe)(PPh

3)2

(q6-CsMe5)(PMe3)IrH(R)(R = H, alkyl, or aryl) cis-IrH,(N,)(PPh,),

(q6-C,Me6)IrH,(SiEt3)C1

259 260 26 1 262 263

The complexes [Ir(NCS),(SCN),-,]3- (n = 0-5) have been characterized. v(IrN) is in the range 300-325 cm-l, v(1rS) at 255-313 cm-I. For n = 2 or 3, pairs of geometrical isomers are formed.264 Skeletal bands have been assigned, with the assistance of a normal-co-ordinate analysis, for the trimetallic complexes IrCl(SnCl,)(HgCl)(CO)(PR,), (R = P-XC,& X = H, MeO, F, or CI). The only isomer formed has the fragment CI ,Sn--Tr--Hg-C1 and trans phosphine ligands.265

A. R. Sanger, Can. J. Chem., 1983, 61, 2214. M. A. Bennett and T. R. B. Mitchell, J. Organomet. Chem., 1983,250, 499. 258 E. Guilmet, A. Maisonnat, and R. Poilblanc, Organometallics, 1983,2, 11 23. 250 J. E. Hoots and T. B. Rauchfuss, Inorg. Chem., 1983,22, 2806. W. R. Roper and K. G. Town, J. Organomet. Chem., 1983,252, C97. a61 A. H. Janowicz and R. G. Bergman, J. Am. Chem. SOC.,1983,105,3929. 262 I. Walker and J. Strlhle, 2. Anorg. Allg. Chem., 1983,506, 13. atuM.-J. Fernandez and P. M. Maitlis, Organometallics, 1983, 2, 164. 86Q H.-H. Fricke and W. Preetz, 2. Anorg. Allg. Chem., 1983, 507, 23. 966 M. Kretschmer, P. S. Pregosin, P. Favie, and C. W. Schaepfer, J . Organomet. Chem., a57

1983, 253, 17.

226

Spectroscopic Properties of Inorganic and Organometaiiic Compounds 11 Nickel, Palladium, and Platinum

The complexes NiL (L

= ethylenediamine or 1,3-diaminopropanederivatives of 2,2'-dihydroxychalcones) give v(NiN), mixed with ligand modes, at 500600 cm-l, ca. 460 cm-l, and ca. 370 crn-l. v(Ni0) is in the range 295-310 Cm-1 266 [Ni(S4),]2-, which X-ray crystallography shows to have an approximately square-planar NiS4 skeleton, has vs(NiS4)(Raman) at 293 cm-l and v,,(NiS4) (i.r.) at 280 NiL [L = piperazinebis(dithiocarbamate)] gives v(NiS) at ca. 350-370 cm-1.z6s F atoms react with palladium metal to produce PdF6, for which v3 is at 711 ~ m - v(MC1) ~ . ~has ~ been ~ assigned for complexes (lo), i.e. 315 cm-l for M = Pd, 330 cm-l for M = Pt.270In complex (11) and related complexes v(PdC1) lies in the range 260-290cm-l, showing that C and C1 are trans to one another.271v(PdC1) was also assigned in PdCl(q3-YC3H4)(CNR)(Y = H or Me, R = Me, g-C,H@Me, p-C6H4C1, etc.) and in PdCl(q3-2-MeC,H4)[C(NHR1)(NR2,)] (R2 = Me or Et, R1 =p-C6H40Me or p-C6H4Me).272 Similarly, v(PdC1) and v(PdBr) were given for Pd(L-L)X4 [X = C1, L-L = bipy, phen, Me2P(CH2)2PMe2,PhzAs(CH,),AsPh,, etc.; X = Br, L-L = Me2P(CH,),PMe,, Me,As(CH,),AsMe,, or o - C ~ H ~ ( A S M ~ , ) , ] . ~ ~ ~

\ /

NMe,

I:

C

M But,P

/ \

0'

I .C

%O

(10)

( 1 1) n

The v(PtH) for compound (12) (P P = Ph2PCH2PPh2)is at 2024 (R1 = R2= Et, Cy, bridging v(PtHzPt) band in [(R1,P),Pt( pH)2PtY(PR23)2]+ or Ph for Y = H; R1 = R2 = Et for Y = Ph; R1 = Ph, R2 = Cy for Y = H) is a very broad, weak i.r. feature, 1500-2000 cm-l. The complexes with terminal hydride give v(PtH,) at 2150-2250 ~ r n - l . , Raman ~~ spectra of [Pt,H,(dppe),]'S. A. Patil and V. H. Kulkarni, Znorg. Chim. Acta, 1983, 73, 125. 267 268

268

270

A. Miiller, E. Krickemeyer, H. Bogge, W. Clegg, and G. M. Sheldrick, Angew. Chem., Znt. Ed. Engl., 1983, 22, 1006. S . V. Larionov, L. A. Kosareva, V. N. Ikorskii, and E. M. Uskov, Russ. J. Inorg. Chem., 1982, 27, 976. A. A. Timakov, V. N. Prusakov, and Yu. V. Drobyshevskii, Russ. J. Inorg. Chem., 1982, 27, 1704. E. Ambach, U. Nagel, and W. Beck, Chem. Ber., 1983, 116, 659.

J. Granell, J. Sales, J. Vilarrasa, J. P. Declerq, G. Germain, C. Miravitlles, and X.Solans, J . Chem. SOC.,Dalton Trans., 1983, 2441. A. Scrivanti, G. Carturan, and B. Crociani, Organometallics, 1983, 2, 1612. 273 L. R. Gray, D. J. Gulliver, W. Levason, and M. Webster, J. Chem. SOC.,Dalton Trans.. *71

1983, 133. 274 276

J. R . Fisher, A. J. Mills, S. Sumner, M. P. Brown, M. A. Thomson, R. J. Puddephatt. A. A. Frew, L. Manojlovic-Muir, and K. W. Muir, Organometallics, 1982, 1, 1421. F. Bachechi, G. Bracher, D. M. Gorve, B. Kellenberger, P. S. Pregosin, L. M. Venanzi, and L. Zambonelli, Znorg. Chem., 1983,22, 1031.

227


show v(PtH,) at 2030cm-l, with a feature assigned as v(PtHPt) at 700cm-l; the i.r. only shows a v(PtH,) band, at 2008 ~rn-l.,'~ The complexes trans-[PtCl,(CH,=CH,)(R-an)] (R-an is a substituted aniline) show that v(PtC,) and v(J3N) are both increased by the presence of electronreleasing groups in R-an.277Skeletal modes were also assigned in trans-IptX,(CH,=CH,)(pyrazine)] and trans-[Pt,X,(CH,=CH,),(pyrazine)] (X = C1, Br, or I).278 H-Pt -Pt-CO I

I

Table 7 Vibrational assignments in nickel, palladium, and platinum complexes Species

Ref.

NiL,(N,), (L = 3- or Csubstituted pyridines) INiL,la+ (L = aminopropanols) NiL, (L = 4-hydroxy-L-prolinato) Ni(RIz),(sf),(H,O). (RIz = alkylimidazole,sf = substituted phenolate anion, n=Oorl) NiL,*-, NiLs4- (L = oxamate or -OOCCONH,I ML, (M = Ni, Pd, or Pt, L = H,NNHCS,-) NiL, 0.= aromatic hydroxyoxime) Ni(octaethylporphinat0) Ni(pyO)oz+ Co,-,Ni,P,S, (x = 0-2) Ni(S,CNPr*,), NiCl, (matrix-isolated) PdPYaCla MOPSI(skeletal unit, M = Pd or Pt) E S , } ( M = Pd or Pt, X = C1, Br, or I, L = O-ethyldithiocarbamate)

245

tranr-[PtH(P-C)PR,] (P-C = But,PCMe,CH,; R = Et, Ph, etc.) tranr-m(L)(PBut,),If (L = NH, or CO) [PtH(L)(PBu'sPh)al+ IPtWPPhd31+ [PtH(PButs)aI+ [PtH(~0lv)(PBut~)~1+ (soh = HSO, NH3, MeCN, etc.) fruns-[PtX,(C,H,)L] (X = C1 or Br, L = NH3, py, aniline, or imidazole) PtCI,(NH,),(OH), (various isomers) PtL(C0,) (L = l,2-diaminocyclohexaneor phen) ci~-[pfCl*LJ[L = Ph,P(CH,).SPh, n = 1 0; 21 (pop = PaO&'-, X = C1, Br, or I, XI= MeT)

}

I

}

PtLCla (L = 8-aminoquinoline, phen, etc.) PtLaClB (L = theophylline, 2-aminopyridine, etc.) cis- and trans-[PtLCI,] [L = Ph,As(CH,),AsPh,, n

I-

=

241 281

249 15 282 14 13

25 1 242 98 29 283 284 285 286 287

288 289 290 29 1 256 32

292 4-12

or 161

293

C. B. Knobler, H. D. Kaesz, G. Mighetti, A. L. Bandini, G. Banditelli. and F. Ronati, Inorg. Chem., 1983, 22, 2324. 277 G. A. Foulds and D. A. Thornton, J. Mol. Struct., 1983,98, 309. a78 G. A. Foulds,D. A. Thornton, and J. Yates, J . Mol. Struct., 1983, 98, 315. 270

228


Dzh point-group symmetry could be used to assign v(Pt0) and v(PtX) modes in the platinum(rv) complexes [Pt(o~alato),X,]~(X = C1, Br, I, SCN, or OH).

vs(PtO) and v,,(PtO) modes were always at higher wavenumber than in the plat inum(n) complexes [Pt(oxalat o),I2-.27 In [Pt2C1212(CO)2]-,v[PtCl(trans to CO)] bands are at 309 and 314 cm-l, while the v[PtI(trans to Pt)] band is at 149 cm-1.280 Other assignments involving nickel, palladium, and platinum complexes are summarized in Table 7.13-15.2 9 . 3 2 . 9 8,242,245,247.24 9,251,258.2 81-2 9 3

12 Copper, Silver, and Gold

v(CuN) bands were assigned for a number of Cu' and Ag' complexes of 2(410-520 ~ m - 9 . ~ ~ ~ amino-l,3,4-thiadiazole and 2-ethylamino-l,3,4-thiadiazole The i.r. and Raman spectra of CuX(PBu',), (X = C1, Br, or I) are all indicative of a cubane-like tetrameric structure. v(CuP,) is in the range 104-92cm-l, with v(CuX,,) at 150 cm-l (Cl), 120 cm-l (Br), or 104 cm-l (I).295 [ C U & ~ ] ~ (13) gives a v(CuS) band at 254 cm-l, with v(SS) at 453 cm-1.2961.r. bands due to

I

\

13+

G. Rimkus and W. Preetz, Z. Anorg. Allg. Chem., 1983, 502, 73. N. M. Boag, P. L. Goggin, R. J. Goodfellow, and I. R. Herbert, J. Chem. SOC.,Daltori Trans., 1983, 1101. 281 Y.Inomata, T. Takeuchi, and T. Moriwaki, Znorg. Chim. Acta, 1983, 68, 187. 282 R. H. Haines and W. J. Louch, Znorg. Chim. Acta, 1983, 71, 1. 2R3 V. I. Berezin, V. V. Ganin, A. B. Kovrikov, I. V. Lipnitskii, and N. L. Rogalevich, 2%. Prikl. Spektrosk., 1983, 38, 434. 284 V. S. Kravchenko, G. D. Zegzhda, V. P. Morosov, and Z. I. Sour, R w s . J. Znorg. Chem., 1983, 28, 852. 285 G. Faraglia, L. Sindellari, L. Chiavegato, and S. Sitran, Znorg. Chim. Acta, 1983,76, L103. 286 A. B. Goel and S . Goel, Znorg. Chim. Acta, 1983, 69,233. 287 R. G. Goel and R. C. Srivastava, J. Organomet. Chem., 1982,244,303. 288 R. G. Goel and R. C. Srivastava, Can. J. Chem., 1983, 61, 1352. P. E. auf der Heyde, G. A. Foulds, D. A. Thornton, H. 0. Desseyn, and B. J. van der Veken, J. Mol. Struct., 1983, 98, 1 1 . 290 R. Kuroda, S. Neidle, I. M. Ismail, and P. J. Sadler, Znorg. Chem., 1983, 22, 3620. 2g1 G. Garzon, C. Rosas, and C. Marina de Rivas, Rev. Colomb. Quim., 1982, 11, 9. 292 P. Umapathy and R. A. Harnesswala, Polyhedron, 1983, 2, 129. 293 W. E. Hill, D. M. A. Minahan, C. A. McAuliffe, and K. L. Minton, Inorg. Chim. Acta, 1983, 74, 9. 294 A. C. Fabretti, G. Peyronel, A. Giusti, and A. F. Zanoli, Polyhedron, 1983, 2, 475. 2g5 R. G. Goel and A. L. Beauchamp, Znorg. Chem., 1983,22, 395. 296 A. Muller and U. Schimanski, Znorg. Chim. Acta, 1983, 77, L187. 27B 280


229

both terminal and bridging chlorine were seen for CuLCl, (L = 5,7-dichloro-, v(CuX) and v(CuN) bands 5,7-dibromo-, or 5,7-di-iod0-8-aminoquinoline).~~~ were identified in CuLX (X = C1 or Br, L = acetonitrile or methacrylonitrile). Thus in the acetonitrile complexes v(CuN) was at 266 (Cl) or 253 (Br) cm-l, v(CuC1) at 225 cm-l, and v(CuBr) at 160 ~ m - ~ . * ~ * Other copper-containing compounds for which vibrational assignments have been given are listed in Table 8.13,14,33,34,247,249,260,281,299-802

Table 8

Vibrational assignments in copper complexes

Species

Ref.

[CuLSla+(L = aminopropanols) CULX, (X = C1 or Br, L = 3-amino-I-propanol or its methyl derivatives) CuL, .nH,O (L = Chydroxy-L-prolinato) Cu(RIz),(s~,(H,O). (RIz = alkylimidazole, sf = substituted phenolate anion, n=Oorl) cis- and trans-[bis-(~-alaninato)Cu~~] Copper glutamate dihydrate [CuL,]*+ (L = 2-amino-4-picoline-N-oxide, n = 1, 2, or 4) Copper-pyridine-N-oxide complexes CULa (L = aromatic hydroxyoxime) Cu(octaethylporphinat0) CuLX, [L = 1,2-bis(benzothiazolyl)ethane, etc., X = C1, Br, I, or NCS] KaCu$n I-&

247 299 281 249 33 34 300 30I 14

13 250

302

Fourier-transform far4.r. spectra have been reported for silver atoms and

Ag, clusters in zeolite Nay. A band at 80 cm-l may be due to Ag,+, with one at 130 cm-l due to larger Surface-enhanced Raman spectra (s.e.r.s.) for NCS- ions at silver electrodes gave evidence for the formation of an Ag-S surface bond, with v(AgS) at 200-21 5 cm-1.304 v(AuC) is in the range 560-575 cm-l in Au(C,F,)[CH(R)PPh,] (R = H, Me, Et, or Ph).30S1.r. bands due to v(AuCl,,) were seen at 285 and 300 cm-l in (14).308The solid-state vibrational spectra of [ACl,][AuCl,] (A = S or Se) show that the AuC1,- ion is distorted considerably from D a AuC13(TT) (TT = 1,3,5-trithiane) gives three v(AuC1) bands in the i.r., which is consistent with a C,, square-planar metal v(AuC1) (ca. 300 crn-l) was assigned in AuCI(C4Ph4)L(L = py, PPh?, PCy,, or CNBLI').~'~ 897

J. Casabo, M. Izquierdo, J. Ribas, and C. Diaz, Transition Met. Chem., 1983, 8, 110.

'@*J. Zarembowitch and R. Maleki, Spectrochim. Acta, Part A, 1983, 39, 43, 47.

T. Lindgren, R. SillanpLii, T. Nortia, and K. Pihlaja, Znorg. Chim. Acta, 1983,73, 153. D. X. West, Inorg. Chim. Acta, 1983, 71, 251. A. Malek and J. Fresco, Chern. Scr., 1983, 22, 146. Y. Natsume and I. Yamada, Solid State Commun., 1983, 47, 839. G. A. Ozin, M. D. Baker, and J. M. Parnis, Angew. Chem., Int. Ed. Engl., 1983, 22, 791. 804 J. M. Weaver, F. Barz, J. G . Gordon, and M. R. Philpott, Surf. Sci., 1983, 125, 409. R. Uson, A. Laguna, M. Laguna, and A. Uson, Znorg. Chim. Acta, 1983,73, 63. R. Uson, A. Laguna, M. Laguna, and M. Abad, J . Organomet. Chem., 1983,249,437. ao' A. Finch, P. N. Gates, T. H. Page, and K. B. Dillon, J. Chem. Soc., Dalton Trans., 1983. MK)

1837.

S . R. Wade and G . R. Willey, Inorg. Chim. Acta, 1983, 72, 201. R. U s h , J. Vicente, M. T. Chicote, P. G . Jones, and G. M. Sheldrick, J . Chem. SOC.. Dalton Trans., 1983, 1131.


230

13 Zinc, Cadmium, and Mercury

Raman spectra of aqueous zinc nitrate solutions show that the band due to Zn(OH,),,+ at 386cm-l decreases in intensity and increases in frequency as the temperature increases. This is due to replacement of H,O by NO,- in the primary co-ordination shell of Zn2+.310 v(M0) and v(MX) modes were assigned from the i.r. and Raman spectra of MX2.nDMF (M = Zn, Cd, or Hg, X = CI, Br, or I, n = 1 or 2). For M = Zn and n 1, the low value of v(ZnX) suggests that these are X-bridged dimers, possibly of C,, local The complexes Zn(dmpd)X, (dmpd = 2,2dimethyIpropane-l,3-diamine,X = C1 or Br) give skeletal modes as expected for pseudo-tetrahedral complexes of local C,, symmetry. The complexes M(dmpd)X, (M = Cd or Hg) are pseudo-octahedral polymers with local symmetry of C, for N2MX4.312 The Raman spectra of aqueous ZnBr, solutions can be interpreted in terms of the presence of Zn(OH1)62+and [Zn(OH,)4-,BT,],-~(n = 2, 3, or 4).,13 v(CdC1) (238 cm-l) shows that [CdCl,L,].L (L = 1,Z-ethanediol) is an infinite-chain polymer, with bridging Cl atoms.314 The Schiff base N,N'ethylenebis(salicylideneimine), (H,Salen), forms complexes M(Sa1en) (M = Cd or Hg). These have v(M0) at 505 (Cd) or 520 (Hg) cm-l and v(MN) at 580 (Cd) or 550 (Hg) 1.r. and Raman spectra have been reported, together with a normal-coordinate analysis of C(Hg),, for C(HgX), (X = CN-, HCOO-, MeCOO-, or CF,COO-), also normal-co-ordinate analyses only for X = F-, C1-, Br-, I-, or SMe-. The Hg-C stretching force constant is ca. 20% lower than in related MeHgX compounds. This was thought to be due to the effects of non-bonded interactions between mercury atoms.316 Several papers have been published that examine critically the vibrational spectra of mercury(r1) halide complexes containing tertiary phosphine ligands, in the light of known crystal structures. It was concluded that slight structural changes can give significant changes in spectra. Hence structural elucidation from such spectral data alone is very d i f f i ~ u l t . ~ ~ ~ - ~ * ~

-

D. E. Irish and T. Jaw, Appl. Spectrosc., 1983, 37, 50. 0.A. de Oliveira, A. P. Chagas, and C. Airoldi, Znorg. Chem., 1983, 22, 136. "* F. Cariati, G. Ciani, L. Menabue, G. C. Pellacani, G. Rassu, and A. Sironi, Znorg. Chem., 'lo

'11

1983,22, 1897. '13

E. Kalman, I. Serke, G. Palinkas, G. Johansson, G. Kobisch, M. Maeda, and H. Ohtaki,

'14

2.Natwforsch., Teil A , 1983, 38, 225. F. A. Schroder, J. W. Bats, H. Fuess, and E. J. Zehnder, Z. Anorg. Allg. Chem., 1983,

'16

499, 181. H. A. Tajmir-Riahi, Polyhedron, 1983, 2, 723.

'16 'l'

'la 'lo

J. Mink, Z. Meic, M. Gal, and B. Korpar-Colig, J . Organomet. Chem., 1983, 256, 203. N. A. Bell, M. Goldstein, T. Jones, and I. W. Nowell, Znorg. Chim. Acfa, 1983, 69,155. N.A. Bell, M. Goldstein, T. Jones, and I. W. Nowell, Znorg. Chim. Acfa, 1983, 75, 21. N. A. Bell, T. D. Dee, M. Goldstein, and I. W. Nowell, Znorg. Chim. Acta, 1983.70.21 5.


23 I

Raman intensity measurements were used to deduce mean molecular and bond-derived polarizabilities for HgX3- (X = C1, Br, or I).320 I.r./Raman coincidences for [Pr,N]IHgBr,] show that the solid-state structure is noncentro~ymmetric.~~~ Vibrational spectra of (Ph2Te)HgX2(X = C1, Br, or I) are consistent with a novel tetrameric structure, involving two different types of Hg-X-Hg bridge. v(HgX,) and v(HgX,,) wavenumbers were assigned.322 Table 9 summarizes those other zinc, cadmium, and mercury species for which @,I@ 8,247--860. MS. 281,282,302,328-8 32 made.2,13,16,34,@ vibrational assignments have Table 9

Vibrational assignments in zinc, cadmium, and mercury complexes

Species

Ref.

[ZnL$+ (L = aminopropanols) Z&L (L = 2-acetyl- or 2-benzoyl-pyridine hydrazone) Zn(RIz),(sf),(H,O). (RIz = alkylimidazole, sf = substituted phenolate anion, n=Oorl) ZnLX, [L = 1,2-bis-(2-benzothiazolyl)ethane, etc., X = C1, Br, I, or NCS] ZnL, * nHpO (L = 4-hydroxy-L-prolinato) Zn(octaethy1porphinato) cis-[Zn(glycine),J Ha0 Zinc glutamate dihydrate ML, (M = Zn, Cd, or Hg, L = HJ'l"NCS,-) ML (M = Zn or Cd, L = piperidinobisdithiocarbamato) K,Cua1-$4 ZnTiF, 6H10 (N,H,)ZnTiF, 5HaO [MX,py]- (M = Zn or Cd, X = C1 or Br) [Me4NI[ZnC141 MXPLI [M = Zn, Cd, or Hg, H = C1, Br, I, or CF3CO0, L = 4,6dimethylpyrimidine2(1H)-one] [Me,NI[CdCl,I [n-CeH17NHSloICdCI4I HdCWa Wg[As(mait~ 1),](NO 8)s >a [(L-L)MJ,Hg(SCN)a (L-L = bipy or phen, M = M o or W) HdSCN)a (Th)(HgaCl&(Th = thiamine cation) HgXZ(bipy), HgX2(bipy) (X,Z = C1, Br, or I )

247 248

-

-

8ao

8a1

249 250 28 1 13 16

34 282 268 302 2 99 323 324

325 198

326 327 328 329 330 331 332

J. G. Contreras and G . V. Seguel, Bol. SOC.Chil. Quim., 1981,26, 12. J. G . Contreras and G. V. Seguel, Spectrosc. Lett., 1982,15,671. F. W. B. Einstein, C. H. W. Jones, T. Jones, and R. D. Sharma, Znorg. Chem., 1983, 22,

3924. S. P. Perlepes, T. F. Zafiropoulos, M. E. Kanellaki, J. K. Kouinis, and A. A. Galinos, Chem. Chron., 1982, 11, 37. ap4 V. Srinivasan, C. K. Subramanian, and P. S. Narayanan. Indian J . Pure Appl. Phys., 1983, 21, 271. R. Battistuzzi and G. Peyronel, Polyhedron, 1983, 2, 471. 8N N. B. Chanh, Y. Haget, C. Hauw, A. Meresse, L. Ricard, and M. Rey-Lafon, J. Ph.vs. Chem. Solids, 1983, 44, 589. D. M. A d a m and P. D. Hatton, J. Phys. C, 1983, 16, 3349. 3*B E. C . Alyea, S. A. Dias, G. Ferguson, and P. Y. Siew, Can. J . Chem., 1983,61,257. M. P. Pardo and M. Cano, J. Organomet. Chem. 1983,247,293. 890 D. M. Adam and P. D. Hatton, J. Chem. SOC.,Faraaiay Trans. 2, 1983,79, 695. 3s1 N. Hadjiliadis, A. Yannopoulos, and R. Bau, Inorg. Chim. Acta, 1983,69, 109. J. G . Contreras and G. C. Seguel, Bol. SOC.Chil. Quim., 1982,27, 5. 3p8

232

Spectroscopic Properties of Inorganic and Organometallic Compounds 14 The Actinoids

In addition to work on ThtV (and Utv and Uv') crown-ether and diaqua(oxydiacetato)sulphato-thorium(~v),~~ Raman spectra were reported for ThC14,ThBr,, and M2ThX, (X = C1 or Br, M = K or Cs). v(ThX) in the anions showed quite a strong cation dependence, i.e. v(ThC1) is at 282 cm-l for K+ but 310 cm-l for Cs+.333 Raman spectra of actinoid(v), except Pa, and actinoid(v1) complexes in 2M Na2C0, solutions show that the M02+wavenumbers do not shift with increasing atomic number of the actinoid but that v,(MO,~+)decreases regularly with increased atomic number of M. The Raman spectra of solid Na3[MV02(C0,),] show that v,(MV02)is higher than in solution and does show a dependence on the atomic number of M.334 A detailed study of U(OMe), was reported above.lBv(U=O) wavenumbers were assigned in UOF4.nL (n = 3, L = SbF,, TaF,, or NbF,; n = 2, L = SbF, or BiF,). Increasing the Lewis-acid strength of L gave an increase in v(U=O), due to increased electron withdrawal from UF,0.336 1.r. spectra of U0,(S2PR12)2.R20Hand [U0,(S2PR1,),CI]- (R1 = Me, Et, Pri, OMe, OEt, Ph, etc., R2 = Me or Et) contain a strong band due to v,,(UO,) near 930 cm-l, a weak or absent feature due to v,(UO,) (850--900crn-l), and 8(UO2) cn. 255

Other reports of vibrational assignments for dioxouranium(v1) species are given in Table 10.1D~337-345 Table 10 Dioxouranium(vr) species .for which vibrational data have been assigned Species Ref. 337

[UOzLzX2]2(HL = benzylhydroxamic acid, X = OAc, &SO,, &CO,,or CI) .L (L = thf, DMSO, etc.) UOJCF3C(0)CHC(O)CF3]2

338 339 340 341 342 343 344 345 19

A. D. Westland and M. T. H. Tarafder, Can. J . Chem., 1983,61, 1573. 334 C. Madic, D. E. Hobart, and G. M. Begun, Inorg. Chem., 1983,22, 1494. 336 J. H. Holloway, D. Laycock, and R. Bougon, J. Chem. SOC.,Dalton Trans., 1983, 2303. 336 A. E. Storey, F. Zonnevijlle, A. A. Pinkerton, and D. Schwarzenbach, Inorg. Chim. Actn. 1983,75, 103. 337 C. D. Flint and P. Sharma, J . Chem. SOC.,Faraday Trans. 2, 1982,78,2155. 838 C. D. Flint and P: Sharma, J . Chem. Soc., Faraday Trans. 2, 1983,79, 317. 899 C. D. Flint and P. A. Tanner, Polyhedron, 1983,2, 623. 340 V. N. Serezhkin, L. B. Serezhkina, M. A. Soldatkina, V. F. Zolin, and B. V. Lokshin. Koord. Khim., 1983, 9, 92. 841 K. C. Satpathy, R. Mishra, and G. C. Pradhan, Acta Cienc. Ind., Ser. Chem., 1982,8, 139. M2 L. V. Kobeta and N. N. Khod'ko, Russ. J. Znorg. Chem., 1982,27, 1472. 8(3 L. V. Kobeta, I. M. Kopashova, and N. G. Bend, Russ. J . Inorg. Chem., 1983,28,862. 844 P. C. Kundu and A. K. Bera, Indian J. Chem., Sect. A , 1982,21,1132. 84s P. C. Kundu and S. Bhattacherjya, Indian J. Chem., Sect. A , 1982,21, 586. 33s


233

Vapour-phase i.r. spectra were reported for UX, (X = F, C1, or Br). v,,(UX) bands were seen at 550 cm-l (F), 345 cm-l (CI), and 233 cm-l (Br).346vs for UF, in solid Xe consists of a single, sharp feature.3471.r. spectra of UF, in liquid Xe, Kr, N20,or CH., have been measured and assigned, together with gas-phase data.348Bands due to v(UF) and v(UC1) were identified for UF,-,CI, (0 n 6) dissolved in liquid xenon. The compounds were prepared by the reactions of Tic&, BCl3, or HCI with UF,.34B UF, cooled in a supersonic jet gave v3 in the i.r. with a Q-branch position of 627.680cm-l. It was possible to detect the 236U/238U isotopic shift (0.650 & 0.005 cm-l).

<
Mn' > Fe", i.e. there is decreasing dx-x*,, bonding in that order. Co"' gives a very weak v(C=N), suggesting very little back-bonding in this case.2o6

N Nc

NN

C

II

NNH,

v(CN) in (q3-C,H,)M(CO)S(CNSnMe,) ( M = Mn or Re) is 80-100 cm-1 lower than in (q3-C3Hs)M(C0),(CNMe), owing to d-p,+ interaction between Sn and N.207 The complexes [Tc(CNR),]+ (R = But, Me, C6HI1, or Ph) all have v(CN) in the range 2130-2140 cm-l. This is consistent with extensive x-donation from Tc' to the x* orbitals of the isocyanide ligands. The presence of two v(CN) bands for R = But suggests & symmetry for the cation.2o8 C. Anderson, R . Larsson, and €3. Yom-To\. Iiiorg. Clrim. Actn. 1983, 76, L185. D. E. Wigley and R. A. Walton. Itzorg. Chew.. 1983. 22. 3138. 204 F. R. Lemke. D. E. Wigley, and R . A . M'alton. .I. Orgrrtionief. Chem.. 1983. 248. 321. 203 D. A. Bohling and K . R . Maiin. liiorg. Ckeni., 1982, 22, 1561. 206 D. T. Plummer and R. J. Aiigelici. Inorg. C'lieni.. 1983. 22. 4063. "' N. Mol, H . Behrens. H.-J. Seibold. and P. Merbach. J . Orgonornef. Cliem., 1983, 248, 329. 'OR M. J. Abrams, A . Davison. A. G. Jone5, C . E . Costello. and H . Pang, Itiorg. Chern.. 1983, 22, 2798. 202

203

Spectroscopic Properties of'Inorganic and Organometallic Compounds

260

The cation in [Fe(NCBr),](FeBr4),-2BrCN has v(CN) at 2215 cm-l, compared to the value of 2184 cm-1 for the free BrCN molecule.2D* A characteristic shift of v(CN) to lower wavenumber was found in the bridged complexes [Ru(NH,),],L"+ (L = a dicyanobenzene, 3- or 4-cyanopyridine, or dicyanonaphthalenes, n = 4, 5, or 6). For isomeric L, ortho- and para-type bridging ligands give the greatest shifts. This is related to the degree of Ru -+x* back-bonding.210 MXzL and MX2L2[M = Co, X = C1 or Br; M = Zn, X = C1; L = (71), R = Me or Ph] give increases in v(CN) on complex formation. This shows that co-ordination occurs via the N of the C=N group. v(NN) was generally in the range 1150-1 180 cm-1.211 The complexes Co3(q-C5H5),(p,-CNR)( p3-S) (R = Me, Ph, or C,Hll) give an intense band near 1550 cm-l, due to the bridging v(CN) mode.212 The Rh' and Rh" complexes [Rh'(DiNC),]+ and [Rh'1(DiNC)41,]2+ [DiNC = (72)] have v(CN) higher than in the free ligand. Hence the ligand is acting primarily as a a-donor.213

- P -Ni-lll /

\vi:

N

N

4

C (72)

Me

N

C 1 CH2Ph

Et0,C

(73)

(74)

v(CN) modes in Ni(PCy3),(PhCH2CN)are at 2250 and 2240 cm-l, i.e. this is a a-PhCH2CN complex. The x-bonding in (73), however, is revealed by v(CN) being at the low value of 1780 cm-1.214 and cis-[PtCI,(PPh,)(CNR)] The i.r. spectra of tr~ns-[PtCl(PPh~)~(CNR)1+ [R = (74) or related species] give values of v(CN) 75-100 cm-l lower than in the free ligands. There was no significant shift of v(C=C) on complexation.216 A detailed assignment of ligand modes was proposed for cis- and trans(PhCN),PtCI,. v(CN) of benzonitrile is shifted to higher wavenumber on co-ordination.21e v(C=N) increases only slightly on formation of MeCNSCuX (X = C1 or Br). This was interpreted in terms of back-bonding from Cu to N.,17 A similar result was found for the analogous methacrylonitrile K. F. Tebbe and R. Frohlich. 7. Anor.c. A l l y . Clietii.. 1983. 498, 7. D. E. Richardson and H . Taube, J . Am. Chert/. .So(,.. 1983, 105, 40. *11 D. Demertzi and D. Nichollr. Iiiorg. Chini. Acto. 1983. 73. 37. "12 J. Fortune, A . R. Manning. and F. S. Stephenr. J . C h w . Soc.. Chem. Comtnun., 1983. 1071. M . L. Winzenburg, J . A . Kargol, and R. J . Angelici. J. Org~o/iornct.Cliem.. 1983. 249. 415. G. Favero, A. Morvillo. and A. Turco. J . Or.qcrtio/ric,f.Clwirr.. 1983. 241. 25 I. "15 C. Herdeis and W. Beck, Cheni. Ber.. 1983, 116. 3205. '16 H. H. Eysel. E. Guggolz, M. Kopp. and M . L. Ziegler. Z. Atmrg. Allg. Cliem.. 1983. ?09

210

499, 3 1 . f17

J. Zarembowitch and R. Maleki, Spectrochim. Acto. Port A. 1983, 39, 43. J. Zarembowitch and R. Maleki, Spectrochim. Arto. frrrt A. 1983. 39. 47.

Vibrational Spectra of Some Co-ordinated Ligands

26 1

Nitrosyls and Thionitrosy1s.-The i.r. spectra were reported for V(CO),(NO) and related species in which some of the CO ligands had been replaced by phosphine ligands. In the parent compound v(N0) was at 1695 cm-l and v(C0) at 2100,2050, and 1990 cm-l. These are the highest known v(C0) values for any vanadium carbonyl. In conjunction with the rather low v(NO), this suggests that the electronic ground state may be described thus: (OC)5V-=N+=Oo (OC),V = N + - C - , with a significant contribution from the latter [V(NO),(Bu'NC),]+ has v(N0) at 1939 and 1833 cm-l, close to the values in the chromium analogue.22o v(N=S) modes in NbCl,(NSCI) (1332 and 1310 cm-l) are very close to the wavenumbers in free NSCl, but v(SC1) is at 505 cm-l, compared to 415 cm-l in the free ligand. The bonding is thought to be very weak.221 A variety of M(chelate),(NO), complexes [M = Cr, Mo, or W, chelate = M%AsS,-, Me,PS,-, (MeO),PS,-, or Me,NCS,-] all give two v(N0) bands, as expected.222 v(N0) in {Mo[HB(Me,pz),](NO)XY} follows the following trend in X and Y (values in cm-l): 1,SR (1679) > &OR (1675) > SR,SR (1667) > 1,NHR (1656) > SR,OR (1651) > OR,OR (1646) > SR,NHR (1635) > OR,NHR (1632). This is broadly consistent with the donor capacities of the atoms in X and Y.223 v,(NO) is near 1800 cm-l and v,,(NO) near 1650 cm-l in Mo(NO),L,Cl, (L = PPh3, py, MeCN, CH2=CHCN, or PhCN, L2 = dppe or bipy).,,* In the cationic molybdenum dinitrosyls [Mo(NO),L,( MeCN),I2+ (L = PPh, or py), [Mo(NO),( MeCN)J2+, and [Mo(NO),(bipy),12+v,(NO) is in the range 18051830 cm-l and v,,(NO) in the range 1690-1750 ~rn-l.,,~ A number of surface nitrosyl species were identified from the i.r. spectra of NO adsorbed on molybdena-alumina catalysts.22s [(?5-C,Me5),W(NO),]+ has v(N0) at 1730 and 1645 cm-l, some 25 cm-l lower than in the q5-C5H5analogue. This reflects the better electron-donating capacity of C, Mefi.,,' The i.r. spectra of Mn(CO),(NO)(CNR) (R = Me or Et) are consistent with the geometry shown in (75).22eThe presence of two i.r. bands due to v(N0) for ReCl,(NO),(SbPh,),, at 1723 and 1655 cm-l, shows that the two nitrosyl groups are cis.,,@ v(NS) in the new cation [Re(CO),NSI2+ is at 1371 cm-l, about 80 cm-l aso

K. L. Fjare and J. E. Ellis, J. Am. Chem. SOC.,1983, 105, 2303. M. Herberhold and H. Trampisch, Znorg. Chim. Acta, 1983, 70, 143. J. Hanich, P. Klingelhofer, U. Muller, and K. Dehnicke, 2. Anorg. Allg. Chenz., 1983. 506, 68.

a81

2a*

M. Herberhold and L. Haumaier, Chem. Eer., 1983, 116,2896. J. A. McCleverty, A. S. Drane, N. A. Bailey, and J. M.A. Smith, J. Chem. SOC.,Dalton Trans., 1983, 91. D. Ballivet-Tkatchenko, C. Bremard, F. Abraham, and G. Nowogrocki, J. Chem. SOC., Dalton Trans., 1983, 1137. D. Ballivet-Tkatchenkoand C. Bremard, J . Chem. SOC.,Dalton Trans., 1983, 1143. J. Valyon and W. K. Hall, J. Catul., 1983, 84, 216. P. Legzdins and D. T. Martin, Organometallics, 1983, 2, 1785. M. Moll, H. Behrens, K. H. Trummer, and P. Merbach, Z . Nnturforsch., Teil B, 1983. 38, 411.

z29

D. Fenske, N. Mronga, and K. Dehnicke, Z . Anorg. Allg. Chem., 1983,498, 131.

262

Spectroscopic Properties of' Inorganic and Organometallic Compounds

I

ON-Mn

$0

I 'co

CNR (75)

higher than in any previously known thionitrosyl complex. The v(C0) modes were also at very high wavenumbers.z30 The presence of v(N0) at 1720 cm-l for NO adsorbed on iron supported on KOH-doped alumina shows that an FeO-NO complex unit is formed.231 The i.r. spectra of M+[Fe(CO),(NO)]- (M = Na or K) in solution show ion pairing to be important, and tight ion pairs involving cation/nitrosyl interaction were observed: for M = Na in THF solution [Fe(CO),(NONa)] gives v(C0) at 1990 and 1885 cm-l and v(N0) at 161 5 cm-l. [Fe(CO),(NO)]-Na+ gives v(C0) at 1978 and 1875 cm-l and v(N0) at 1646 cm- 1 . 2 3 p Further evidence that the excited state of Na,[Fe(CN),(NO)]. 2H20, populated by irradiation at 514.5 nm, involves population of the x*-NO orbital has been given. v(N0) in the excited state is shifted by more than 100 cm-l to lower wavenumbers. '3 v(N0) for Fe(NO)(S,CNPr',), is at 1695 cm-l, very low for a linear Fe-N-0 system. It is within the range normally found for bent M-N-0 units. However, unit, has v(N0) at even the Co analogue, which does possess a bent Co-N-0 lower wavenumbers (1610 ~ m - 9 . ~ ~ ~ Assignments of v(N0) bands have been made for complexes of nitrosyl(protoporphyrin IX dimethyl ester)iron(II) with nitrogenous bases235 and five- and six-co-ordinated ferrous nitrosyl myoglobin.z36 1.r. evidence has been found for the reversible electrochemical formation of the Ru"' complex [Ru(NO)CI,]-, with v(N0) at 1920 cm-l, compared to 1850 cm-1 in the parent Ru" complex.237v(N0) modes were found for both anionic and cationic species [RU(NO)(NH,),],[RU(NO)C~,]~ .4H20 and [Ru(NO)(NH,),L][Ru(NO)Cl,] (L = OH or Cl), but it was not possible to differentiate between these unambiguously. The NH3modes were identified by d e u t e r i a t i ~ n . ~ ~ ~ Complex (76) gives v[NO(bridging)] at 1550 cm-l. The anion Os3(CO)l,(NO)gave a very low value for v(NO), 1462 cm-l, and it probably has the same ~tructure.~~ [RUCI(NO)~(PP~~)~]+BF,has two v(N0) bands in the solid-phase i.r., at R. Mews and C . 4 . Liu, Angew. Chem., h f . Ed. Engl., 1983, 22, 162. A. Kazusaka, H. Suzuki, and I. Toyoshima, f. Chem. SOC.,Chem. Commun., 1983, 150. 232 K. H. Pannell, Y.-S. Chen. K . Belknap, C. C. Wu, 1. Bernal, M . W. Creswick, and H. N. Huang, Znorg. Chem., 1983, 22,418. 233 T.Woike, W. Krasse, P. S. Bechthold. and S. Hausuhl, Solid Stare Commun., 1983.45.499. 234 G . A. Brewer, R . J. Butcher,'& Letafat, and E. Sinn, ftiorg. Chem., 1983, 22,371. 235 T.Yoshimura. Bull. Chem. SOC. Jpn.. 1983, 56, 2527. 236 H. C. Mackin. B. Benko, N. T. Yu, and K . Gersonde, FEBS Lett., 1983, 158, 199. 23i V. T. Coombe, G . A. Heath, T. A . Stephenson, and D. A. Tocher. J . Chem SOC., Cheni. Commun.. 1983, 303. N. M . Sinitsyn. V. N. Kokunova. and A. A. Svetlov, R N S S . Inorg. ~. Chem., 1982, 27, 1317. m R. E. Stevens and W. L. Gladfelter, Inorg. Cliem., 1983, 22, 2034. 230

231


263

unit, as 1870 and 1685 cm-l. Thus there is one linear and one bent Ru-N-0 confirmed by X-ray diffraction. In solution there are four v(N0) bands, and this was interpreted in terms of the presence of two isomers, one trigonalbipyramidal (77) and one square-pyramidal (78).240 v(NS) bands were assigned (1299-1310 cm-l) in Ru(NS)X,L3 (X = C1 or Br, L = PPh3 or AsPh3).,11 The v(N0) band in [ O S C ~ ~ ( N O ) ( S ~ C ~ is~at ) , ]1825 ~ - cm-l (1805 cm-l for 16NO),55 cm-l higher than in the C1-bridged O S C I ~ ( N O ) . ~ ~ ~ The symmetric and antisymmetric NS stretches in OsCl,(NS), are at 1388 and 1326/1308 cm-l, respectively. In [OsCl,(NS),Cl]- (79) they are at 1298 and 1215 cm-l, respectively. The latter are still typical of terminal NS groups, although lower than in the neutral species.243

The species CpCo(NO), can only be identified by i.r. spectroscopy, as it is extremely reactive. It has v(N0) bands at 1609 and 1692 cm -1.244 Two reports have given evidence for the formation of surface nitrosyl species on Rtrt246 and Pt/SiO, or R/Ag/SiO, 5 Phosphorus Donors

The presence of v(PF) at 798 cm-l shows that co-ordinated MeN(PF,), is present in Nb,Cl,(PhPMe,) 6 [MeN(PF2)21.247 v(PH) was assigned in the secondary phosphine complexes (80) (M = Cr, Mo, or W, R = OH, OMe, PhNH, Et2N,CI, Br, or I); all lie in the range 2290-2370

"*" L. K . Bell, J . Mason. D. M . P. Mingos, and D. G . Tew, h r g . Chern., 1983,22, i41

191.

B. Czeska. F. Weller, and K. Dehnicke. Z . Anorg. Allg. Chem., 1983, 498, 121. R. Weber, U. Miiller. and K. Dehnicke. Z. Anorg. Allg. Chem., 1983, 504, 12. y44 P. N. Becker and R . G. Bergman, f. Am. Che!??. Soc., 1983, 105, 2985. 245 B. E. Hayden, Surf. Sci., 1983. 131, 419. 2'6 K. P. de Jong, G . R . Meima, and J. W. Gem. Appl. Sirrt: Sci.. 1982, 14. 72. L. G. Hubert-Pfalzgraf. Inorg. Clrim. Acta, 1983, 76, 1233. 242

3497.

K. N . Udupa. K. C. Jain. M . 1. Khan. and U. C. Agarwala, Inorg. Chirn. Acm, 1983. 74.

264


H I Ph - P -M(CO), I

R

(81)

cm-1.248Complexes (81) (R1 = Me or C,H,Me, XR2, = PMe, or AsPh,) both show a characteristic vas (C=C=O) band near 2100 cm-1.248 Ligand modes have been assigned for the bridging phosphine in complex (82), e.g. v(NH) at 3320 cm-l and v(NP,) [and y(NH)] at 721, 915, and 921 cm-1.250 A number of i.r. ligand bands were listed for CpM(CO),-substituted phosphazenes (M = Fe or Ru), e.g. in complex (83) v(PN) modes were seen at 1210 and 1240 ~ m - ~ . ~ ~ ~

v(PH) is at 2330 cm-l in {[(Me,Si),CH],PH)Fe(CO), and at 2350 cm-l in { [(Me3Si)2CH]2PH}Co,(C0)7.252 v(PF) modes have been assigned in Fe(CO),L

{L = F2POC(CF3),CN,FP[OC(CF,),CN],, or F2POCNC2(CF3)40}(848-878 cm-1).253 Os3(CO)ll[PBut2(NH,)]has v(NH) of the phosphine ligand at 3398 and 3480 cm-l. The bridging P,S-ligand in complex (84) has v(NH) at 3395 [Ir(cod)(PNP)]+ [cod = 1,5-cyclo-octadiene, PNP = (Ph2P),CHC5H4N]has v(C=N) at 1595 cm-l, compared to 1580 cm-l for the free PNP ligand. This is similar to the analogous rhodium complex, in which PNP is known to be tridentate.25s v(C=C) modes in Ni(CO)4-,[P(C=CPh),Ph,_,l, (n = 2 or 3, rn = 3,2, or 1) are all very close to the positions in the free ligand~.,~, Some phosphine ligand modes were assigned for M,(dppm),CI,-,(SnCl,), ( M = Pd or Pt, n = 0, 1, or 2).257The complexes (85) (M = Pd or Pt) have z4N

249

A. Marinetti and F. Mathhey. Organometnllics, 1982, 1, 1488. F. R . Kreissl, M . Wolfgruber. W. Sieber, and H . G . Alt. Angew. Chem., Inr. Ed. E&.,

1983, 22. 149. J. Ellerrnann and W. Wend, J . Orgonomet. Cliem., 1983, 258, 21. E31 H . R. Allcock, L. T. Wagner, and M. L. Levin, J. Am. Cheni. Soc., 1983, 105. 1321, 2.io A. H. Cowley and R . A. Kemp, lrtorg. Cliem., 1983, 22, 547. 2,i3 D. P. Bauer and J. K. Ruff, Diorg. Chem.. 1983, 22, 1686. zG4 W. Ehrenreich, M . Herberhold, G . Suss-Fink. H.-P. Klein, and U. Thewalt, J . Orgunornet. Chem., 1983, 248, 171. M. P. Anderson. C. C. Tso. B. M. Mattson. and L. H. Pignolet, Znorg. C h ~ m . 1983, , 22, 3267. 2.i6 H. Hengefeld and R. Nast, J . Organomet. Chem., 1983, 252, 375. 5' 0. L. AIves, M. C. Vitorge, and C. Sourisseau, N o w . J . Chim., 1983, 7, 231. 2.io


265

v(P,N) at 920 cm-l (Pt) or 850 cm-l (Pd). Protonation gives complex (86), with a lower P-N bond order, and v(P,N) is at 825 cm-2 for both complexes.2hR

6 Oxygen Donors

Molecular Oxygen, Peroxo, Aquo, and Related Complexes.-The v(0,) bands in [vO(0,),(C,04)]3- and [VO(O,),(bipy)]- are at 878 and 856 crn-', respectively. v(V=O) bands were in the expected regions.259 Complexes MTaO, (M = K, Rb, or Cs) give a band characteristic of the peroxo group at ca. 870 Reversible co-ordination of 0, by MnX,(PR,) complexes is said to occur for the complex with X = NCS only if v(CN) of the NCS ligand lies outside the range 2130-2140 cm-1.261 MnBr,(PMe,), prepared under strictly anhydrous conditions, does interact with 02,to give the highly coloured complex (Me,P)MnBr2-O2,shown by i.r. to be a superoxide. The latter, however, undergoes an irreversible transformation to (Me3PO)MnBr2.262 [Mn(OH),$- has been prepared as Ca2+and Sr2+salts. v(0H) gives a strong, narrow i.r. band at 3668 cm-l in the Ca2+ salt, together with diffuse bands, 2700-3600 cm-I, due to hydrogen-bonded OH groups. The Sr2+salt gave only the latter.263 Table 9 gives the H 2 0 vibrational modes assigned for M(NCS)s(dmtp),(HzO)z (M = Mn, Fe, Co, Ni, or Cd. dmtp = 5,7-dimethyl[l,2,4]triazolo[l,5-a]pyrimidine).264 v(0H) was assigned for Cr(OH)(Re04)4.4H20 (3 1oO-3200 crn-l) and Cr(OH),(Re04)-2H,0 (3200-3400 ~ r n - l ) . ~ ~ ~ H. Schmidbaur, S. Lauteschlager. and B. Milenski-Mahrla. J. Orgonomet. Chem., 1983. 254,59. 250 N. J. Campbell, M. V. Capparelli, W. P. Griffith, and A. C. Skapski. Inorg. Chim. Acta. 1983.77, L215. *O0 G. A. Bogdanov, G. K. Yurchenko, and 0.V. POPOV,Russ. J. Inorg. Chem., 1982, 27. 121 1. C. A. McAuliffe, H. F. Al-Khateeb. D. S. Barratt, J . C. Briggs, A. Challita, A. Hosseiny, M. G . Little, A. G . Mackie, and K . Minten, J . Chem. Soc., Dalton Trans., 1983,2147. 262 H. D. Burkett, V. F. Newberry. W. E. Hill. and S. D. Worley. J. Am. Chem. Soc., 1983, 105,4097. 2133 B. N. Ivanov-Emin, N . .4. Nevskaya, B. E. Zaitsev, and T. M. Ivanova, Russ. J . Inorg. Chenr., 1982,27, 1755. ati4 J. Dillen, A. T. H. Lenstra, J. G . Haasnoot, and I. Reedijk, Polyhedron, 1983,2,195. 285 L. L. Zaitseva, A. V, Velichko. and A. Yu. Vakhrushin, Russ. J. lnorg. Chem., 1982, 27, 1284. SS*

266 Table 9

Spectroscopic Properties of Inorganic and Organometallic Compounds Vibrational assignmentslcm-' .for co-ordinated water molecules in M(NCS),(dmtP),(H,O), rock POHz

M Mn Fe co Ni

Cd

3370 3370 3375 3375 3355

3245 3250 3255 3258 3 240

1688 I 690 1657 1666 I685

695 723 740 755

645 660 665 692

685

650

Resonance Raman spectra were obtained for aerated cytochrome d from 105 cm-l) attributed to 0-0 stretching.266 E. coli K12; these showed absorptions (1078-1

H L \ /O\ OC-Ru-0-Ru-CO oc' \H/ \co

=,

[Fe(L)OH], [L = N,N'ethylenebis(salicylamine)] gives v(0H) of the unit (87) at 3600 cm-l. An OH deformation of this unit was identified at 880 cm-l, shifting to 621 cm--l on de~teriation.~~' v(OH) was assigned for complex (88) (L = PPh,, PMe,, or AsPh,) (see Table

Table 10 Assignmentslcm-' ~fv(0H) modes in complex (88)

L

4OH) 3625, 3575 3640, 3625 3620. 3570

Oxygen adducts of Co" complexes with tetradentate Schiff-base ligands derived from ethylenediamine and substituted acetylacetones or benzoylacetones have i.r. bands, 1 130-1 150 cm-l, due to the superoxide-like oxygen ligand.269 Diamagnetic Co(sa1-Hpen)O, [H,(sal-Hpen) = (89)l gives Raman bands at 1260 and 510 cm-l that are assigned to ~ ( 0 0 and ) v(CoO), respectively. The R. K. Poole, B. S. Haines. J . A. M. Hubbard, M. N. Hughes, and N. J. Campbell, FEBS Lett., 1982, 150, 147. 297 L. Borer. L. Thalken, C. Ceccarelli. M. Glick, J. H. Zhang. and W. M . Reiff. Inorg. Chenl.. 1983,22, 1719. 268 D. F. Jones, P. H. Dixneuf, A. Benoit. and J.-Y. le Marouille. horg. Chem., 1983, 22, 29. MU K. Kasuga. T. Nagahara, A. Tsuge, K. Sogabe. and Y. Yamamoto, Bidl. Chem. SOC.Jpn.. 1983,56, 95. 266


267

former is very high.2701.r. was used to investigate oxygen adducts of five-coordinate mercaptocobalt(1r) porphyrins, synthetic analogues for the active site in cytochromes P450.27 Sr[Rh(OH),] has v(0H) at ca. 3400 cm-l and (a very broad band) 3200 cm-l. G(Rh-OH) was at ca. 500 cm-1.272

Pt(C,F,),(H,O) has v(0H) at 3660 and 3600 cm-l. In Pt(C6F5),L(L = Me,CO, MeEtCO, etc.) there are only small shifts in the ketonic v(C=O) with respect to the free ligand; hence there is a very weak interaction between Pt and the ketone.273The complexes trans-P,Pt(Rx)(OO-But) (P = tertiary phosphine, Rx = CF,, Ph, or Ph-o-CN) all have v ( 0 0 ) of the t-butylperoxo group at about 890 cm-1.274The complexes (R,P),PtO, (R3 = Cy,, Bu'Ph,, Bu',Ph, or But,Bun) have v(Pt0,) in the range 817-826 cm-l. The peroxocarbonato complexes (R,P),PtCO, show v(C=O) at 1675 cm-l and v(00) at 775 cm-1.276 Acetylacetonates and Related Complexes.-1.r. and Raman spectra of M(acac), (M = VO, Pd, or Cu) and their 3-C-bromo analogues were reported and assigned. Changes in ligand modes on bromination reflect the changes in electron d i s t r i b ~ t i o n . ~ ~ ~ OEt

OEt

W. Kanda, H. Okawa. and S. Kida. J . Chem. Soc., Chem. Colnmrtn., 1983, 973. P. Doppelt and R. Weiss, N o w . J . Chim., 1983.7. 341. t 7 % B. N. lvanov-Emin. N. A. Nevskaya, B. E. Zaitsev. and V. I. Tsirel'nikov, Rum. J. Inorg. Chem., 1983,28, 557. G. Lopez, G. Garcia, J. Galves, and N. Cutillas, J . Organornet. Chern., 1983, 258, 123. 274 G. Strukul, R. A. Michelin, J. D. Orbell, and L. Randaccio, Inorg. Chem.. 1983.22. 3706. 275 A. B. Goel and S. Goel, Znorg. Chim. Acfa, 1983, 77, L5. B. Vlckova, B. Strauch, and M. Ebert, Proc. Coqfi Coord. Chern., 1983,9,455. z71

268

Spectroscopic Properties o f Inorganic and Organometallic Compounds

Fe[Cl(COOEt),], has v(C=O) at 1582 cm-l, compared to 1762 cm-l in Cl,C(COOEt),, showing the acetylacetonate-like binding, i.e. (90).277 [Ir(acac-C3)(COD)(phen)]has v(C0) bands of acac at 1615 and 1570 cm-l. These are lower than usual for a C-bonded acac, but this bonding was confirmed by X-ray diffraction Complex (91) has i.r. bands due to the 0,O’-chelating acac ligand at 1510 and 1570 cm-1.278In complex (92) (R1= R2 = H, Me, Pr, or Ph, R1 = Ph, R2 = Me) v[C=O(free)] is in the range 1640-1670 cm-l, with v[C=O(complexed)] at 1575-1622 cm-l. Complexes (93), on the other hand, only have v(C=O) in the range 1570-1630 cm-l and v(Cu0,Cu) at ca. 500 cm-1.280 Me

Me

yQy p 0 R2

R’ 0,

R1

R2yy

O\

cu o/ ‘0

0

/ \

cu

o/ . ,

Jff \

R’

/

R2

R2

---

0

cu/ / \

\--’

‘R’

/

Me

Me

(92)

(93)

Au(C,F,),(acac) gives bands due to acac at 1530, 1560, and 1570 cm-l. The bridging N, in [Au(C,F,),N,], gives v(NN) at 2095 cm-l, i.e. higher than for Au-N, terminal bonds.281 Adducts of lanthanide tris(acety1acetonates) with acetylacetone imine have been prepared: MA3.2L (M = La, Pr, Nd, Eu, Gd, or Tb) and MA3.L (M = Dy, Ho, Er, Tm, Yb, or Lu). Acac bands, especially v(C-0), are at higher wavenumbers than in MA, itself. Thus, adduct formation leads to a decrease in the strength of the M-O(of acac) bonds.2as Several i.r. bands of uranyl hexafluoroacetylacetonatocomplexes UO,(hfac),B correlate linearly with the relative basicity of the neutral base ligand B. For example, vs(C=O) and v,,(C=O) and v,(C-C) and v,,(C-C), respectively, increase and decrease with increasing basicity of B.283

W. Petz and S. Kremer, Z . Naturforsch., Teil B, 1983, 38, 30. L. A. Oro, D. Carmona, M. A. Esteruelas, C. Foces-Foces, and F. H. Cano, J. Organornet. Chem., 1983,258, 357. 278 K. Hiraki, Y. Fuchita, and T. Uchiyama, Inorg. Chirn. Acta, 1983, 69, 187. 280 S. K. Mandal and K. Nag, Inorg. Chem., 1983, 22, 2567. 281 R. Uson, A. Laguna, M. Laguna, and M. Abad, J . Organomet. Chem., 1983,249,437. 282 G . V. Trembovetskii, E. V. Smirnov, I. A. Murav’eva, and L. I. Martynenko, Russ. J . Inorg. Chem., 1983, 28, 342. 283 R. G. Bray and G. M. Kramer, Inorg. Chem., 1983, 22, 1843. 277

269


Carbonato and Carboxylato Complexes.-The complex (94) has v,,(CO,) at 1642 cm-l and v,(C02) at 1350 and 1298 cm-l. Hence the benzoates are unidentate.284 Quite detailed ligand-mode assignments were made in anhydrous Cr(OOCR), (R = Me, Et, Pri, or CHCl,). These show that there is more than one type of carboxylate present, possibly two symmetrically bidentate and one unsymmetrically bidentate. 85 In the complex cis-[Cr(NA),en,]Br (NA = nicotinate) v(C=O) bands were seen at 1635, 1380, and 1355 cm-1.28* The i.r. spectrum of W,(O,CCF,), is consistent with the presence of four equivalent bidentate carboxylate ligand~.,~'1.r. data for [Me4N]a[M(02CCFS),J (M = Mn, Co, Ni, or Cu) suggest the presence of unidentate O,CCF, groups, especially the values of vas(C02)and v , ( C O , ) . ~ ~ ~ Complex (95) gives v(C=O) of the formate ligand at 1616 cm-l and v(CH) at 2850 cm-l, shifting to 2125 cm-l for the deuterio

9 (p-Oxalato)tetrakis(acetylacetonato)di-iron(rI1) shows bands due to v(C0) cm-l) and S(OC0) (805 cm-l), characteristic of tetradentate bridging oxalato groups (96). The usual bands of the acac ligand were also observed.2B0 Complexes (97) (X = C1 or Br, R = Me or CF,) give v,,(CO,) and v,(COz) as expected for bidentate chelating c a r b o x y l a t e ~In .~~ the ~ i.r. spectrum of complex (98) (R = H) the formato ligand has v(C0,) at 1547 and 1366 cm-l. For R = Me the analogous acetato bands are at 1528 and 1454 cm-1.282 1.r. bands said to be characteristic of unidentate oxalato groups, at 1615 and 1 585 cm-l, were seen for cis- and trans-[Co(en),NO,(C,O,)]* 2H,O? The v,(CO,) and va,(CO,) bands from [Ni(ida),12- (ida = iminodiacetato) show unidentate carboxylate co-ordination, compared to Ni(ida) 2H20, where bidentate co-ordination is more ( 1675

-

D. M. Hoffman, N. D. Chester, and R. C. Fay, Organometallics, 1983,2,48. R. Kapoor and R. Sharma, 2.Natwforsch., Teil B, 1983,38,42. J. C. Chang, L. E. Gerdom, N. C. Baenziger, and H. M. Goff, Znorg. Chem., 1983,22, 1739. D. J. Santure, K. W. McLaughlin, J. C. Huffman, and A. P. Sattelberger, Znorg. Chem.. 1983,22,1877. 888 M. Puri and R. D. Verma, Indian J. Chem., Sect. A , 1983, 22, 418. 2*@ J. H. Memfield and J. A. Gladysz, Organometallics, 1983, 2, 782. ago M. Julve and 0. Kahn, Znorg. Chim. Acta, 1983, 76, L29. D. A. Tocher, R. 0.Gould, T. A. Stephenson, M. A. Bennett, J. P. Ennett, T. W. Matheson, L. Sawyer, and V. K. Shah, J. Chem. Soc., Dalton Trans., 1983, 1571. P. J. Brothers and W. R. Roper, J . Organomet. Chem., 1983,258,73. 2ga J. N. Cooper, C. A. Pennell, and B. C. Johnson, Inorg. Chem., 1983,22. 1956. 294 I. Lukes, M. Ebert, and I. Smidova, Znorg. Chim. Actu, 1983, 76, L99. 284

270


OJ

\

R

v(C=O) and v(C0) bands of the oxalato group were assigned under D2,, symmetry for the complexes trans-[Pt(~x),X,]~-(X = CI, Br, I, SCN, or OH). v(C=O) modes were higher and v(C0) lower than in the platinum(I1) complex [Pt(ox),]2-.295 L2Cu[3-py(CO,)] (L = PPh,) contains unidentate carboxylate bonding, with v,,(CO,) at 1615 cm-l and v,(COz) at 1392 cm-1.296The squarate complex Cu,(tmed),(CO)(C,O,) gives i.r. bands due to the squarate at 1640, 1530, and 1450 cm-l. Hence it is not symmetrically bonded through all four oxygen atoms. This was confirmed by X-ray diffraction, showing a bridging unit (99) (tmed = N,N,N’,N’-tetramet hylethylenediamine).2g7

The carboxylate gives one strong v(C=O) band in the i.r. spectra of (RC02)6Zn,O (R = Me, Et, Pri, But, etc.) (1570-1607 cm-9. This is characteristic of high symmetry and bridging c a r b o ~ y l a t e s . ~ ~ ~ 1.r. spectra for M(02CCF3)3L( M = Pr, Nd, or Sm, L = 2,2’-bipyridine or I ,lo-phenanthroline) show that the trifluoroacetato groups are bidentate, giving the lanthanoid a co-ordination number of 8.299 Complexes MX4*nL(M = Th or U, X = O2CCF3or 02CCC13,L = a -0 or an S=O ligand) give complex i.r. spectra due to the carboxylate ligands. There seem to be both unidentate and bidentate or bridging groups. L is bound via oxygen in all cases.3ooThe C032-stretching modes in actinide(v) and actinide(VI) complexes in aqueous solutions show that the carbonato group is complexed, but it was not possible to decide the mode of ~ o - o r d i n a t i o n . ~ ~ ~ 295

G. Ftimkus and W. Preetz, Z . Anorg. Allg. Chem., 1983, 502, 73. Cariati, L. Naldini, A. Panzanelli, F. Demartin, and M. Manassero, Inorg. Chim. Acta,

2 ~ F. 6

1983, 69, 117. G. Doyle, K. A. Eriksen, M. Modrick, and G. Ansell, Organometallics, 1982, 1, 1613. R. M. Gordon and H. B. Silver, Can.J. Chem., 1983, 61, 1218. 290 S. N. Misra and M. Singh, J. Indian Chem. SOC.,1983, 60, 115. K. W. Bagnall, 0. V. Lopez, and L. Xing-Fu, J. Chem. Soc., Dalton Trans., 1983, 1153. 301 C. Madic, D. E. Hobart, and G. M. Begun, Inorg. Chem., 1983, 22, 1494. 287


271

Lr., and Mossbauer, spectra show that RSn(02CCF3), (R = Et or Pr) contain two different types of O,CCF, groups. In R,Sn(O,CCF,), both of the trifluoroacetato groups are bidentate. R,SnO,CCF, is polymeric in the solid, with five-co-ordinate Sn, but monomers are present in 1.r. spectra of Ph,SnO,CCF, are also in agreement with the presence of polymers in the solid (bridging carboxylate, five-co-ordinate tin) but monomers (unidentate carboxylate, four-co-ordinate tin) in Keto, Alkoxy, Ether, and Related Complexes.-Co-deposition of Mg and excess acetone at liquid-nitrogen temperature produced an unstable charge-transfer complex, with a characteristic v(C=O) at 1595 cm-l, together with a stable adduct, with v(C=O) at 1685 cm-l, compared to 1705 cm-l for free Me,C=O at - 190 0C.303 One v,(COC) and two v,,(COC) bands of co-ordinated THF, ca. 860, 1020, and 1060 cm-l, were seen for all of the complexes Cr(THF),X, (X = CI, Br, or I) and [Cr(THF),X,]- (X = C1, Br, 1, or NCS). The shifts from free THF are all slightly greater for the more stable, neutral species than for the anions.306 v(C=O) in MoO,(RX), [RX = hydroxamate of the form RN(0-)C(=O)C6H4X,R = H, Me, or Ph, X = OMe, H, Cl, or NO,] is very low (1485-1555 cm-l) owing to the greater importance of the form (100) rather than (101) in the complexes.,06

Although n.m.r. data show that O,, of guanosine, inosine, or 1 -methylinosine (= L) is co-ordinated to rhodium in [Rh(PPh,),(CO)L]+, there is no significant

shift in v(C=O) in their i.r. v(C=O) of the amide ligand is reduced by 70-75 cm-1 on formation of the complexes AgNO, - 2L (L = dimethylformamide or dimethyla~etamide).~~~ Fourier-transform i.r. spectra of Eu3+in DMF solutions show that a species Eu(DMF),~+,of C,, symmetry, is formed and that x is probably equal to 8.309 Compound (102) (= L) forms complexes (ML)(NO,), with La3+, Pr3+, and Eu3+that show shifts to low wavenumber of 40-60 cm-l for v(C0C). This is due to metal-ether 0 interaction. Nitrate bands were all typical of co-ordinated, C,,, groups.31oPrL.H,O (HsL = cyanuric acid) shows broad bands in the range 302 A.

Midha, R. D. Venna, K. Brown, and R. V. Parish, Indian J. Chem., Sect. A. 1983,22.

211.

T. N. Srivastava and J. Singh, Indian J . Chem., Sect. A, 1983, 22, 128. C. Hisatsune, Spectrochim. Acra, Part A , 1983, 39, 853. 305 P. J. Jones, A. L. Hale, W. Levason, and F. P. McCullough, Inorg. Chem., 1983, 22, 2642. 308 P. Ghosh and A. Chakravorty, Inorg. Chem., 1983, 22, 1322. 307 D. W. Abbott and C. Woods, Inorg. Chem., 1983, 22, 597. 308 V. P. Komarov and I. S. Shaplygin, Rum. J. Inorg. Chem., 1982, 27, 1685. 309 J. C. G. Bunzli and J. R. Yersin, Hefv. Chim. Acta, 1982, 65, 2498. 310 0. A. Gansow and A. R. Kausar, Znorg. Chim. Acta, 1983,72,39. ao4 I.

272


1350-1650 cm-l. It is believed to be polymeric, with bridging cyanurate ligands.,ll v(C=O) modes in ThC14L3(L = MeCONMe,, EtCONMe,, EtCONEt,, or Bu'CONMe,) are all decreased (by 50-80 cm-l) in comparison with the free ligand.,12 Complexes (Ph,SnCl), - L. H 2 0 ( L =: 18-crown-6 or 15-crown-5) have v,,(COC) slightly lower than in the free crown ethers. A similar observation was made for (R2SnX,);18-crown-6~2H,0(R = Me, X = Cl, IZ = 2; R = Ph, X = C1 or NCS, n = l).,13 v(C0C) modes of the crown-ether ligands in SnX,L (X = C1 or Br, L = 12-crown-4, 15-crown-5, or 18-crown-6) show that the tin only interacts strongly with two or three of the polyether oxygen atoms.314 v(C=O) in R1,Sn(R2CONR:30),is decreased by 40-1 10 cm-l from the freeligand values. Hence co-ordination of C=O to the metal gives five-membered chelate rings at Sn.J15 Ligands Containing O-N or 0-P Bonds.-Raman spectra of aqueous solutions of NaNO, could be interpreted in terms of the presence of free aqua NO,- ions, solvent-separated ion pairs, contact ion pairs, and ion aggregates. All gave characteristic components of the symmetric stretching band.31gSimilar results were obtained for MNO, ( M = NH4, NMe,, Li, K. or Rb). The ammonium derivatives gave only one species, however.:'17 The complexes MX,.OP(NCS), (M = Ti, Zr, Hf, or Sn, X = C1; M = Ti or Zr, X = Br) all gave i.r. and Raman spectra showing that they have a cisoctahedral structure and that the OP(NCS), is O-bonded.,la Cr(NO,),*xN,O, (x = 1 or 2) both give v(N0) of NO+ and bands of symmetric bidentate nitrato groups, i.e. they are (NO)[Cr(NO,),] and (NO),[CrDiethylphosphonoformato (103 ; depf) complexes [Cr(depf),]+, G. B. Seifer, N. A. Chumaevskii, N. A. Minaeva, and Z. A. Tarasova, Russ. J. Inorg. Chem., 1983,28,498. 314 K. W. Bagnall, X. F. Li, P.-J. Pao, and A.-G. M. Al-Daher, Can. J. Chem., 1983,61,708. 313 P. J. Smith and B. N. Patel, J. Organomel. Chem., 1983,243, C73. 314 P. A. Cusack, B. N. Patel, and D. J. Smith, Inorg. Chim. Acta, 1983,76, L21. 316 M. K. Das, M. Nath, and J. J. Zuckerman, Inorg. Chim. Acta, 1983,71, 49. 316 R. L. Frost and D. W. James, J. Chem. SOC.,Faraday Trans. 1, 1982,78,3223. 317 R. L. Frost and D. W. James, J. Chem. SOC.,Faraday Trans. 1, 1982,78, 3235. 318 V. V. Skopenko, A. I. Brusilovets, and A. V. Sinkevich, Ukr. Khim. Zh., (Russ. Ed.), 1983, 311

49, 3. 319

A. A. Natsina, E. A. Ukraintseva, L. A. Sheludyakova, and I. I. Yakovlev, Russ. J. Inorg. Chem., 1983,28,1017.


273

0 EtO-P -C-OEt\o lo /

(103)

Fe(depf),, and M(depf), (M = Fe, Cu, or Zn) were characterized by i.r. spectroscopy. All are polymeric, with bidentate, bridging depf ligands, co-ordinated via two PO0 oxygens. Mn(depf), contains both bidentate and tridentate ligands, the latter also co-ordinated via C=O. The complexes M(depf), (M = Co or Ni) contain only tridentate ligands and may be monomeric.32o v(P0) bands in [(Cl,PO)ReCI,(NSCl)] and [(C1,PO)ReCI3(NSC1),] are lower than in free POCI,, owing to Re-0 c o - ~ r d i n a t i o n . ~ ~ ~ General assignments of the Raman spectra of [M(py0)J2+ (M = Co or Ni) were given. v ( N 0 ) bands were at 1210 and 1188 cm-l for M = Co and at 1213 and 1185 cm-l for M = Ni, all lower than in free py0.322 ~(-0) decreased by 25-90 cm-l from OPR, on formation of Pd(OPR3),(NO,), (R = Pr, Bu, i-pentyl, or Ph) owing to P d - O = P co-ordination. The NO, modes were assignable under C,, Bis-(2,2’-bipyridyl)nitritocopper nitrate gave bands due to the -ON0 ligand at 1350, 1115, and 850cm-l in the i.r.324 The NO,- ion is found to have almost symmetrical bidentate binding to the Cd in Cd(N0,),.4H,0.326 Bands due to both terminal (unidentate) and bridging (bidentate) nitrato groups were seen in the i.r. spectrum of dimeric {Hg[A~(mesityl),](NO,),)~.~~~ The internal nitrate modes of EU(NO,)~~were all consistent with bidentate nitrato c o - ~ r d i n a t i o n . ~ ~ ~ v(P0) decreases by 10-70 cm-l from the free-ligand values on formation of the complexes Ln(TTFA),L (TTFA = thenoyltrifluoroacetonate,L = Bu,PO,, Ph,PO, etc., Ln = La, Nd, Ho, Er, or Yb).328 1.r. bands for [YL2(N03),]N03* H 2 0 and [LnL,(NO,)(OH)(H,O)]NO, [Ln = La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, or Ho, L = 2-(2’-pyridyl)benzimidazole] confirm the existence of both co-ordinated (C,”)and free (D,,,) nitrate Raman and i.r. spectra of [U02(N03),]2-show that there are two types of co-ordinated nitrato groups. It was suggested that the anion probably has the structure trans-U02(ON02)2(02N0)2, i.e. both uni- and bi-dentate groups.33o 380

C. M. Mikulski, B. Marks, D. Tuttle, and N. Karayannis, Inorg. Chim. Acfa, 1983, 68,

381

U. Miiller, W. Kafitz, and K. Dehnicke, 2. Anorg. Allg. Chem., 1983, 501, 69.

119.

J. F. Arenas, J. I. Marcos, and J. C. Otero, J . Raman Specfrosc., 1983, 14, 7. A. Shorokhov and V. S. Shmidt, Rws. J. Inorg. Chem., 1983,28, 701. 3p4C. Simmons, A. Clearfield, W. Fitzgerald, S. Tyagi, and B. Hathaway, J. Chem. SOC., Chem. Commun., 1983, 189. M. T. Carrick, D. W. James, and W. H. Leong, Ausf.J. Chem., 1983,36, 223. 3~ E. C. Alyea, S. A. Dim, G . Ferguson, and P. Y. Siew, Can. J . Chem., 1983,61,257. J. C. G. Biinzli, B. Klein, G.-0. Pradervand, and P. Porcher, Znorg. Chem., 1983,22, 3763. S . I. Anufrieva, N. I. Snezhko, L. I. Martynenko, and N. I. Pechurova, Russ. J. Znorg. Chem., 1982, 26, 1577. A. Mishra, M. P. Singh, and V. K. Singh, J. Indian Chem. SOC.,1982, 59, 622. s80 C. D. Flint and P. Sharma, J. Chem. SOC.,Faraday Trans. 2, 1982,78,2155. 348

818 N.

274


Previous assignments of v(P=O) in actinoid tetrachloride complexes MC1,(OPPh3) need revision in the light of work on UCI,(OPPh,). Two such modes are now recognized, and the new assignments are given in Table 1 1.331MC14L2 and MC14L (M = Ce or U, L = uni- or bi-dentate phosphine oxide, arsine oxide, sulphoxide, or amide) give decreases in v(E=O), 45-180 cm-l, compared to the free ligand. Hence co-ordination takes place via oxygen.332v(P=O) modes at 1192 cm-l, in U02(N03)2[(PriO)2P(0)CH2C(O)NEt2], together with v(C=O) at 1607 cm-l, suggest that there is bidentate co-ordination involving both P=O and C = 0 . 3 3 3 Table 11 Assignrnents/crn-' qfv(P=O) modes in MCI,(OPPh,), v( P =0)

M Th Pa

1070, 1046 1070, 1045 1068, 1041 1068, 1040 1071. 1043

U

NP Pu

1.r. studies show that pyridine-N-oxide derivatives containing electronreleasing substituents form strong 2 : 1 complexes with SnCI,. Derivatives containing electron-neutral or -withdrawing substituents, however, form weak 1 : 1 complexes.334 Ligand modes were assigned for the 0,Obridging dimethylphosphinato ligands in complex ( 104) and ( Me,P02)20(SbC13)2.The latter gave four v(P0,) bands: out-of-phase and in-phase v,, at 1070 and 1042 crn-l, respectively, and out-of-phase and in-phase vq at 1019 and 998 cm-l, respectively.338" M e Me \

Ligands Containing 0-S

or O-Se

/

Bonds.-The

i.r. spectra of NaM2[(V02)3-

(S04),(H20),]~(5-x)H20 (M = K, Rb, or Cs) contain both uni- and bi-dentate sulphato groups.336 331

G . Bombieri, F. Benetollo, K. W. Bagnall, M. J. Plews, and D. Brown, J. Chem. SOC., Dalton Trans., 1983, 343.

J. Barry, J. G. H. du Preez, T. I. Gerber, A. Litthauer, H. E. Rohwer, and B. J. van Brecht, J . Chem. SOC.,Dalton Trans., 1983, 1265. 338 S. M. Brown, E. N. Duesler, and R. T. Paine, Inorg. Chem., 1983,22,286. 334 C. L. Wild, M. Spahis, R. D. Blankenship, J. W. Rogers, and R. J. Williams, Polyhedron, 333

1983,2, 379. 335 S. Blosl, W. Schwarz, and A. Schmidt, 2. Naturforsch., Teil B, 1983,38, 143. 336 A. A. Ivakin, I. G . Chufarova, A. P. Yatsenko, 0. V. Koryakova. N. I. Petunina,

M. P. Glazyrin, Russ. J. Inorg. Chem., 1983, 28, 919.

and


275

1.r. data for Ru(XC,H,SeO,), and R U ( X C ~ H ~ S ~ O(X , ) ~= Y H or halogen. Y = C1 or Br) are all consistent with 0,O'-seleninato co-ordination. The pres-

ence of three v(Se0) bands for the tris complexes suggests octahedral coordination, with D , symmetry. The bis complexes are thought to be polymeric. with bridging halide.337 The complexes LnL8(C10& (Ln = lanthanoid, L = dipropyl sulphoxide) give i.r. spectra indicating co-ordination of the L via the oxygen atom. with ionic perchlorato groups. 338 It has been suggested that the t2 stretching mode of SO4 is diagnostic of the sulphato bonding mode in uranyl sulphato complexes. It was not wholly unambiguous, however, and needed supplementing by other physical The SO, modes of K,[UO,(SO,)F,J~H,O were consistent with the presence of bridging, bidentate sulphato groups (Table 1 Table 12 Sulphato-mode assignmentslcm-l for K2[U02(S04)F2 J H20 V(SO4)

(r3

V(SO4)

(4)

WSOd 860,)

(tn)

1223, 1140, 1044 989 643, 619, 586

(4

460,421, 414 [+ vWF)modes]

Al(SO,F), has v(S0) bands at 1 180 and 1360 cm-l, characteristic of bidentate, bridging fluorosulphato groups. Only one v(SF) mode was seen (812 cm-l); hence there was only one type of SO,F group.""

Ligands Containing 0-C1 &&.-There is i.r. evidence for the presence of Mg(C1O4), - in [Bu4N][Mg(CIOc.),].The perchlorato ligands all appear to be bidentate, with v(CI0) at 960. 1 ~ 3 0 ,1 1 4 0 , and 1210 cm-l and 6(ClO,) at 460. 485, 620, and 660 ~rn-l.,,~ The i.r. spectrum of gaseous Zr(ClO,), shows the structure to be the same as in the Ligand modes were assigned for [Cu(bipy),(0,C102)]+.The co-ordination of the C104 must be very weak, as the bands were only shifted slightly from the 'ionic' values.344 The i.r. and Raman spectra of Zn(CIO,), and C102Zn(C10,), show that the bonds between Zn and C104 are highly ionic. Jt appears that the Zn(ClO& is polymeric, with bridging tridentate CIO, groups.345 C. Preti, L. Tassi, and G . Tosi, Spectrochim. Acta, Part A , 1983, 39, 1.

~3'

M. A. Banares Munoz, R. J. Ruano Casero, and M. E. Perez Bernal, An. Quim. B,

1982,

78, 39 1.

L. B. Serezhkina, V. N. Serezhkin, and M. A. Soldatkina, Russ. J. Inorg. Chem., 1982, 27, 987. wo M. A.

Soldatkina, L. B. Serezhkina, and V. N. Serezhkin, Russ. J. Znorg. Chem., 1983.

28,709.

S. Sin& and R. D. Verma, Polyhedron, 1983, 2, 1209. 2.K. Nikitina and V. Ya. Rosolovskii. Russ. J . InorR. Chem.. 1982. 27, 1256. A. V. Dudin, V. P. Babaeva, and V. Ya. Rosolovskii, Russ.J . Znorg. Chem., 1983,28,950. s44 J. Foley, D. Kennefick, D. Phelan, S. Tyagi, and B. Hathaway, J . Chem. SOC.. Dalfon Trans., 1983, 2333. 346 J. L. Pascal, J. Potier, and C. S. Zhang, Compt. Rend., 1982, 295, 1097. sll

276

Spectroscopic Properties of Inorganic and Organometallic Compounds 7 Sulphur and Selenium Donors

Cp,Hf(S2CNR1R2) and CpHf(S,CNR1R2), (R1 = H, R2 = CBHOor C7H13; R1= Et, R2 = MeC,H,) give dithiocarbamato bands characteristic of chelating ligands.346 (C,Me,),VS, has a strong i.r. band at 552 cm-l, due to the v(SS) mode of the ring (105).347 v(CN) modes of the dithiocarbamate ligands in MRJR1)(S2CNR2,),(M = Nb or Ta, R1 = Me, Pr", Pri, But, or Ph, R2 = Et) all show that they are bidentate.348 MoL4 [L = (106)] contain eight-co-ordinate molybdenum, with extensive metal-to-ligand x-backb~nding.:~~~

s\s/s\s/s

I Mo

I Mo

( 107)

The complex [Mo,(NO)~(S~),(S,)OH]~has v(OH) at ca. 3580 cm-l and v(S5) at 474/425 cm-l, due to the bridge (107).350v(C-=S) and other ligand modes were assigned for Mo(S,S)(x-allyl)(CO),L (S,S = methylxanthate, N-ethyldithiocarbamate, or N,N-diethyldithiocarbamate, L = PPh3), Mo(S,S)(x-ally1)(CO),(L-L) (L-L = bipy, phen, etc.), [Mo(S,S)(x-allyl)(L-L)],( p-CO), (L-L = dppe), and [Mo(S,S)(~-allyl)(CO),],(p-L-L) (L-L = 4,4'-bipy, e ~ c . )1.r. . ~ and ~ ~ Raman spectra of Mo2S2X3(SeX2) (X = C1 or Br) showed that the Sex, species were indeed 1.r. and Raman spectra of Re(NR1)(S2CNR2,),and Re(OR3)(NR1)(SzCNR22)2 (R1 = Me, Ph, or p-tolyl, R2 = Me or Et, K:'= Me or Et) suggest that (i) the trisdithiocarbamate complexes possess cis six-co-ordinate geometry, with one unidentate dithiocarbamate group, and (ii) two t m n s isomers of the alkoxy complexes are present in solution.363 A number of ligand bands were identified from the resonance Raman spectrum of the Fe-S flavoprotein-electron-transfer flavoprotein d e h y d r ~ g e n a s e . ~ ~ ~ The bridging SO group in [Ru(NO)X2LI2SO(X = C1 or Br, L = PPhs or AsPh,) has v(S0) at 1100 cm-1.355 v(CS) band assignments for M(pmdtc)(pip)(OH),H,O (M = Ru or Rh, Hpmdtc = pentamethylenedithiocarbamic acid, pip = piperidine), [Pt(pmdtc),(pip),]Cl,, and [Pd(pmdt~)~(pip)~] * 2 H 2 0 show that in the Ru"', Rh'", and PtIV S. Kumar, G. S. Sodhi, and N. K. Kaushik, Russ. J. Inorg. Chern., 1983, 28, 196 S. A. Koch and V. Chebolu, Organometallics, 1983, 2, 350. 348 L. S. Tan, G. V. Goeden, and B. L. Haymore. Inorg. Chem., 1983, 22, 1744. 348 J. Selbin, Inorg. Chim. Acra, 1983, 71, 201. 360 A. Muller, W. Eltzner, H. Bogge, and E. Krickemeyer. Angew. Chem., Int. Ed. E n d . . 1983. 346

347

22, 884.

M. F. Perpiiian, L. Ballester, and A. Santos, J. Organomet. Chem., 1983, 241, 215. S. V. Volkov, V. L. Kolesnichenko, N. G. Timoshchenko. and N. G. Aleksandrova. Ukr. Khim. Zh. (Russ. Ed.), 1983, 49, 563. 813 G. V. Goeden and B. L.Haymore, Inorg. Chem., 1983,22,157. 354 J. Schmidt, J. Beckmann, F. Frerman, and J. T. McFarland, Biochem. Biophys. Res. Commun., 1983, 113, 784. 356 K. K. Pandey, Spectrochim. Acta, Part A , 1983. 39, 925. 351 352

Vibrational Spectra of Some Co-ordinatedLigands

277

complexes the dithiocarbamate is bidentate whereas in the Pd" complex it is unidentate.366 The splitting between v(C=S) and v,,(CS) of the trithiocarbonate group is a good criterion for the degree of covalent bonding. In ionic compounds the splitting is less than 50 cm-l, but in Co"' or Ni" trithiocarbonato complexes it is 100-160 cm-l. In purely covalent compounds such as (C,H,)CS, it is near 200 cm-1.361

(C6F,),Co(THT), (THT = tetrahydrothiophen) gives v(CS) at 670 cm-', compared to 683 cm-l in the free ligand. This is consistent with Co-S coComplexes (108) (n = 0, L = halide, CN-, NCS-, etc.; n = 1, L = phosphine, py, H 2 0 , etc.) give dithiocarbamate bands 1480-1550 cm-l and 1 ~ 1 0 6 cm-l, 0 due to v(CN) and v(CS), respectively.369

1''

Q

Shifts in internal ligand modes in COL, on formation of I2 adducts C0L,.I2 (L = tris-morpholine-4-carbo-dithioor -diselenato) .show that the form R2N+=CX2,- (X = S or Se) makes a greater contribution in the a d d ~ c t . ~ ~ O mi(S4)2]2-gives bands due to the S,2- ligand at 480,430, and 375 cm-l in the i.r. Only the 480 cm-l feature is seen in the Raman spectrum, and hence this is assigned as vs.361 Complexes (109)(M = Pd or Pt) give an intense i.r. band at 1535 cm-l (Pd) or 1545 cm-l (Pt), showing considerable double-bond character in the C-N bond of the co-ordinated dithiocarbamate.366"

c1 (109)

Vibrational spectra have been obtained and assigned in some detail for LMC12 [M = Pd or Pt, L = alkylaminodithioxodi-h6-phosphane, e.g. (Et2N),P(S)P(S)(NEt,),] and LCuCI. v(PS) is lowered by up to 80 cm-lon co-ordination. V. K. Sinha, M. N. Srivastava, and H. L. Nigam, Indian J. Chem., Sect. A, 1983. 22. 348. J. Roger, J. N. Pons, and M. Stem, Rev. Chim. Miner., 1982, 19, 663. 868 M. M. Brezinski and K. J. Klabunde, Orgunometallics, 1983, 2, 1116. 369 J. Doherty and A. R. Manning, J. Organomet. Chem., 1983,253, 81. 9ao G. Crisponi, P. Deplano, and E. F. Trogu, Znorg. Chim. Acta, 1983,75, 135. 361 A. Muller, E. Krickemeyer, H. Bogge, W. Clegg, and G. M. Sheldrick, Angeiv. Chem.. Znt. Ed. Engl., 1983, 22, 1006. A. Mantovani, J. Organomet. Chem., 1983, 255, 385. 356 357

278


In addition, v(PP), v,(PS), and v,,(PS) are all i.r. active in the complexes, i.e. the ligand symmetry is lower in the complexes. A11 of the Pd and Pt complexes contain the unit (1 1.r. spectra were reported for M2(p-SPR12)2(PR23)2 (M = Pd or Pt, R1, R2 = alkyl, aryl, etc.). v(PS) was lower than in the free secondary phosphine sulphides, showing the lower P-S bond order in the p-SPRl, ligand~."~ 1.r. spectra of Pt(HNSCCSNH) and its deuteriated analogue ( 3 3 4 0 0 0 cm-l) were measured, and normal-co-ordinate analyses were carried out for two different 1 : 1 metal :ligand models of C,,, symmetry. Strong coupling occurred between many of the ligand modes.365 (PhsP),Cy(SzCPh) gives vas(CS2)and v,CCS2) at 1015 and 925 cm-l, respectively. In [(Ph,P),Cu(S,CPEt,)]+ va,(CS2)is at 1040 cm-1.366 OR \ ,OR SAP\

OR (1 11)

Complex (111) (R = Me, Et, Pr', Bu", Bu', or Bus) all have v(P-OR) at 1020-980 cm-l, v(C-OR) at 1190-1 130 cm-l, vs(PS2)at 545-500 cm-l, and v,,(PS,) at 645-635 cm-I. The PS, modes in Sb(S,PR,), are at rather lower wavenumbers.367 8 Potentially Ambident Ligands Cyanates, Thiocyanates, Selenocyanates, and Their Is0 Analogues.-Spi n isomers were characterized by i.r. for C ~ S - F ~ L ( N C[L S )= ~ derivative of tris(Zpyridylmet hyl)amine]. The 5T2state gave a strong v,,(NCS) doublet, 20602080 cm-l, while the l A l state gave a strong doublet, 2100-2120 cm-1.368 A full assignment has been given for the vibrational modes in Ru(NCS),'-; the'symmetry selection rules for Oh symmetry were obeyed. The v(CN) modes were at 2148 (alg), 2104 (eg),and 2100 (tl,) cm-1.36B N,- reacts with Ru,(CO),, to give new isocyanato complexes such as [Ru,(NCO)(CO),,]-, with v(NC0) at 2189 cm-l, and [RU,(NCO)(CO)~,]-, 2230 cm-1. Together with v(C0) data, the latter suggested the structure (112).370 D. Troy, J.-P. Legros, and G. P. McQuillan, Inorg. Chim. Acta, 1983, 72, 119. B. Messbauer. H. Meyer, B. Walther, M. J. Heeg, A. Rahman, and J. P. Oliver, Inorg. Chem., 1983, 22, 272. 365 D. Miernik and B. B. Kedzia, Bull. Acad. Pol. Sci., Ser. Sci. Chim., 1982, 30, 71. 366 C. Bianchini, C. A. Ghilardi, A. Meli, and A. Orlandini, Inorg. Chem., 1983,22, 2188. 367 D. B. Sowerby, 1. Haiduc, A. Barbul-Rusu, and M. Salajan, Inorg. Chim. Actu, 1983. 68, 87. 368 F. Hojland, H. Toftlund, and S. Yde-Andersen, Actu Chem. Scand., Ser. A. 1983.37, 251. '"' H.-H. Fricke and W. Preetz, 2.Naturforsch., Teil B, 1983, 38, 917. ;"OD. E. Fjare, J. A. Jensen, and W. L. Gladfelter, Inorg. Chem., 1983, 22, 1774. 363

A64


279

Complexes ML2(NCS), (M = Co, Ni, or Cd, L = hydrazides of propionic, butyric, hexanoic, and octanoic acids) give v(CN) and v(CS) characteristic of M-NCS bonding. The hydrazides are co-ordinated via the hydrazide nitrogen and carboxyl The complexes M(bipy)(NCS), (M = Co or Mn) have NCS bands showing that M-NCS-M bridges are present in the polymeric structures, e.g. for M = Co bands are at 2093 and 21 12 The isomeric species [M(NCS),(SCN),-,J3- (M = Rh, n = 0-4; M = Ir, n = 0-5) have been characterized and the ligand modes assigned. While v[CN(N)] and v[CN(S)] were in the region 2095-2170 cm-l, v[CS(N)] was at 810-835 cm-l and v[CS(S)]at 695-710 ~ r n - l . ” ~ [Pd(NCS)(trenMe,)]+ {trenMe, = tris-[2-(dimethylamino)ethyl]amine} is always Pd-N bonded, according to the v(CN) wavenumbers, irrespective of the counter-ion. This should be compared with [Pd(NCS)(Et,dien)]+,where changing the counter-ion can induce the formation of Pd-S forms.374 Evidence for the formation of a surface Ag-SCN species by the adsorption of NCS- at a silver electrode came from the surface-enhanced Raman spectrum of this 1.r. spectra show that only bridged NCS or NCO groups were present in the bimetallic complexes L,M1(NCX)M2,(SCN),, between M1 and M 2(M1= Mn, Fe, Co, Ni, or Cu, M 2= Ag or Hg, L = pyridine). Hence all of the complexes are Characteristic i.r. bands show that NCS is N-bonded to Zn or Cd but However, i.r. S-bonded to Hg in M(NCS)2L [L = Me2NC(S)S2C(S)NMe2].377 [the intensity of v(CN)] reveals exclusively Hg-NCS bonding in H&(hexamethylenetetra-amine)(NCS),, the first such example. v(Hg-NCS) was seem at 550 cm-1.378 1.r. spectra of Ph,Pb(SeCN) in various solvents show that ionic, N-bonded and Se-bonded forms are possible, depending upon the donor power and dielectric constant of the solvent

’m R. I. Machkhoshvili, T. V. Shalamberidze, and R. N. Shchelokov, Russ. J. Inorg. Chem..

1982, 27, 973.

W. Dockum, G . A. Eisman, E. H. Witten, and W. M. Reiff, Iliorg. Chem.. 1983.22, 150. 12, 23. 374 S. N. Bhattacharya and C. V. Senoff, Inorg. Chem., 1983, 22, 1607. 375 M. J. Weaver, F. Ban, J. G . Gordon, and M . R. Philpott, Surf. Sci., 1983, 125. 409. 370 S. B. Sharma and T. N. Ojha, Indian J . Chem., Sect. A, 1982, 21, 1049. 377 A. K. Srivastava, R. K. Agarwal, V. Kapur, and P. C. Jain, J . Indian Chem. Soc., 1983. 60,496. 378 I. S. Ahuja and C. L. Yadava, Inorg. Chem. Acta, 1983, 76, L l . 37B M. Onyschuk and I. Wharf, J . Organomet. Chem., 1983, 249, C9. x2B. 373

H.-H.Fricke and W. Preetz, Z . Anorg. Aflg. Chem., 1983, 507,

280


Ligands Containing N and 0 Donor Atoms.-1.r. data suggest that in VOS04-2L (L = isonicotinic acid hydrazide) V is unidentate, co-ordinating through the 0 atom H

/O\

(H3N)3Con*-0-

\

CO"'(NH~)~

H

I o=c=o

I

Complex (113), involving a bridging Hedta ligand, has bands at 1570 and 1620 cm-l, assigned to the p-carboxylato and unidentate C0,- groups, respecti~ely.~ Skeletal ~' modes and the observed Av(C02) (= vaS - v,) of 220 cm-l show that the glycinate is acting as an N,O-chelate, with unidentate carboxylate, in complex (1 14). The v(NH,) (3210 cm-l) and 6(NH2) (1 610 cm-l) values are also consistent with amino-group co-ordination.382 The complex (1 15) gives v(C=O) of the ylide at lower wavenumbers than in the free ligand; hence the co-ordination is via oxygen, as

H2

O

O

H2

11 ,o, ,Mo11 /N.YH, c 1I 0 I 'O'C

H,C"\ I

o+-=o

+SMe, I

Mo,

OH,

OH,

----+0

v(NH,) wavenumbers in M(Hapo),2+ [M = Mn, Co, or Ni, Hap0 = (116)] show that the NH2 is un-co-ordinated, i.e. the ligand is attached only by NO. Cu(apo),, on the other hand, gives evidence for bidentate co-ordination, of (117).384 Ligand-mode assignments in ML2 (M = Fe, Co, Ni, or Cu, HL = aromatic hydroxyoximes) are consistent with N,O-co-ordination of L.s8r, Z . M. Musaev, Ya. S. Usmankhodzhaeva, 0. F. Khodzhaev, and N. A. Parpiev. Uzb. Khim. Zh., 1982, 13. 381 P. Leupin, A. G . Sykes, and K. Wieghardt, Znorg. Chem., 1983, 22, 1253. M. Chaudhury, J. Chem. SOC.,Dalton Trans., 1983, 857. 383 I. Kawafume and G . E. Matsubayashi, Znorg. Chim. A d a , 1983, 70, 1. 384 A. E. Lamders and D. J. Phillips, Znorg. Chim. Acta, 1983, 74, 43. 386 C. Zhou, X. Chen, and C. Yuan, Huaxue Xuebao, 1983, 41, 623. 3nu


28 1

Complexes (1 18) (R = Me or Et) give bands typical of M-NO, bonding, i.e. v,,(NO,) at 1375 cm-l and v,(NO,) at 1315 cm-l. The analogous nitrato complexes give bands typical of unidentate nit rat^.^^ All four complexes M(tmc)CI2 and M(tmc),CI, [M = Co or Zn, tmc = (Me,NNH),CO] give i.r. spectra [v(CH), amide-I, and amide-TI bands] showing co-ordination via the carbonyl and one of the Me,N groups.385

Methyl pyruvate aroylhydrazones form metal complexes ML2 (M = Co, Ni, Cu, or Zn), for which the i.r. spectra show that the ligands are tridentate, with the negative charge strongly delocalized (119) (R = Ph or O - C ~ H , O H ) . ~ ~ ~ Quite detailed ligand-mode assignments have been made for WiLJ2- and [NiLJ4- [L = oxamate (-OOCCONH,)]. Bonding occurs via N and 0.38Q The resonance Raman spectrum of the Schiff-base complex (120) contains v(C=N) at 1615 cm-1 and the phenyl-ring stretch at 1580-1590 cm-l. They were differentiated by their resonance profiles.B Q O

Detailed i.r. studies, including deuteriation, show that ML2-nHo0(M = Ni, Cu, or Zn, L = 4-hydroxy-~-prolinato) and CuCI(L)-H,O contain L coordinated via the N atom of the pyrrolidine ring and the 0 atom of the carboxylato group. For CdC12(HL),however, only the carboxylate is c o - ~ r d i n a t e d . ~ ~ ~ R. P. Wirth, L. L. Miller, and W. L. Gladfelter, Organometallics, 1983, 2, 1649. L. K. Peterson, R. S. Dhami, and K. I. Tht, Inorg. Chim.Actu, 1983,70, 59. 388 A. Mangia, P. L. Messori, C. Pelizzi, and G . Predieri, Inorg. Chim. Acra, 1983, 68, 137. 3RD G. Schoeters, D. Deleersnijder, and H. 0. Desseyn, Spectrochim. Acta, Part A , 1983. 3A9

387

39, 71.

M. Datta, D. H. Brown, and W. E. Smith, Spectrochim. Actu, Part A , 1983, 39, 37. m1 Y. Inomata, T. Takeuchi, and T. Moriwaki, Znorg. Chim. Actu, 1983, 68, 187. 390

282


Characteristic v(C-N) (ca. 1400 cm-l), v(C=O) (ca. 1640 cm-l), and v(C0) (ca. 1335 cm-l) were assigned for the new Schiff-base complexes (121) (M = Pd or Pt) and related The i.r. spectra of platinum(n) nucleotide complexes, e.g. Pt(S’-GMP).Clz.xH,O (5’-GMP = guanosine-5’-monophosphate),suggest N, binding of the 5’-GMP. Q 3 1.r. and Raman spectra were used to differentiate between uni- and bi-dentate 1.r. alone bonding of l-methyluracil in a number of its platinum was used to characterize the bonding in platinum(rv) complexes or ethanolamine and ethanethiolamine. 95 R

v(N0) of the ligand in C~(2am4PicO),~+ (2am4Pic0 = 2-amino-4-picoline-Noxide) is close to the free-ligand value, even though the complex is believed to be Cu-0 bonded. The expected decrease from the free-ligand value is not seen because v ( N 0 ) in the free ligand is already reduced by hydrogen The complexes (122) (R = Me, Et, Ph, or Pr’) all give a strong i.r. band due to v(C=N) in the range 1630-1670 ~ r n - l . ~ ~ ’ 1.r. and Raman spectra of the Ag’, Hg”, and MeHg+ complexes of l-methylthymine and its N-3 deuteriated derivative were observed and assigned, showing complexation at N-3.3@8 It was suggested that in a variety of thorium(1v) complexes of antipyrine or 4-aminoantipyrine the former is only co-ordinated via oxygen whereas the latter is N,O-bidentate. Cp(CO)F&C(Me)OAIEt2NButfiPh2]has v(C=O) of the Lewis-acid stabilized acyl at 1460 cm-l, i.e. it contains the unit ( 123).*O0 The complexes (124) (Fc = ferrocenyl, R = C1, Bu, or C8H1,, Ar = Ph, py, p-C,H,Cl, or o-C6H4N02)have v(C=NN=C) at 1605 cm-l and v(C0) at 1240 ~m-l.~Ol @ @

392 E.Ambach, U. Nagel, and 393 H. A. Tajmir-Riahi and T.

W. Beck, Chem. Ber., 1983, 116, 659. Theophanides, Can. J. Chem., 1983, 61, 1813. 3@4B. Lippert, D. Neugebauer, and G. Raudaschl, Inorg. Chim. Acta. 1983,78. 161. 385 A. Syamal and B. K. Gupta, Transition Met. Chem., 1983, 8, 36. 398 D. X. West, Inorg. Chim. Acta, 1983, 71, 251. 397 S. J. Loeb, J. F. Richardson, and C. J. Willis, Inorg. Chem., 1983,22,2736. F. Guay, A. L. Beauchamp, C. Gilbert, and R. Savoie, Can. J. Spectrosc., 1983, 28, 13. 39g R. K. Agarwal, A. K . Srivastava, and T. N. Srivastava, Proc. Natl. Acad. Sci., India, Sect. A , 1981, 51, 79. 400 J. A. Labinger, J. L. Bonfiglio, D. L. Grimmett, S. T. Masuo, E. Shearin. and J. S. Miller. Organometallics, 1983, 2, 733. 401 S. R. Patil, U. N. Kantak, and D. N. Sen, Inorg. Chim. Acta, 1983, 68, 1.

283


Me

C=N

/

/c=oL

Fe A1 / / P-N

1.r. and Raman spectra were obtained for triorgano-tin and -lead derivatives of N-acetylamino-acids, e.g. MR,(AcGlyO) (M = Sn, R = Me, But, or Ph; M = Pb, R = Me or Ph; AcGlyO = N-acetyl-a-alanineor N-acetylmethionine). The data were consistent with five-co-ordination at the metal, the ligands being bidentate, via a unidentate carboxylate and the oxygen of COamido.There was no evidence for co-ordination by the NH groups.4o2

Ligands Containing N and S Donor Atoms.-2-Amino-l-cyclopentenedithiocarboxylate (ACDA) (125)forms a complex V(ACDA)4for which v(NH) modes are at 3210 and 3290 cm-l, v(C=C) at 1615 cm-l, v(C-N) at 1290 cm-l. v(C-S) at 900 and 950 cm-l, and v(VS) at 460 ~m-l.~O:~

The novel diazenidohydrazido complexes {Mo[NaC(S)SR2][NH2NC(S)SR2][R1,NCS,I2} (Rl, R2 = Me or Et) give i.r. spectra which show that the unit (126) is pre~ent.~" 1.r. spectra for complex (127) (L = MeNC, EtNC, PhCH2NC, or Pr3, R = a variety of aryl groups, Ar = 4-XCsH4, X = MeO, Me, F, C1, Br, etc.) are consistent with the -q2-N,Sa-ordination The resonance Raman spectra of Fe" and Fe"' complexes of 2-formylpyridine thiosemicarbazone (128) show that there is appreciable dx-dx M-S backbonding in the Fe" complex. This shows a progression of peaks arising from successive vibrational levels of V ( C S ) .N,S-Bonding ~~ was indicated for Fe" and Fe"' complexes of N,N-di-(2-pyridyl)thio~rea.~~~ 402

G. Roge, F. Huber, H. Preut, A. Silvestri, and R. Barbieri, J . Chem. Soc., Dalton Trans.. 1983 595.

R. ' 0 4 R. 406 H. 4a4 H. 407

D. Bereman and J. R. Dorfman, Polyhedron, 1983, 2, 1013. Mattes and H. Scholand, Angew. Chem., Int. Ed. Engl., 1983, 22. 245. C. Ashton and A. R. Manning, Inorg. Chem., 1983, 22, 1440. Beraldo and L. Tosi, Inorg. Chim. Actu, 1983, 75, 249. S. Burman and D. N. Sathyanarayana, J. Coord. Chem., 1982, 11, 219.

284


1.r. spectra were reported for 40 Co, Ni, Pd, Pt, and Cu complexes of RHNC(S)NC(NH,), (R = H, Me, or Et). N,S- or N,N-co-ordination occurred, depending upon the metal or the pH of the medium.408 Deuteriation experiments enabled some ligand modes to be assigned quite reliably in [Rh(MetH)Cl,(H,O)] (MetH = L-methionine). The ligand coordinates via the amino N and S. Another form is [Rh(HMet)CI,(H,O)], where the ligand is present in zwitterion form and co-ordinated via the carboxyl 0 and the S atom.409RhIII, TrII', Pd", and Pt" complexes of cyclohexanone thiosemicarbazone are shown (by i.r.) to co-ordinate via the thiocarbonyl S and the hydrazine N.410 Raman and i.r. spectra of cysteinylcysteine and its Ni and Zn complexes show that in the complexes the dipeptide is co-ordinated by sulphur only.411 Pd-S co-ordination is established in Pd(S=NNMe,),Cl, by the presence of v ( N N ) at 1132 cm-1 and v(NS) at 772

( 128) The ligand (129), btz, has v(C=N) at 1614 cm-l and v(CS) at 660 cm-l. In

Cu(btz),+ v(C=S) is at lower wavenumber but v(CS) is almost unshifted. The wavenumber shifts and intensity changes indicate strong coupling between vibrations in the Cu(N=CC=N) ring.413Resonance Raman spectra enabled ligand modes to be identified in copper(1r)-substitutedliver alcohol dehydrogenase, a type-I copper analogue.414 1.r. spectra of the solid complexes RHgL (R = Me or Ph, L = monoanion of 2-thiouracil) gave evidence for the presence of both exocyclic S and pyrimidine N.*16

Ligands Containing S or Se and 0 Donor Atoms.4.r. spectra of V(XC6H4SeO2),, VO(XC,H,SeO,),, and V,O,(XC,H,SeO,),CI, were all consistent with 0,O'seleninato co-ordination. The V"' derivatives appeared to have D3 symmetry (X = H, m-C1, p-C1, rn-Br, p-Br, or p-Me1416 v(SOz) modes for the SOz ligand in complexes (130) [M = Cr, Mo, or W, PR, = PPh,Me, P(OMe),, or P(OPr'),] and related complexes are all as expected 408 400 410 411

414 413 414

C. R. Saha and N. K. Roy, J . Coord. Chem., 1983, 12, 163. A. E. Bukanova, T. P. Sidorova, N. A. Ezherskaya, and L. K. Shubochkin, Rum. J. Inorg. Chem., 1983,28, 555. S . Chandra, Synth. React. Inorg. Met.-Org. Chem., 1983, 13, 89 R. Panossian, M. Asso, and M. Guiliano, Spectrosc. Lett., 1983, 16, 463. G. Tresoldi, G. Bruno, F. Cruatti, and P. Piraino, J. Organomet. Chem., 1983, 252, 381. M. G. B. Drew, T. R. Pearson, B. P. Murphy, and S . M. Nelson, Polyhedron, 1983,2,269. W. Maret, M. Zeppezauer, J. Sanders-Loehr, and T. M . Loehr, Biochemistry, 1983. 22. 3202.

415

*16

G. C. Stocco, A. Tamburello, and M. A. Girasolo, Inorg. Chim. Acta, 1983,78,57. G . Graziosi, C. Preti, and G. Tosi, Transition Met. Chem., 1982, 7, 267.

285

Vibrational Spectra of Some Co-ordinatedLigands

for +(S)-co-ordination, i.e. v,,(SO,) at ca. 1150-1250 cm-l and v,(S02) at ca. 920-1 100 Co-ordination of SO, in Mo(CO),(PPh,),(SO,)L is dependent upon L, which is one of a variety of alkyl isocyanides. For L = CNCy or CNBu' there appeared to be a mixture of +(S) and q2-S02.418 1.r. bands due to the bridging CF,S03- ligand were identified in Mo,(H,O),(CF,SO,)~ and Mo,(CF,SO~)~."~ Complex (131) gives v(C=O) of the bridging thiocarbaniate, which shows that the 0 of the ligand is not co-ordinated to the metal.420

co

4

v,(Se02) and v,,(SeO,) modes in the seleninato complexes M(XC,H,SeO,), (M = Mn or Fe, X = H, p-C1, m-Cl, p-Br, m-Br, or p-Me) were all consistent with 0,O'-chelation of the seleninato ligands, e.g. for M = Fe and X = p-Br v,,(SeO,) is at 807 cm-1 and v,(SeO,) at 720 v,(S02) and v,,(S02) were assigned for Fe(L),(CO),(SO,) (L = a wide range of tertiary phosphines). There was no systematic variation with the nature of L. The values were reasonable for planar +SO, ligands.*,, S,S-Dithiocarbonato-ligandassignments were made for Pd(PR,)(CS,O), and these are summarized in Table 13. In some cases, however, there was evidence for S,O - i ~ o m e r s . ~ ~ ~ Table 13 Dithiocarbonato-ligand-modeassignmentslcm-' in Pd(PR,)(CS,O)

PR,

2V,,(CS)

PPh

1685 1685 I 690

PEtPh, PCY 3

v(C =0)

V a d W

1605 1605 1610

845

840 840

Pt(PCy3),S02 gives v(S0) at 1162 and 1029 cm-l from the Pt-SO2

unit.

6(S02) is at 508 cm-1.424[Pfen2(Me2S0),I2+ has v(S0) of the co-ordinated DMSO at 1150 cm-l, due to the Pt-S co-ordinated ligand. The ethylenediamine ligand

gave v(NH) and 6(NH,) as expected.42s Spectroscopic studies showed that DMSO co-ordinates to a PtIrl surface by Pt-S bonds4,* W. A. Schenk and F. E. Baumann, J. Organomet. Chem., 1983,256, 261. G. J. Kubas, G. D. Jarvinen, and R. R. Ryan, J. Am. Chem. SOC.,1983, 105, 1883. 410 J. M. Mayer and E. H. Abbott, Inorg. Chem., 1983, 22, 2174. 4a0 R. J. Angelici and R. G. W. Gingerich, Organometallics, 1983, 2, 89. 4a1 G. Candrini, W. Malavasi, C. Preti, G. Tosi, and P. Zannini, Spectrochim. Actu, Part A , 417

418

1983, 39, 635.

P. Conway, S. M. Grant, A. R. Manning, and F. S. Stephens, Inorg. Chem., 1983,22, 3714. 4a9 P. G. Jones and G. M. Sheldrick, Z . Naturforsch., Teil B, 1983,38, 449. 4a4 J. M. Ritchey, D. C. Moody, and R. R. Ryan, Inorg. Chem., 1983, 22, 221. 4a6 S. Lama, D. Minniti, R. Romeo, and M. L. Tobe, Inorg. Chem., 1983,22, 2006. 4a6 B. A. Sexton, N. R. Avery, and T. W. Turney, Surf. Sci.. 1983, 124. 162.

7 Mossbauer Spectroscopy BY J. D. DONALDSON, S. J. CLARK, AND S. M. GRIMES

1 Introduction

The literature reviewed in this report shows how the use of y-resonance methods has developed in a wide variety of applications. A considerable number of papers on Mossbauer spectroscopy in the period covered by this Report appear in the proceedings1of the New Delhi International Conference on the Mossbauer Effect. The sixth volumes of the literature services ‘The Mossbauer Effect Data and Reference and ‘Mossbauer Spectroscopy Abstractsv3were published in 1983 and continue to provide valuable publication, title, and abstract information, respectively. The layout of this chapter is altered this year by a change in position of the section dealing with the important and rapidly developing conversion-electron technique and by minor changes within the sections. This introductory section covers books and review articles and is followed by sections that deal with theoretical developments and with advances in instrumentation and methodology. Sections 4,5, and 6 contain detailed reviews of all aspects of iron-57, tin-119. and other isotopes, respectively, except for those aspects dealing with conversion electron and back-scattering, which are considered in Section 7. The isotopes (energies in keV in parentheses) that have been mentioned during the year include 57Fe(14.412), 61Ni(67.4), 67Zn(93.26), 73Ge(13.3), 83Kr(9.3), !IvRu(89.36), llsSn (23.875). l”Sb (37.15). ln5Te(35.46), 1271(57.6), lsel (27.72), i:3DCs (81.0). lS3Srn(35.8), lSIEu(21.64), Is5Gd(86.54)’ lslDy (80.7), lssEr (80.56). lS0Tm(8.4), 170Yb (84.26), ls1Ta (6.24), le80s(155.0), le7Au(77.33, and 237Np (59.54).

Books and Reviews.-An issue* of Stud. Ph.vs. Theor. Chem. dealt with the applications of Mossbauer spectroscopy to physics, chemistry, and biology. The issue contained sixteen review articles on the following topics : introduction to Mossbauer spectroscopy, by Thosar, Srivastava, Bhargava, and lyengar ; instrumentation for Mossbauer spectroscopy, by Longworth; the study of metals by Proc. Indian Nut. Sci. Acad. Phys. Sci., Special Vol., 1982. ‘Mossbauer Effect Reference and Data Journal’, ed. J. G. Stevens, V. E. Stevens, R. M. White, and J. L. Gibson, Mossbauer Effect Data Center, University of North Carolina, U.S.A., 1983, Vol. 6. ‘Mossbauer Spectroscopy Abstracts’, ed. P. W. C. Barnard, PRM Science and Technology, 261A Finchley Road, London, 1983, Vol. 6. B. V. Thosar, P. K. Iyengar, T. K. Srivastava, and S. C. Bhargava, Stud. Phys. Theor. Chem., 1983,25.

286

M6ssbauer Spectroscopy

287

Mossbauer spectroscopy, by Cranshaw ; selective-excitation double Mossbauer spectroscopy, by Balke and Hoy ; the intensity-tensor formulation for dipole transitions such as 67Feand its application to the determination of the e.f.g. tensor, by Zimmerman; static and dynamic crystal-field effects in Fe2+Mossbauer spectra, by Price and Varret; calculation of charge density, e.f.g., and internal magnetic field at the nuclear site using MO cluster theory, by Marathe and Trautwein ; paramagnetic hyperfine structure, by Spantalian; Mossbauer studies of biomolecules, by Huynh and Kent ; magnetic interactions in superconductors studied by Mossbauer spectroscopy, by Shenoy; stochastic theory of relaxation effects on Mossbauer lineshape, by Dattagupta; spin relaxation, by Bhargava ; theory of zero-field splitting, spin-lattice coupling constants, and nuclear quadrupole interactions of S-state ions in solids, by Sharma; radiofrequency, acoustic, microwave, and optical perturbations of Mossbauer spectra, by Srivastava; Mossbauer spectroscopy of rare-earths and their intermetallic compounds, by Taneja and Kimball ; Mossbauer spectroscopic studies of ferroelectric compounds, by Date and Gonser. A special issue of ‘Hyperfine Interactions’ contained papers commemorating the 25 t h anniversary of Mossbauer spectros c o ~ yThe . ~ following topics were surveyed in this journal : Mossbauer spectroscopy in physical metallurgy; Mossbauer spectroscopy of implanted sources; experimental techniques for conversion-electron Mossbauer spectroscopy ; the impact of Mossbauer spectroscopy in chemistry; Mossbauer studies of valence fluctuations; zinc-67 Mossbauer spectroscopy ; Mossbauer spectroscopy with indium-191 ; the understanding of nuclear structure through Mossbauer experiments; isomer-shift reference scales; Mossbauer spectroscopy and magnetism. A review article emphasizing historical developments in the use of the technique also appeared.6 Recent developments in y-resonance spectroscopy of implanted sources, with particular emphasis on implantation in metals and semiconductors, have been re vie wed,'^^ as has the topic of Mossbauer spectroscopy with electron^.^ A general article on relaxation measurements in Mossbauer spectroscopy stressed methods of observing populations within the electronic and hyperfine levels that are out of thermal equilibrium.1° Two reviews11*12by Hartmann-Boutron on the theory of relaxation effects in Mossbauer spectroscopy published during the year dealt with basic concepts and methods of calculating lineshapes. have reviewed the use of Mossbauer spectroscopy to study Hiroshi et chemical bonding, with particular emphasis on oxide glasses. The applications of Mossbauer spectroscopy to studies of a number of systems have been sur-

13 H.

De Waard, Hyperfine Interact., 1983. 13. 1983, 34, 517. H. De Waard in ref. 1, p. 5. L. Niesen in ref. 5, p. 65. D. Liljequist, Scanning Electron Microsc., 1983, 3, 997. lo P. Imbert, Rev. Phys. Appl., 1983, 18, 457. l1 F. Hartmann-Boutron, Rev. Phys. Appl., 1983, 18, 413. l2 F. Hartmann-Boutron, Rev. Phys. Appl., 1983, 18, 431. l3 K. Hiroshi, H.Hideo, and I. Hiroshi, Kagaku Sosetsu, 1983, 41, 6714.

* F. J. Berry, Phys. Bull.,

288


veyed in articles on zeolites,14 metals and alloy^,^^-^^ semiconductors,le liquid ferroelectric compounds,20corrosion products,21122and amorphous metals.23Reviews have also appeared describing the use of y-resonance methods in studies of catalysis,24d i f f ~ s i o nsurface , ~ ~ m a g n e t i ~ m , ~electrode-electrolyte ~g~~ interfaces,28relaxation phenomena,29and laser annealing of ~ e m i c ~ n d u c t o r ~ . ~ ~ Mossbauer spectroscopic results are discussed in reviews on instrumentation for the characterization of rnaterials3l and on atomic and nuclear methods in fossil-energy Review articles on the following systems also contain references to y-resonance spectroscopic data : europium actinide chemistry,34 tellurium iron f e r r i t i n ~ ,haemery~~ thrin,38 catechol dioxygenase~,~~ f e r r ~ c e n e ,hydrido ~~ complexes ‘of transition metals,41 amphibole^.^^ Other review articles, published during the past year, that mentioned Mossbauer spectroscopic results were concerned with hydropro~essing,~~ pharmaceutical^,^^ and materials of biological or medicinal interest.45 2 Theoretical

The basic principles and applicationsof the Mossbauer effect have been discussed46 in terms of nuclear hyperfine interactions,including electrical-monopole,electricalquadrupole, and magnetic-dipole interactions. The results obtained were used S. L. Suib, K. C. McMahon, and P. Dimitros, Am. Chem. SOC.Symp. Ser., 1983, 218,301. V. S.Litvinov, S. D. Karkishev, and V. V. Ovhinnikov, ‘Nuclear y-Resonance Spectroscopy of Alloys’, 1982, 143 pp. lo A. Ikhlef. T. Vieira, R. Viler, and G. Cizeron, Mem. Etud. Sci. Rev. Met., 1983, 80, 377. l7 J. E. Frackowiak, Pr. Nauk. Uniw. Slask. Katowicach, 1982,513, 28. la V. Fano, I. Ortalli, E. Maniezzi, and R. Pergolari, Chem. Phys., 1983,9,365. V. Ya Rochev, Adv. Liq. Cryst., 1982,5 , 79. 2o S. K. Date and U. Gonser, Stud. Phys. Theor. Chem., 1983, 25, 882. a1 M. A. Dembrovskii, D. S. Zakhar’in, and F. Kh. Chibirova, Zashch. Met., 1983,19,365. J. Chen and F. Yu, Huaxue Tongbao, 1982, 12, 723. e3 U. Gonser and R. Preston in ‘Glassy Metals 11’. ed. H. J. Gunterodt and H. Berg, Springer Verlag, Berlin, 1983. 24 Y.R. Ding in ref. 1, p. 161. J. Mullen in ref. 1, p. 29. 26 T. Shinijo, Oyo Butsuri, 1983, 52, 298. 87 J. C. Walker in ref. 1, p. 21. D. A. Scherson, E. B. Yeager, J. Eldridge, M. E. Kordesch, and R . Hoffman, Gov. Rep. Announce. Index, 1983, 83, 1OOO. 29 S. Morup in ref. 1, p. 91. 80 G.Langouche, NATO Adv. Study Inst. Ser., Ser. E, 1983, 69, 590. 31 R. M. Fisher, J. Met., 1983,42. ‘Atomic and Nuclear Methods in Fossil Energy Research’, ed. R. H. Filby, Plenum, 1982. 38 S. J. Lyle, Annu. Rep. Prog. Chem., Sect. A , Phys. Inorg. Chem., 1983,79, 359. 84 J. M. Friedt, Radiochim. Acta, 1983,32, 105. F. J. Berry, Annu. Rep. Prog. Chem., Sect. A , Phys. Znorg. Chem., 1983, 79, 121. B. W. Fitzsimmons, Annu. Rep. Prog. Chem., Sect. A , Phys. Inorg. Chem., 1983,79,227. E. C.Theil, Adv. Znorg. Biochem., 1983,L1,1. 38 R. G. Wilkins and P. C . Harrinstop, Adv. Znorg. Biochem., 1983, L1,51. L. Que, Adv. Inorg. Biochem., 1983, 5, 167. 40 G.Marr and B. W. Rockett, J. Organomet. Chem., 1983,257, 209. 41 D. S. Moore and S . D. Robinson, Chem. SOC.Rev., 1983, 12, 415. F. C. Hawthorne, Can. Mineral., 1983, 21, 173. Is H. Topsoee, NATO Adv. Study Znst. Ser., Ser. C, 1983, 105, 329. 44 R. K.Gilpin, L. A. Pachia, and J. S . Ranweller, Anal. Chem.. 1983,55, 45 I. Ortalli, Gas. Fis., 1982,23, 283. W. Hu and F. Yu,Nucl. Tech., 1983,3, 57. l4 l5


289

to correlate the hyperfine structure of the 57Fenucleus with Fe Mossbauer parameters. The theory behind zero-field splitting, spin-lattice coupling constants, and nuclear quadrupole interactions of the ions Fe3+(6S),E u ~ + ( ~ Sand ) , Gd3+(8S) has been reviewed,“’ as has the physical basis for crystal-field interactions on 57Fe resonance The magnetic-hyperfine splitting of the Mossbauer spectra of microcrystals has been Below the superparamagnetic blocking temperature the magnetization is not fixed, which leads to a reduction in the magnetic splitting that can be described in terms of a low-temperature approximation. The description includes expressions for particles with special types of anisotropy and for particles in an external magnetic field. The use of the spectra of the microcrystals to give information on particle size and on the prevailing magnetic anisotropies is also discussed. An algorithm has been suggestedsofor the Mossbauer spectrum of an atom undergoing one-dimensional Brownian motion in an arbitrary potential. The algorithm was shown to reproduce accurately and simultaneously the low- and high-frequency dependence of the spectrum. Zimmermannbl has discussed the intensity-tensor formulation for dipole transition in 57Fein terms of how it is calculated and how it is affected by changes in symmetry. This was then extended to a consideration of the determination of the e.f.g. tensor under the headings ‘Single crystals with equivalent lattice sites’, ‘Line intensity in the case of polarization’, and ‘Thickness corrections in the Mossbauer spectra of textured materials’. The uses of MO calculations in the interpretation of various parameters, including shifts obtained by chargedensity calculations, splittings by e.f.g. calculations, and magnetic-hyperfine splittings by internal-field calculations, have been described.52 The phase effects, appearing in a system consisting of a Mossbauer source and a Mossbauer absorber both vibrating at ultrasonic frequency, were investigated the~retically.~~ The intensity of the transmitted recoil-less radiation was shown to depend upon both the absolute phase shift between the vibrations of the source and those of the absorber and on the effective dephasing due to the finite propagation time of the electromagnetic wave between them. The relationship between this distance effect and the general relativity theory was discussed. An examination was carried out on the electronic and recoil-less nuclear absorption of y-radiation, and the authors concluded that, within the linear absorber approximation, the ideal absorber thickness lies between 2/pe and l/pe, where w e is the electronic mass-absorption coefficient of the absorber.54 The authors also show that the best value depends upon the nature of the background counts, and, for cases where the linear-absorber approximation is invalid, they described graphs that can be used to determine the thickness. R. R. Sharma in ref. 4, p. 242. D. C. Price and F. Varret in ref. 4, p. 316. S . Morup, J. Magn. Magn. Mater., 1983, 37, 39. 60 W. Nadler and K. Schulten, Phys. Rev. Lett., 1983, 51, 1712. 61 R. Zimmermann in ref. 4, p. 273. 6s V. R. Marathe and A. Trautwein in ref. 4, p. 398. 68 N. Ognyanov and L. Tsankov, J. Phys., 1983,44, 865. 64 G. T. Long, T. E. Cranshaw, and G. Longworth in ref. 2, p. 42. I7

4*

290

Spectroscopic Properties of Inorganic and Organometallic Compounh

Remarks have been made55on the accuracy of the determination of the Mossbauer-Lamb factors by linewidth measurements. The error of the f-factor determination due to the linear approximation of the linewidth function can be kept lower than 1 "/d of the broadening of the absorber and source lines, and the range of effective thickness used in the experimental study is taken into account. For good Mossbauer sources, graphs are given to permit the determination of the slope of the linear approximation as a function of various factors. The diffraction of synchrotron radiation on Mossbauer nuclei has been observed,66and the measured time distribution of resonance-scattering quanta has been shown to be radically different from the law of single nuclei. The decay of excited nuclei in crystals has directional character and proceeds more rapidly. Solution of the inverse problem of Mossbauer spectroscopy in the case of ultrasonic modulation leads to acoustic oscillation parameters and acoustic properties, and an approximating function to determine the oscillating parameters has been ~ e l e c t e d . ~ ~ Calculations have been carried out on the electron densities at the nuclei for the elements from Li to Am, and the relationship of these volume dependences with the hyperfine field for the elements dissolved in Fe has been studied.68 A number of papers published during the year has been concerned with theories applicable to Mossbauer resonance spectral lineshapes. A mechanism has been proposed describing how any distribution in isomer shifts in an amorphous material containing Fe3+ will broaden the Mossbauer doublet.sR The known variance in shifts in amorphous Y,Fe,O,, for example is shown to be sufficient to account for the broadening of its y-resonance spectrum from that expected for quadrupole-energy distribution in a random-packed structure. A general expression for the spectral distribution of y-rays emitted from nuclei in bound systems such as solids has been derived.60This expression is valid even in the presence of non-stationary relaxation processes associated with atomic motion and has been used to calculate the effect of a relaxing thermal spike on the shape of Mossbauer resonance lines. A theory has also been constructed to account for the effects of decaying atomic states on resonance lineshapes61 The theory considers the general case in which the nucleus interacts with its environment via electric-monopole as well as electric-quadrupole and magnetic-dipole coupling. A method was suggested62for the calculation of the effect of the precession of the magnetic moment of superparamagnetic particles on the shape of Mossbauer spectra and in which the Fokkar-Planck equation for the evolution of the distribution of magnetic moments in the discontinuous model was substituted for normal differential equations. The theory of y-magnetic resonance in E. Fritzsch and H. Kubnsch, Radiochem. Radional. Lett., 1983, 55, 331. A. 1. Chechin, N. V. Andronova, M. V. Zelepukhin, A. N. Artem'ev, and E. P. Stepanov, Pisma Zh. Eksp. Tear. Fiz., 1983, 37, 531. 67 A. R. Arakelyan, R. G. Gabrielyan, A. R. Aslanyan, and Kh. V. Kotandyan, Phys. Status Solidi B, 1983, 118, K69. C. T. Page, J. H. Dale, L. Chow, J. N. Farrell, W. D. Josephson, and L. D. Roberts, Phys. Rev. B, 1983, 27, 6037. M. E. Lines and M. Elbschutz,Phys. Rev. B, 1983, 9,5308. 6o A. Gupta, Phys. Lett. A , 1983, 96, 431. 61 A. Gupta and R. K. Rama, Hyperfine Interact., 1983, 14, 111. O2 G. N. Belozerskii and B. S. Pavlov, Fiz. Tverd. Tela, 1983, 25, 1690. 55

s6

Mcssbauer Spectroscopy

291

paramagnetic crystals in the presence of electric spin relaxation has also been discussed, and a general theory for lineshape applicable to the spectrum with and without quadrupole interaction has been derived.63The theory was used in a calculation of 57Felineshapes for different values of the electronic relaxation rate, and the results obtained were used in investigation of the dynamics of the electronic-nuclear system. The application of stochastic theory to relaxation effects in Mossbauer spectroscopy has been reviewed,B4as have lineshape spinlattice relaxation effects.B6 Correlation effects for interstitial-type self-diffusion in b.c.c. and f.c.c. crystals have been considered,B6 and self-correlation functions for long-range monovacancy diffusion mechanisms in f.c.c. lattices have been cal~ulated.~~ In the latter case a simple method for obtaining the experimental solid-state angle corrections was introduced for diffusion-broadened Mossbauer spectra from single-crystal sources. Broadening of Mossbauer resonance lines is one of the parameters obtained by considering a model for a thin film in the critical region where the decay in fluctuations in magnetism is described by a diffusion and a damping process.68 The influences of protein dynamics on Mossbauer spectra have been constochastic model was used to describe classic relaxa~ i d e r e dA. ~non-adiabatic ~ tion in paramagnetic ferrichrome A.70The model for systems showing ionic spin relaxation permits the detailed analysis of Mossbauer spectra, showing relaxation effects. The predictions of the model are tested by considering the spectra of ferrichrome A in the temperature range 4.2 K to 115 mK, where the spin-spin interaction is the dominant relaxation mechanism. The magnetic-hyperfine fields of some orthoferrites have been calculated from a theoretical and quadrupole distribution fits have been made of high-statistics Mossbauer spectra of some amorphous An equation has been derived to describe the time dependence of the y-emission of 67Fenuclei while accounting for the hyperfine structure of the emission and the effect of electronic r e l a ~ a t i o nThe . ~ ~ time dependence of the Mossbauer signal has a hyperfine structure at electronic rates of greater that 5.5 natural linewidth. A theoretical description has been produced7*to describe the transmission of Mossbauer y-quanta irradiated by a coherently radiofrequencyvibrating source and emerging through a system consisting of n resonant absorbers coherently vibrating with different frequenciesand amplitudes. General results for spectral distribution and for full intensity of radiation were derived from the theory. A. V. Mitin and N. V. Polyakov, Phys. Status Solidi B, 1983, 115, 477. S. Dattagupta in ref. 4, p. 586. S. C. Bhargava in ref. 4, p. 628. oa D. Wolf, Phifos. Mag. A , 1983, 47, 147. I7 K. Ruebeonbauer, Hyperfine Interact., 1983, 14, 139. W. Korneta and 2. Pytel, J. Phys. C, 1982, 15, L1099. 6e E. K. Knapp, S. F. Fischer, and F. Parak, J . Chem. Phys., 1983,78,4701. 70 G. R. Hoy, M. R. Corson, and B. Balko, Phys. Rev. B, 1983,27,2652. 71 M. Ya. Flyagin and A. N. Men, Phys. Status Solidi B, 1983, 115, 277. M. E. Lopez-Herrara, J. M. Greneche, and F. Varret, Phys. Rev. B, 1983, 28, 4944. 78 A. V. Mitin and N. V. Polyakov, Kazan Fiz.-Tekh. Znst., 1983, 25, 2180. N. Ognyanov and L. Tsankov, J . Phys. (Les Ulis, Fr.), 1983,44, 859.

''

292


A theory has been developed76for the Mossbauer y-quanta absorption and scattering by polarized 57Fenuclei in crystals when n.m.r. transitions between sublevels and the nuclear ground state are introduced. This technique provides information on the spin-spin interactions of nuclei. 3 Instrumentation and Methodology Recent developments in Mossbauer instrumentation including spectrometers, drive waveforms and systems, data-acquisition systems, absolute-velocity measurement devices, source preparation, detection methods, equipment, highpressure cells, and furnaces have been reviewed.7sThree report^^^-^^ describe the design and construction of microprocessor-based y-resonance spectrometers and data-processing systems. A microprocessor-controlled spectrometer has also been constructed for use in thermal-scan Mossbauer experiments,80and the design of a double-resonance y-resonance spectrometer has been described. 81 A system consisting of a Mossbauer spectrometer coupled directly to ion-implantation equipment was shown to be useful for in situ low-temperature studies of ionbombarded metals.82In this system the Mossbauer spectra are measured at low temperatures directly after the end of implantations into cooled targets. Use of the system was illustrated by studies on the implantation syntheses of iron hydride and iron nitride. A spectrometer suitable for both transmission and scattering 57Femeasurements has been c o n ~ t r u c t e d ,and ~ ~ a computer-based delayed-coincidence y-resonance spectrometer has been described.84Kalvius and his co-workersB5described both a microprocessor-controlled spectrometer for frequency-modulation techniques using piezoelectric materials and its use for the accurate determination of hyperfine splittings in g7Znspectroscopy. A rotating-target device capable of withstanding a 22 MeV p-beam with currents of up to 500 pA was used to produce the strong 57C0sources required for Mossbauer scattering experiments.86 Typical production rates achieved in the compact cyclotron used to prepare the sources are I Ci 57C0in ten days. The preparation of implanted y-resonance sources has been described,87 and the mechanism of implanted-ion trapping on thick targets has been investigated.88 The improvements in Mossbauer spectroscopic measurements that can be T. Sh. Abesadze and A. Ya. Dzyublik, Ukr. Fiz. Zh. (Russ. Ed.), 1983, 28, 563. Longworth in ref. 4, p. 122. 77 N. Bhattacharjee, V. A. Pethe, S. Kumar, P. K. Mukherjee, M. K. Sanyal, and K. D. Sabnis in ref. 1, p. 934. 78 V. S. Indurkas, A. L. Khandwe, and P. K. Ptawardhan in ref. 1, p. 915. C. Jin and X. Xiong, W d , 1982, 11, 498. 8o G. Noelle, H. Ullrich, J. B. Mueller, and J. Hesse, Nucl. Instrum. Methods, 1983, 207, 459. S. M. Cheremisin and A. Yu Dudkin, Prib. Tekh. Eksp., 1983, 2, 29. 88 G. K. Wolf, F. Schreyer, G . Frech, and F. Wagner, Springer Ser. Efectrophys., 1983, 11, 76

lo G.

313. 84

N. S. Kolpakov and K. E. Nilov, Prikl. Yad. Spektrosk., 1982, 11, 219. J. S. Eck, B. Curnutte, M. Edwards, and K. F. Purcell in ref. 1, p. 923. T. Obenhuber, A. Forster, W. Potzel, and G . M. Kalvius. Nucl. Instrum. Methods, 1983, 214, 361.

8o

E. Huenges, J. Loock, H. Morinaga, and F. Parak, Nucl. Instrum. Methods, 1982,203, 1. I. Dezi in ref. 1, p. 141. A. Kotlicki, J. J. Wlodarczyk, and A. Wojtasiewicz, Nucl. Instrum. Methods, 1983,213, 565.

Mossbauer Spectroscopy

293

achieved using lead-loaded plastic scintillators have been as has the use of gas-discharge electron detector^^*^^^ and proportional c ~ u n t e r s ~ ~ ~ ~ " for y-resonance studies. A continuous-flow detectorg0 containing He gas with 4-6 % CHI was shown to be capable of measuring Auger and internal conversion electrons from 57Fe,the maximum value of the effect for 300 nm thick 57Fefilms being 880 %. A simple technique using resonance detectors to measure very small resonance line shifts has been devised and applied to llsSn spectra.g4 A simple inexpensive continuous-flow cryostat for measuring Mossbauer spectra in the temperature range 77-300 K has been c o n ~ t r u c t e dA . ~Michelson ~ interferometer with an (AI,Ga)As laser diode has been usedes to obtain velocity calibrations on a Mossbauer spectrometer operating in the constant-acceleration mode. The very small size of the laser diode means that this optical system for velocity calibration can be made very compact. The development of and theoretical background applicable to y-resonance drive systems have been ~urveyed.~' A number of papers published in the review year have been concerned with the data-handling systems used in Mossbauer spectroscopy. A new universal met hod for determining background in both transmission and scattering y-resonance has been devised.9* For transmission the amplitude spectrum of the background in the region of the photopeak of a y-source is interpreted but, in scattering geometry, the region of the absorption peak of the sample is interpolated. The background levels determined by the method were shown to be independent of the composition of the source or absorber and of the activity of the source. Computer programs, MOSAUT and MOSIMP, have been writteng9to analyse Mossbauer spectra. A criterion for the quality of a solution is defined as a least-squared X2 of individual fits. Various variables are changed to try to improve X2, and the program terminates when alteration of any of the variables fails to improve the fit. A method of fitting complex spectra based on Gauss-Newton formulae with modified factors was achieved by adding a correction term to the first approximation of the Taylor expansion.lOO The use of the method was illustrated by fitting the IlRSnspectra of Pt-Sn-Al,O, catalysts and the 57Fespectra of magnetitecontaining volcanic rock. A general mathematical expressionlol has been used to permit the calculation of experimental data by stripping or fitting methods or by a combination of the two methods. The problems associated with reduction T. Bressani, P. Macciotta, C. Muntoni, and S. Serci, Nucl. Instrum. Methods, 1983,211,231. V. V. Nemoshkalenko, 0.N. Razumov, and N. A. Tomashevskii, Zuvod. Lab., 1983,49,66. Yu. F. Babikova, 0. M. Vakar, A. A. Kasimovskii, and Yu. V. Petrikin, Prib. Tekh. a s p . , 1983,40. Or Y. Zhang, J. Zhu, X. Wang, C. Wang, Z. Zhou, B. Tan, and Y . Xia, Zhongguo Kexue Jishu Duxuse Xuebuo, 1982, 12, 60. I. A. Chumakov, A. B. Dubrovin, and G. V. Smirnov, Nucl. Instrum. Methods, 1983,216, 505. I. Mandzhukova, V. Elev, and N. Markova, Nucl. Instrum. Methods, 1983, 213, 477. O6 S. Das, M. Battacharya, and R. Battacharya, Cryogenics, 1983, 23, 479. B. F. Oterloo, Z. M. Stadnik, and M. E. A. Swolfs, Rev. Sci. Instrum., 1983, 54, 1575. O7 E. Konkeleit in ref. 1, p. 143. OB Yu.F. Babikova, N. S. Kolpakov, K. E. Nilov, and I. E. Shtan, Prib. Tekh. Eksp.. 1983,44. E. Vcrbiest, Comput. Phys. Commun., 1983, 29, 131. loo R. Cai, Kexue Tongbao, 1983, 28, 416. lol S. Li, Z. Li, and Q. Wong, Kexue Tongbao, 1983, 28, 890. so

@*

294

Spectroscopic Properties qf Inorganic and Organometallic Compounds

solutions for spectral fitting have been considered and applied to Mossbauer and n.m.r. data.lo2An. algorithm using indexation for approximation functions and their parameter-vector formation in the least-squares method for minimization problems was suggested.10:3 The algorithm is especially effective for data processing when approximation is needed with several different functions but with different sets of fixed and variable parameters including Mossbauer spectra. N i c k o l ~ v ' ~ ~ has described a mathematical method for fitting of Mossbauer spectra of amorphous magnetic materials. The method consists of positioning and synthesis of the spectrum followed by subtraction of 2,3,4,5 lines beginning from the outside 1,6 lines. The resulting spectra contain only 1,6 components, which makes it simpler to find the hyperfine magnetic field in the sample. Matz et a/. have shownlo5that a previous method of analysing hyperfine-field distributions of amorphous samples is applicable to the analysis of unresolved ll9Sn spectra from crystalline samples, although only rough estimates of the contributions of individual subspectra to the total spectrum can be obtained. A computer-fitting program for Mossbauer spectra has also been described by Varret.lo6 A statistical correlation method was shown to provide a means of performing unrestricted comparison of y-resonance spectra.lo7The use of the derivative of the Mossbauer spectra has been considered,lo8 and the technique of selectiveexcitation double Mossbauer spectroscopy has been reviewed.lo9 In two interesting papers Burger and Vertes llomdescribe a capillary technique that they devised to obtain the Mossbauer spectra of solutions. They used Corning Vycor porous glass ('thirsty glass') as a matrix to contain the solutions for Mossbauer spectroscopic studies. Figure 1 shows the spectra of the low-spin tris-(2,2'-dipyridyl)iron(11) ( a ) as a frozen solution at 80 K, (6) trapped in porous glass and measured at 80 K, and (c) trapped in porous glass and measured at ambient temperatures. The Mossbauer parameters obtained from the spectra in Figures l a and l b appear to be identical, and the data obtained at room temperature (Figure 1c) show only the expected reduction with temperature. This is taken to mean that Mossbauer spectra can be obtained at room temperature from solutions trapped in porous glass and that any interaction between the glass surface and the solute is negligible for this system. The subordinate role of this interaction in such systems can be explained on the basis of recent differentialscanning calorimetric data, which show that bulk water has a higher affinity for the surface in the pores of thirsty glass than solvate water bound by solutes. Thus bulk water covers the internal surface of the carrier separating it from the species in solution. In order to establish that the Mossbauer spectra arise from the liquids and not Yu. P. Pyt'ev, Vestn. Mosk. Univ.,Ser. 3, Fiz. Astron., 1983, 24, 19. K. Churakov, N. G. Volkov, G . A. Kononenko, and V. M. Tsupko-Sitnikov, INIS Atomindex, 1983, 14, 759 193. lo4 S. Nikolov, Solid State Commun., 1983, 48, 761. lo6 W. Matz, K. Melzer, and F. Krueger, Exp. Tech. Phys., 1983, 31, 149. lo6 F. Varret in ref. 1, p. 129. lo7A. Delunas, V. Maxia, and S. Serci, Nucl. Instrum. Methods, 1983, 213, 563. lo*R. Vanleerberghe and P. Van Acker, Nucl. Instrum. Methods, 1983, 206, 339. looB. Balko and G. R. Hoy in ref. 4, p. 159. 'lo K. Burger and A. Vertes, Nature (London), 1983, 306, 353. ll1 K. Burger, A. Vertes, and I. Zay, Inorg. Chim. A d a , 1983, 76, L247. lof

lo3A.

Messbauer Spectroscopy

295

from the precipitate of solid crystals in the pores of the glass carrier or from the adsorption of a solid layer on the internal surface of the capillaries, the behaviour of model systems in which both solute and solvent are liquids was studied. A typical example is provided by the spectrum of a mixture of tetramethyltin and chloroform trapped in porous glass and measured at room temperature; where both components of the mixture are liquids a single-line spectrumis obtained and the shift ( 6 = 0.10 mm s-l from SnO,) was taken to mean that some solvation interaction between Me,Sn and chloroform takes place. Similar work with systems containing only liquid phases such as Fe(CO), in methanol, Me,SnCl in chloroform, and SnT, also gives rise to well defined Mossbauer resonance and prdves that y-resonance spectra can be obtained from liquid samples in the glass. In the case of SnCl, and of solutions of SnI, there is evidence for interaction between the tin moiety in the liquid and the glass surface on the pores because there is a considerable decrease in shift due to co-ordination of silicate oxygens with the tin species.

I

I

L

-4

-2

.

1

1

0

1

+2

.

.

+4 r / m m s-'

Figure 1 The s7Fespectra of a 0.01M aqueous solution of tris-(2,2'-diprridyZ)iron(11)(a) frozen and measured at 80 K, (b) trapped in porous glass and measured at 80 K, and (c) trapped in porous glass and measured at ambient temperature (Reproduced with permission from Nature (London), 1983, 306,353)

A patent112describes an identification system for determining the presence of Mossbauer isotope-containing tagging materials in explosives,weapons, currency, tax stamps, etc. The detector used includes a Mossbauer isotope-detecting substance identical to the taggant and a sensing element responsive to the presence of the tagging substance. The method is initiated by irradiating the carrier material with radiation from an appropriate source. A number of papers published during the year were concerned with the methodology of the Mossbauer effect in specific applications. Included in these applications are the following: studies on laser quenching of metals,l13 of one-dimensional magnetic systems,l14 and of quasi-one-dimensional systems,l15 na R. K. Soberman, K. Krevitz, and L. L. Pytlewski, U.S. Patent 4,363,965, 14 Dec., 1982. lla S. I. Reiman, V. S. Shpinel, and V. P. Gor'kov, Prikl. Yud. Spektrosk., 1982,11, 205. 11* W. J. M. DeJonge, K. Kopinaga, and A. M. C. Tinns, Ned. Tijdschr. Natuurkd. A , 1983, 49, 25. D. M. Cooper, D. P. E. Dickson, P. H. Domingues, G. P. Gupta, C. E. Johnson, M. F. Thomas, C. A. Taft, and P. J. Walker, J . Magn. Mugn. Muter., 1983, 36, 171.


296

the use of variable-temperature y-resonance for the determination of the effect of oxygen on the Curie point of ferrite spinels,116the measurement of surface magnetic properties of fine particles,'17 electric-field gradients in amorphous materials,l18and studies on surface phenomena in soils.11Q The uses of magnetic-hyperfine splitting of y-resonance spectra to provide information on the particle size and prevailing magnetic anisotropies have been described.lZ0The effect on the Debye-Waller factor for a simple cubic lattice containing Mossbauer impurity atoms has been evaluated.lZ1The component of the Debye-Waller factor was found to increase more rapidly at higher temperatures for a defect lattice than for a perfect lattice because of the presence of the anharmonic term in the expansion of the potential energy of the crystal. Mossbauer-effect measurements have also been used to provide information on visco-elastic properties of matter.12'? A number of papers refer to the use of Mossbauer y-resonance for scattering e ~ p e r i m e n t s . The ~ ~ ~diffraction ,~~~ focusing of Mossbauer y-quanta was achieved,lZ2and full external reflection of the resonance y-quanta was examined during simultaneous diffraction scattering in Laue ge0met~y.l~~ The problem of coherent scattering of Mossbauer radiation in the case of a single rotating crystal was considered,lZ4and it was shown that the resulting additional Doppler shift leads to a frequency dependence of the purely elastic intensity. This intensity was also found to be sensitive to small deviations in the reciprocal lattice vector from the rotating axis because of the narrow width of Mossbauer y-quanta. The integrated reflecting powers of flat surface planes of a silicon crystal parallel to the < 111 > planes have been determined by Mossbauer y-ray diffraction.lZ6 4 Iron

General Topics.-General and Metallic Iron. A new type of 57C0source composed of WoSb, has been patented.lZ7LiAIOz doped with Fe3+in the tetrahedral site has been examined by e.x.a.f.s., Mossbauer, and optical spectroscopy and proposed as a spectroscopic standard for ferric iron.lZ8The Mossbauer parameters given are 8 = -0.026 mm s-l (relative to Fe-Pd) and A = 0.62 mm s-l. Analytical solutions have been derived for both tetrahedral and octahedral cage V. I. Nikolaev, V. S. Rusakov, and N. I. Christykova, Vestn. Mosk. Univ., Ser. 3, Fiz. Astron., 1983, 24, 29. 117 A. H. Morrish and K. Haneda, J. Magn. Mugn. Muter., 1983.35, 105. *l8G. Czjzek in ref. 1, p. 27. ll@ N. A. Bobrov, A. D. Voronin, A. V. Ivanov, V. I. Malinovskin, and V. F. Babanin, Pochroredenie, 1982,86. la* S . Morup, J. Magn. Magn. Muter., 1983, 37, 39. lal P. K. Acharyva, A. K. Tewari, S. Roy, and D. L. Bhattacharya, Phys. Sfatus Solidi B. 116

1983, 118, 41.

F. E. Fujita, Jpn. J. Appl. Phys., 1983, 22, 475. G. Baryshevskii, S. T. Zavtrak, and V. V. Skadorov, Kristullografiya, 1983, 28, 442. A. Aleksandrov, A. M. Afanas'ev, and M. K. Melkonyan, Fiz. Tverd. Tela, 1983, 25,

la* la8V. la' P.

1003.

E. V. Zolotojabko, E. M. Iolin, and A. V. Muromtsev, J. Phys. D, 1983, 16, 697.

la6 la6Y.

Kashiwase and M. Minaira, Jpn. J. Appl. Phys., 1983, 22, 49. F. Parak, J. Loock, and R. Kouzmine, U.S.Patent 4,406,697. lP8 G. A. Waychunas and G. R. Rossman, Phys. Chern. Miner., 1983,9, 212. lP7


297

hopping with correlated field-gradient f l u c t ~ a t i o n sand , ~ ~a~mechanism ~~~~ has been proposed that will allow any distribution of isomer shifts in an amorphous material containing Fe3+to broaden the linewidth of the paramagnetic doub1et.l3' A method has been described for determining the relative intensities of the individual components of the cc-Fe Mossbauer sextet which allows for the effects of the thickness and texture of the a b ~ 0 r b e r . The l ~ ~ emission of light by an enriched 67Fe foil during Mossbauer excitation has been The observed spectra are reported to reflect the electronic structure of the foil and have an intensity of 0.4-0.8 %. Antiferromagnetic ordering has been observed in the low-temperature Mossbauer spectra of epitaxial films of 01-Fe,l~~ and the ~ ~ of ~ Jthe~ interface ~ magnetic properties of surface layers of iron f i l m ~ and between a 67Fefilm and a film of another have been studied. The formation of point defects by the low-temperature neutron irradiation of a-Fe has been investigated.l l3 Low-temperature ion-implant ation experi ments have produced a new phase with a hyperfine field of 30.4 T, a small quadrupole splitting, and a low isomer shift, which was identified with E-phase iron h ~ d r i d e . The ' ~ ~ effects of the substitution of iron by vanadium in x-Fe have been studied.l4I 9

Frozen Solutions and Matrix Isolation. Mossbauer spectra of a 4.2 K frozen solution of 57C0Cl,in applied fields of > 30 kG show contributions from both the S = Q and S = Zeeman levels of Fe3+.142 Mossbauer spectra have been recorded on frozen solutions of the high-spin ferric complex ethylene (o-hydroxyphenylglycinato)iron(In) at 4.2 K in a small applied magnetic field, and a crystalfield model has been derived that provides a three-way correlation of the relevant Mossbauer, e.p.r., and optical-absorption spectroscopic data.14378 K Mossbauer studies of suspensions of 60 A Fe,O, microcrystals in acetone have shown that chemisorbed oleic acid results in an increased surface contribution to the magnetic-anisotropy constant and have demonstrated the absence of the previously reported magnetically dead layer in such parti~1es.l~~

++

+

J. Litterst, A. M. Afanas'ev, P. A. Alexandrov, and V. D. Gorobchenko, Solid Stnte Commun., 1983, 45, 963. l') F. J. Litterst, V. D. Gorobchenko, and G. M. Kalvius, Hyperfine Interact., 1983, 14.21. M. E. Lines and M. Eibshuetz, Phys. Rev. B, 1983, 27, 5308. 131 V. M. Nodutov, VZNZTZ, 1982, 3601. lsa G. N . Belozerskii, Fit. Tverd. Teh, 1983, 25, 2522. 184 R. Halbauer and U. Gonser, J. Magn. Mugn. Muter., 1983, 35, 55. 186 J. Tyson, A. Owens, and U. C. Walker, J. Magn. Magn. Muter., 1983,35, 126. lSI G. Bayreuther and G. Lugert, J. Magn. Magn. Muter., 1983, 35, 50. 18' J. M. Tyson, Diss. Abstr. Znt. B, 1983, 43, 2951. Y. Yoshida, S. Nasu, F. E. Fujita, Y. Maeda, and H. Yoshida, J. Mugn. Magn. Muter., lagF.

1983,31-34,

753.

Y. Yoshida, S. Nasu, and F. E. Fujita, Point Defects, Defect Interact. Met. (Proc. Yamada Conf.), Sth., 1981, 1982, 199. lU F. Schreyer, G. Frech, G. K. Wolf, and F. E. Wagner, Solid State Commun., 1983,46,647. 141 S. Dubiel and W. Zinn, J. Magn. Magn. Muter., 1983, 37, 237. 14' D. L. Nagy, R. Doerfler, G. Ritter, J. Waigel, N. Zeman, and B. Bolner, Phys. Lett. A, 1983,%, 400. K. Spertalian and C. J. Carrano, Chem. Phys., 1983,78,4811. lU S. Moerup, J. Magn. Magn. Muter., 1983, 39, 45. 139

298


A matrix-isolation Mossbauer study of 67Feisolated in NH, and NH,/Ar matrices has shown that atomic iron reacts with only one NH3 to form FeNH,, which is then stable in an ammonia matrix at temperatures up to 77K.145 Bimetallic clusters of 57Fewith Cr, Sn, and Pt have been studied in argon matrices at 4.2K, and MO calculations were performed to determine the probable electronic ground ~ t a t e ~The . ~ compounds ~ ~ y ~ ~ formed ~ between iron and alkenes (ethene and propene) in solid argon have also been inve~tigatedl~~ and the products identified (Figure 2). In ethylene at low temperatures (< 18 K) and with low iron concentrations(< 1 %) the major product was Fe(C,H,). Mossbauer spectra of Fe/C,H, at both 4.2 and 20 K are very similar to those of Fe/C,H,.

-4

-2

0 2 4 Velocity/mm s-'

Figure 2 Mossbauer spectra of CaH4/Fe(0.7%) at 20 K (a) at the time of deposition and (b) after anneding to 60 K. Assignments A Fe(C2H4),B Fe2(C2HJ2,Fe,(CaH4), (P > 2) (Reproduced with permission from Znorg. Chem., 1983, 22, 2813)

Hence the products were assigned to Fe(C3He), Fe2(C3H,),, and Fe(C,H6) (p > 2). The Mossbauer spectra of the products indicate that the electronic

configuration of the iron atoms in the alkene complexes is approximately 4s13d7,in agreement with theoretical work. The Mossbauer spectra of Fe(C,H,) and Fe(C,H,) are also consistent with the proposal that C,H4 and CSH, are primarily x-donors with only minimal d, - - - +- x* back-bonding. Matrixisolated binary carbonyls Fe(CO), and Fe,(CO), (x < 5, y = 8 or 9), formed on co-condensation of iron atoms with noble gas-CO mixtures, have been studied by i.r. and Mossbauer spectroscopie~.~~~ The Mossbauer isomer shift (-0.60 mm s-l) and a very low i.r. stretching frequency of Fe(C0) are evidence for a large dx - - - + x* interaction in this fragment. E. M. B. Saitovitch, F. J. Litterst, and H. Micklitz, Cent. Bras. Pesq. Fis., Report 1981, CBPF-NF-027/81. lP6 H. M. Nagarathana and P. A. Montano, J. Chem. SOC.,Faraday Trans. 2, 1983, 79, 271. 14' H. M. Nagarathana, Diss. Abstr. Znt. B, 1983, 43, 2256. 148 S. F. Parker, C. H. F. Peden, P. H. Barrett, and R. G. Pearsan, Znorg. Chem., 1983, 22, 2813. 14* C. H. F. Peden, S. F. Parker, P. H. Barrett, and R. G. Pearson, J. Phys. Chem., 1983, 87, 2329.


299

The temperature dependence of the Mossbauer spectral parameters of butyl rubber containing a 57Fe-enrichedferrocene tracer has been studied over the temperature range 85-300 K.lSoAn inflection in the parameters was observed at temperatures at which the lifetime of the iron excited state was greater than the relaxation time of the rubber macromolecules. Polyacetylenes doped with ferric chloride have been studied by three groups. All the groups have obtained similar results. Pron et a1.1519152 have shown that the initial high-spin Fe"' complex has Mossbauer parameters characteristic of FeC1,- and the formation of some FeCI,.nH,O. The second group has also found that at dopant levels above 0.01 mole fraction and below 25 K the formerly paramagnetic Fe2+ ions form magnetically ordered The other workers have obtained similar results; they have shown that ferric complex is predominant and have proposed a mechanism for the doping process.154Copolymers containing polynuclear iron carbonyl complexes155and the anomalous recoil-free fraction of ultrafine a-Fe203in Teflon15shave received attention. The liquid-crystal material 4-pentylphenyl-4-heptyloxythiobenzoate has been studied using a "Fe-enriched ferrocene The chemical state and microstructure of Fe-neutralized Nafion membranes have been studied.15*Fe(H20)s2+ octahedra were identified in the ferrous ionomers, while the ferric Nafion salt was found to contain isolated Fe(H20),:3+species that convert to dimers on drying. The magnetic properties of 57Fe-dopedNiCI,, NiBr,, Nil,, and Col, have been investigated,150 and local and co-operative Jahn-Teller distortions in MZrF, (M = Cu or Cr) have been studied.160 Granular thin films composed of small, finely dispersed iron particles in amorphous alumina have been analysed by a number of techniques. The Mossbauer spectra were used to differentiatebetween metallic iron and oxidized iron throughout the sample thickness.ls1~ls2 The Mossbauer spectra of Fe(0) clusters in a zeolite matrix have been measured at room temperature and at 4 K, and isomer shift of the superparamagneticdoublet indicated that no electron transfer to the matrix had occurred.lG3Iron oxide I. G. Gusakovskaya and T. I. Larkina, Zh. Fiz. Khim., 1983, 57, 136. A. Pron, M. Zagorska, Z. Kucharski, M. Lukasiak, and J. Suwalski, Muter. Res. Bull.. 1982, 17, 150. lS' Z. Kucharski, M. Lukasiak, J. Suwalski, and A. Pron, J. Phys. Colloq., 1983, C3, 321. E. K. Sichel, M. F. Rubner, J. Georger, jun., G . C. Papaefthymiou, S. Ofer, and R. B. Frankel, Phys. Rev. B,l983,28,6589. lM H. Sakai, Y. Maeda, T. Kobayashi, and H. Shirakawa, Bull. Chem. SOC.Jpn., 1983, 56, 1616. lS6 J. C. Gressier, G . Leversque, H. Patin, and F. Varret, Macromolecules, 1983, 16, 1577. lS6L. R. K. Rotenberg, H. R. Rechenberg, and F. Galembeck, Solid State Commwt., 1983,45, 665. lS7 D. G. Todoroff, R. Marande, D. Boyd, and D. L. Uhrich, Mol. Cryst., Liq. Cryst., 1983, 95, 367. lS8H. K. Pan, D. J. Yarusso, G. S. Knapp, M. Pineri, A. Aeagher, J. M. D. Coey, and S. L. Cooper, J. Chem. Phys., 1983, 79, 4736. 160 R. J. Pollard, V. H. McCann, and J. B. Ward, J. Phys. C, 1982, 15, 6807. l8 C. Friebel, J. Pebler, F. Steffens, M. Weber, and D. Peinen, J. Solid State Chem., 1983, 46, 253. ls1 J. L. Dorman, D. Fiorani, J. L. Tholence, and C. Sella, J. Mugn. Mugn. Muter., 1983, 35, 117. E. Paparazzo, J. L. Dorman, and D. Fiorani, Phys. Rev. B, 1983, 28, 1154. F. Schmidt and J. Adolph in ref. 1, p. 454. lS0 lS1

300


dispersions in silica gelleaand iron impurities in amorphous barium vanadatels5 have been studied. Octahedral/tetrahedral Fe:3+site-occupancy ratios in Fe3+doped, rapidly quenched MgO have been determined by e.x.a.f.s. and Mossbauer analysis.16s The constraints placed by these data were used to determine the possible defect-cluster geometries and to identify magnesiowustite-type aggregates.

Emission Studies. Mossbauer spectroscopy has been used to estimate the magneticanisotropy energy constant of small 57Co-dopedparticles of (3-Co in vacuo and with chemisorbed H2 or C0.1e7 Several groups have studied the Mossbauer spectra of 57Co-dopedsilicon. Bergholz and his co-workers have examined the pairing reactions of 5 7 Cin~p-type silicoii.168v16Q Samples prepared by diffusion at 1250 "C and subsequent quenching and annealing have identified Co in interstitial and substitutional sites and in pairs of interstitial Co with B, Al, and Ga. Other workers have reported that by lowering the diffusion temperature to 940 "C the largest fraction of the cobalt remains in substitutional sites with a similar fraction pair-bonded with a shallow boron acceptor.170The amorphization process in 57Co-implanteddiamond has been studied.171Study of the changes in Mossbauer line intensity with crystallographic orientation has identified two different cobalt configurations in 57Co-implantedgraphite.172 Mossbauer emission spectra have been used to study the effects of the doubledecay process 67Ni- - - i 6 7 C-~- - + 67Fein 57Ni-labellednickel The Mossbauer spectra of "Co-doped tris(dipyridine)cobalt(rn) p e r ~ h l o r a t e l ~ ~ and P-PdH2have been and Mossbauer studies on pure and 57Co-doped MgO have been d e s ~ r i b e d . l ~Two ~ * lresonance ~~ lines corresponding to Fe2+and Fe3+ were identified, and the temperature dependence of the isomer shifts was studied. Below lo00 K the spectra obtained were in good agreement with a Debye model. A Mossbauer emission study of single crystals of LiNb03 has been described.17*The non-appearance of anomalous 57Fewas interpreted in terms of the substitution of 5 7 Cinto ~ lithium sites coupled with the formation of a lithium vacancy. G. N. Belozerskii and M. I. Kazakov, Vestn. Leningr. Univ. Fir. Khim., 1982, 22, 67. C, 1983, 117-118, 998. lee G. A. Waychunas, J. Muter. Sci., 1983, 18, 195. le7H. Topsoee, B. S. Clausen, S. Moerup, J. Dam Pedersen, and Y. Maksimov in ref. 1, p. 463. le8W. Bergholz, Physica B + C, 1983, 116, 312. leeW. Bergholz, S. Damgard, J. W. Petersen, and G . Weyer, Phys. Status Solidi A , 1983, 75, 289. 170 E. Scheibe and W. Schrecker, Physica B C , 1983, 116, 318. 171 M. De Potter and G. Langouche, Z . Phys. B, 1983, 53, 89. 17a M. De Potter and G . Langouche, Phys. Lett. A , 1983, 97, 404. 173 J. Ladriere, M. Devilliers, and D. Apres in ref. 1, p. 400. 17* M. I. Afanasov, L. A. Kulikov, and A. M. Babeshkin, Radiochem. Radioanal. Lett., 1983, 57, 247. 17&F. Proebst, F. E. Wagner, and M. Karger, J. Less-Common Met., 1982, 88, 201. 170 R. Olivella, J. Tejada, and T. Harami, Radiat. Ef., 1983,73, 179. 17' H. Olivella, E. Molins, and J. Tejada, Phys. Status Solidi B, 1983, 119, K165. 178 J. Fontcuberta, A. Isalgue, X. Obiadors, J. Tejada, and J. C. Joubert, Radiut. E$., 1983, 73, 173. ler 166

L. D. Bogomolova and S. N. Spasibkina, Physica B

+

+


301

Compounds of Iron.-High-spin Iron(@ Compounds. A study of the two-dimen-

sional antiferromagnetic compound Ba2FeF6has been described.17gMossbauer spectroscopy has been used to examine the 231 K structural phase transition in (MeNH3)2FeC14180 and the magnetic properties of the linear-chain polymer Fe(N,H4),Cl,.181 The magnetic effects of the substitution of small amounts of iron into NiC121e2and C O C I , have ~ ~ ~been investigated using Mossbauer spectroscopy and neutron-scattering techniques. In a separate study a set of Fe-Co exchange parameters has been used to examine the variations in iron spin orientation in F ~ C I , - C O . ~ ~ ~ The Mossbauer spectra of compounds from the series M1M20.5Fel.5C13 - 2H201EG and M2,Fe1-,C12-yH201as(M1 = K or Rb, M2 = Mn, Co, or Ni, x = 0.5 or 0.75, y = 4 or 6) have been reported. An octahedral Fe" environment containing four C1- and two cis-H,O molecules was identified in the rubidium compounds, The complex magnetic behaviour of a series of phenanthrolineferrous chloride complexes has been investigated.lE7 Cation distributions in (Fel-xM2)3(P04)2solid solutions have been determined by Mossbauer spectroscopy (M = Mg, Ca, Co, Ni, or Cd),lE8and a co-operative pseudoJahn-Teller effect in mixed crystals of the type Fe,M1-,S 0 4 * 7 H 2 0(M = Mg, Mn, Zn, or Co) has been identified.lEgMagnetic and Mossbauer measurements have been made on the Prussian Blue analogues Fe[M(CN),] (M = Pd or Pt). The N-co-ordinated Fe" ions are shown to have only the high-spin state over the temperature range 4.2-300 K.lgO The high-spin ferrous ion in truns-bis-(4-acetylpyridine)diaquabis(isothiocyanato)iron(rx) has been found to be co-ordinated to three different ligands in a trans-pseudo-octahedral The sign of the e.f.g. was found to be negative in an examination using an applied magnetic field of 6 T. 67FeMossbauer spectra have been obtained for Fe(p-MeC,H,SO,), at 2.3-300 K in zero field and at 2.3-4.2 K in applied magnetic fields of 1 .l-5.6 T. The complex behaves as a fast-relaxing paramagnet in all cases with no evidence of any antiferromagnetic exchange coupling. The spin-Hamiltonian used to fit the spectra was described.lg2 The final thermal-decomposition product of FeC,04 * 2 H 2 0 from Mossbauer data has been identified as a-Fe203,1g3 and the thermal-decomposition products Renaudin, J. Pannetier, S. Pelaud, A. Ducouret, F. Varret, and G. Ferey, Solid State Commun., 1983,47,455. 180 C. Nicolini and W. M. Reiff, Inorg. Chim. Acta, 1983, 68, 55. 181 A. N. Scoville and W. M. Reiff, Inorg. Chim. Acta, 1983, 68, 57. lEa A. Ito, T. Tamaki, Y. Someya, and H. Ikeda, Physica B + C, 1983,120, 207. Y. Someya, A. Ito, and K. Katsumata, J. Phys. SOC.Jpn., 1983, 52, 254. M. C. K. Wiltshire, B. D. HOW~S, and C. H. Burton, J . Magn. Mugn. Muter., 1983,31-34, 17@ J.

1465.

B. Y. Enwiya, J. Silver, and I. E. G. Morrison, J . Chem. SOC.,Dalton Trans., 1983, 1039. B. Y. Enwiya, J. Silver, and I. E. G. Morrison, J . Chem. SOC.,Dalton Trans., 1983,2581. lE7 F. F. Charron, G. D. Eisman, H. Wong, and M. W. Reiff, Inorg. Chim. Acta, 1983,68,233. A. G. Nord and T. Ericsson, 2.Krist., 1982,161, 209. 18* W. Siebke, H. Spiering, and E. Meissner, Phys. Rev. B, 1983, 27, 2730. '00 H. Inoue and E. Fluck, Z . Naturforsch., Teif B, 1983, 388,687. lP1 G. J. Long, G. Galeazzi, U. RUSSO, G. Valle, and S. Calogero, Inorg. Chem., 1983,22, 507. leaJ. S. Hayes, A. R. H u e , J. R. Sans, and R. C. Thompson, Chem. Phys., 1983,78, 127. leaA. S. Brar and K. S. Khabra, Indian J. Chem., Sect. A , 1982, 21, 920.

302


of a series of mixed iron-nickel oxalates have been identified.lg4 A series of Fe" chloride, bromide, iodide, and perchlorate solvates with N,N-dimethylformamide and N,N-dimethylthioformamide has been studied using x.P.s., Mossbauer, and magnetic data.lg5 The results are discussed using the crystal structures of the two perchlorate complexes. Reflectance, i.r., and Mossbauer spectra and magnetic measurements have been used to characterize a series of FeL2X2 compounds (L = quinoline-2-aldoxime or isoquinoline-3-aldoxime, X = C1, Br, I, NCS, or NCSe).lB6The halo compounds were shown to have a bridged, dimeric, cis-octahedral structure, while the other complexes formed monomers. High-spin Iron(rr1) Compounds. The Mossbauer spectra of (NH,),NaFeF, have been reported around the structural phase transition at 159.5 K.lg7Soliton broadening has been observed in the spectra of single crystals of the one-dimensional antiferromagnet K2FeF5,1g8and the critical behaviour of the layered antiferromagnets RbFeF, and KFeF, has been studied.Ig9The Mossbauer spectra of Cs,FeC1,.H20 have been measured in an applied magnetic field.200The Nee1 temperature was measured as 6.75 K and the saturation hyperfine field as 52 T; field-induced spin-flop behaviour was also studied. Zero- and high-field Mossbauer spectroscopy and magnetic measurements have been used to characterize Co( 1,2-pr0panediamine),FeCl,.~~~ The complex was found to be a simple uniaxial three-dimensional antiferromagnet down to TN (-9 K); however, at 4.2 K a field-induced magnetic phase change was observed when H , > 14kG. The temperature dependences of the magnetic susceptibility and Mossbauer spectrum of polymeric [Fe(uridine)Cl,] have been measured over the temperature range 1.7-300 K.,02 Above 23 K the data are consistent with an octahedral Fe3+ and a polymeric structure. Between 2.2 and 23 K a six-line spectrum corresponding to a single iron site was observed, while below 2.2 K both quadrupole and magnetic splittings were found. Mossbauer and X-ray diffraction measurements have identified several phase transitions in the complex [Fe(DMSO),CI][Fe,Cl,O] between 77 and 400 K.,03 The thermal decomposition of [Co(NH,)][FeCI,] has been investigated in air and nitrogen atmospheres.204 S. M. P. Ramani, N. G. Puttaswamy, and R. M. A. Mallya, Phys. Status Solidi A, 1983, 77, 87. le5 W. Linert, V. Gutrnann, 0. Baumgartner, G. Wiesinger, and H. Kirchmayr, Znorg. Chim. Acta, 1983, 74, 123. lo( M. Mohan and M. Kumar, Acta Chim. Acad. Sci. Hung., 1982,111, 377. le7 J. Pebler, E. Herdtweck, W. Massa, and R. Schmidt, Stud. 7norg. Chem., 1983,3, 501. lo8D. M. Cooper, D. P. E. Dickson, G. P. Gupta, C. E. Johnson, and M. F. Thomas, J. Magn. Mugn. Mater., 1983,31-34, 761. loB H. Keller and I. M. Savic, Phys. Rev. B, 1983, 28, 2638. G. P. Gupta, J. A. Bainer, D. P. E. Dickson, C. E. Johnson, and M. F. Thomas, J. Mugn. Magn. Mater., 1983, 31-34, 763. '01 A. N. Scoville, K. Lazar, W. M. Reiff, and C. Landee, Inorg. Chem., 1983,22, 3514. 202 C. Nicoloni and W. M. Reiff, Polyhedron, 1983, 2,424. loa I. G. Gusakovskaya, T. J. Larkina, V. I. Ponomorev, and L. 0. Atovmyan, 2h:Strukt. Khim., 1982,23, 53. 2~ A. S. Brar, S. Brar, and S. S. Sandhu, Bull. Chem. SOC.Jpn., 1983, 56, 899. lS4


303

The Mossbauer data for potassium ferric alum,2o5black Roussin's salt [KFeS,(NO),], tetramethylammonium Roussin's salt,206and single crystals of ferric ammonium sulphate dodecahydrate207have been reported. The magnetic properties of fine particles of ferric sulphate hydrates have been ~ t u d i e d . ~ ~ * ~ A range of superparamagnetic hydrates in the series Fe(OH)SO, .xH20 ( x = 0-1) was obtained by successive dehydration and rehydration processes and examined by X-ray, electron microscopy, i.r., and Mossbauer methods. The final thermal-decomposition product of ferric nitrate has been identified as a-Fe,O, from its Mossbauer spectrum.lg3 Magnetic and Mossbauer measurements on sodium ferric phosphate and ferric molybdate have obtained values of 47 and 13 K, respectively, for their Nee1 temperatures.21oVarious methods, including Mossbauer spectroscopy, have been used to identify three phases in a supposedly pure sample of ferric phosphate.211 I

,

I

I

I

I

I

1

I

1

1

1

1

-0 1 2 3

4 -5 - 6 '1. 0

22.6K

1

2 3

4 -5

-6 '1.

Velocity/mm s-'

Figure 3 Mossbauer-efect spectra of 'FePO,' obtained at 23.0, 22.8, and 22.0 K (Reproduced with permission from Inorg. Chem., 1983, 22, 3012)

In addition to Fe(P0,) the material contained 30 % of glassy Fe,P,O,, and 2 "/, of mixed-valence Fe7(P04), (Figure 3). The expected results were obtained for FePO, and confirmed that it orders magnetically at 23.8 K. The glassy compact ao6 J. aoI '07 'On

M. Roberts, Phys. Lett. A , 1983, 96, 428.

Y. Wang, Huaxue Tongbao, 1983, 18. L. N. Salugina, A. N. Salugin, Yu. A. Maskaev, and G . I. Kileinikov, Relf.Zh. Khim., 1983, Abstr. No. 8 13 686. P. C. Morais and K. S. Neto, J. Appl. Phys., 1983, 54, 307. P. C. Morais and K. S. Neto, Polyhedron, 1.983, 2, 875. R. Salmon, R. Olazcuaga, Z. Jirak, D. Beltron-Porter, L. Fournes, F. Menil, and G. Le Flem, Stud. Znorg. Chem., 1983,3, 567. G . J. Long, A. K. Cheetham, and P. D. Battle, Znorg. Chem., 1983,22, 3012.

304


was found to order at ca. 7 K, whereas Fe7(P04)*remained paramagnetic down to ca. 10 K. Iron(1n) phosphide has also received attention.212 A linear relationship has been observed between the Mossbauer isomer shift and the size of the alkali metal in the series M3[Fe(HC00)6~.xH20 (M = Li, Na, or K).,13 The isomer shifts were found to increase with a decrease in the electronegativity of the cation. Studies on the solid photolysis products of barium and strontium tris(oxalato)ferrates(rrr) and the y-radiolysis products of M,Fe~~~?~~~ (C204)3.XH20 ( M = Li, Na, K, Cs, or NH4) have been p ~ b l i s h e d . Both the barium and the strontium complexes photolysed to a compound with 6 = 1.28 mm s-l and with splittings of 2.21 mm s-' for the strontium complex and 2.61 mm s-l for the barium complex. The spectra were identified with the stable [Fe"(C,O,),( H2O),l2- moiety. For the al kali-metal complexes, other than potassium, y-radiolysis yielded ferrous oxalate, while the latter gave a product identified as K6Fe'1(C,04),.In the series Fe2M110(CH21COO)6. nH20(M" = VO or Mn, n = 2; MI1 = Co, Ni, Cu, Zn, or Fe, n = 3) the quadrupole splittings of the iron(m) were correlated with the electronegativity of the M ion and the ionic character of the M r e n t r a l 0 bond.216 Three papers have been published on the Mossbauer spectra of the thermaldecomposition products of ferric carboxylates. The complexes (NH,),[Fe(oxalate)]. 3H20 and (NH,),[Fe(citrate),]- 2H20,217 FeL,. 3H20 (L = propionate or butyrate),218and Fe2(succinate)2(OH)2and Fe2(adipate),.5H2O2l9 have all been investigated. Other workers have studied the thermal behaviour and Mossbauer spectra of some ferric benzoate complexes.220 A Mossbauer and i.r. study of binuclear complexes between iron(rI1) sulphate and 1,lo-phenanthroline (L) has been described.221Data were given for (FeL,),O(S04)2-4H20,(FeL),(SO,),. 8 H 2 0 , and (FeLS04)20.6H20.The Mossbauer spectra of iron(1n) complexes of diacetyl monoxime thiosemicarbazone have been described and the iron co-ordinations discussed.222 The structural, magnetic, e.s.r., and Mossbauer spectroscopic properties of the five-co-ordinate complex chlorobis-(N-methylbenzothiohydroxamato)iron(rII)have been investigated.223 Zero-field Mossbauer spectra measured between 4.2 and 300 K demonstrate the high-spin state of the Fell' and show unusual temperature dependences for the area and peak-height asymmetry. Applied magnetic-field spectra at 4.2 K show a large, positive zero-field splitting of the 6A ground state. L. Haeggstroem and A. Narayanasamy, J. Magn. Magn. Muter., 1983,30, 249. A. S. Brar, S. Brar, and S. S. Sandhu in ref. 1, p. 691. a14 A. S. Brar, S. Brar, and S. S. Sandhu, Polyhedron, 1983, 2, 421. als B. S. Randhawa, A. S. Brar, and T. K. Bansal, Radiochem. Radioanal. Lett., 4982, 53, yla

359.

Kh. M. Yakubov, K. I. Turte, T. A. Zhemchuzhnikova, and Sh. Kh. Abdullacv, Dokl. Akad. Nauk Tadzh. SSR, 1982,25,734. a17 B. S. Randhawa and P. S. Bassi, Radiochem. Radioanal. Lett., 1983, 59, 171. 'la P. S. Bassi, B. S. Randhawa, and H. S. Jamwal, Thermochim. Acta, 1983,62,209 "* P. S. Bassi, B. S. Randhawa, and H. S. Jamwal, Thermochim. Acta, 1983, 65, 1. 4ao A. Abras, M. M. Braga, and J. C. Machado, Radiochem. Radioanal. Lett., 1983, 57, 177. N. H. Alcala and A. C. Lupiano, An. Quim. Ser. A , 1982, 78, 289. 22a R. Raina, T. S. Srivastava, J. Joglekar, and S. N. Shringi, Inorg. Chirn. Acta, 1983, 76, alb

L197.

K. J. Berry, P. E. Clark, K. S. Murray, C. L. Raston, and A. H. White, Znorg. Chern., 1983,22, 3928.


305

Mossbauer spectra of eleven tris-(P-diketonato)iron(r~r)complexes have been used to investigate magnetic relaxation A correlation, arising from spin-spin relaxation, was reported between the Mossbauer linewidth and the average Fe-Fe distance in the crystals. An investigation of the results of the reaction of some iron(r1)-Schiff-base complexes with semiquinone and hydroquinone ligands has yielded the first example of a high-spin ferric complex with a monodentate p-semiquinone ligand.z25Mossbauer spectra for some 12- and 14-membered dibenzoyltetra-azo macrocyclic complexes of iron(rrr) have been described, and the presence of both cis and trans isomers has been identified.z26

Intercalation Compounds Containing Iron. Millman and his co-workers have continued their studies on FeCI, intercalated g r a ~ h i t e . ~ A ~ ' spin-glass -~~~ transition associated with iron vacancies in the intercalant lattice was found at 1.7 K,227and samples that had been exposed to the air for longer than one year were found to become unstaged as some FeCI, migrated from the sample and some converted to FeC1,-.228 Mossbauer analysis has shown that below ca. 100 K electrons donated from the graphite host freeze onto selected Fe3+ions to convert them into Fez+.zz9 Chlorine atoms surrounding iron vacancies were identified as the probable primary acceptor site for these electrons. A Mossbauer study has been carried out on an .x-picoline intercalate of FeOCl over the temperature range 4.2-300 K.2:30The spectra were paramagnetic for T > 64 K, and above that temperature they showed charge-transfer effects with the presence of 14 % Fe2+at 64 K and the appearance of a site of intermediate valency at 160 K. The formation of free electrons and ferricinium guest species in 57Fe-labelledferrocene has been confirmed by Mossbauer s p e c t r o ~ c o p y . ~ ~ ~ Trreversible phase transitions were found between the host and guest layers of the intercalate. The intercalation compounds Fe,NbSz (x = $, 3, or *) and FetSn+NbS, have been examined, and the electronic configuration of the iron atoms has been assigned to a formal high-spin Fe2+state.z32J33 Low-spin and Covalent Compounds. The effects of different ligands (L = NOz-, OH2, NH3, N2H5+, enH+, or NO+) on the Mossbauer parameters of some A decrease in quadrupole pentacyanoferrate(r1)complexes have been described.234 splitting with increasing isomer shift was observed. In a related study, mixedmetal bimetallic complexes containing the Fe(CN)5L3- centre were investigated.235Mossbauer spectra were recorded at 298 and 77 K to determine the Ia4 S.

Yamauchi, Y . Sakai, H. Nishioji, and T. Tominga, Int. J. Appl. Rudiat. Isor., 1983,

34,977. Ia6

J.-P.M.Tuchagues and D. N. Hendrickson, Inorg. Chem., 1983,22, 2545.

W. V. Malik, R. Bembi, R. Singh, S. P. Taneja, and D. Raj, Inorg. Chim. Ada, 1983. 68, 223. S. E. Millman and A. D. Zimmerman, J. Phys. C, 1983, 16, L89. S. E. Millman, Synth. Met., 1983, 5, 147. S. E. Millman and G. Kirczenow, Phys. Rev. B, 1983, 28, 5019. aso G. A. Fatseas, P. Palvadeau, and J. P. Veniem, Stud. Inorg. Chem., 1983, 3, 627. H. Schaefer-Stahl, Muter. Res. Bull., 1982, 17, 1437. M. Katada, K. Sato, Y.Hirasawa, and H. Sano in ref. 1, p. 497. M. Katada, K. Sato, Y. Hirasawa, and H. Sano, Radiochem. Radioanal. Lett.. 1982, 54, 293. aM A. S. Brar and S. K. Mammdar, Solid State Comm.,1983,45, 981. K. J. Moore, L. Lee, and J. D. Peterson., Inorg. Chem., 1983, 22, 1244.

306

Spectroscopic Properties of'Inorganic and Organornetallic Compounds

extent of the interaction between the metal centres, and it was concluded that the remote metal centres in general behave as electron-withdrawing substituents on the bridging ligand. Mossbauer spectra have been obtained for a series of complexes Fe(CN),L3- and Fe(CN),L2- (L = an imidazole, pyrazole, pyridine, or pyrazine).23s The results were discussed in terms of the o- and x-donor characteristics of the ligands. A Mossbauer study of the thermal decomposition of [Co(NH,),]Fe(CN), in air and nitrogen has been described.204Magneticsusceptibility and Mossbauer data have been used to characterize the xanthate iron(m) complexes Fe(R-xant), ( R = Me, Et, or Pr') as low-spin compounds.237 From its Mossbauer spectrum a new modification of Fe[S,CNEt,],Br has been found to be paramagnetic at temperatures as low as 1.2 K.238Whereas the isostructural chloride becomes ferromagnetically ordered at 1.52 K, Mossbauer spectra recorded for K,[Fe(c=CR),] and related compounds have shown that the acetylide ion behaves as a o-donor and strong x-acceptor and forms low-spin complexes.239Mossbauer spectra of bis-(q-Cp)iron(II) derivatives (Cp = cyclopentadienyl) enclosed in a- and P-cyclodextrin have been recorded between 78 and 320 For all the compounds the quadrupole doublet observed at low temperatures was found to collapse into a singlet on heating. This was explained in terms of the reorientation of the guest molecule in the clathrate host. A series of papers by Silver et a f . on the Mossbauer spectra of ferrocene complexes has been continued. Work has been published on substituent effects in ferrocenyl carbenium ions,231protonation of ferrocenyl ketones,242bridged ferrocenyl carbenium ions and related protonated ketones,243the structure and reactions of [l]ferrocenophen~phanes,~~~ and diacetylferrocene-metal halide complexes.246 Mossbauer and n.m.r. studies on 1 , l -divinylferrocene homopolymer have shown that radical polymerization leads to the formation of a saturated cyclopolymer containing a three-carbon-bridged ferrocene, whereas cationic polymerization gives an unsaturated structure with ferrocene units either in the main chain or pendant.246Other workers have found a decrease of the recoil-free fraction in poly(viny1ferrocene) and acrylonitrile-vinylferrocene The decrease, which occurs between 80 and 130 K, was accompanied by line broadening and rotational narrowing. These data were interpreted in terms of a n anharmonic, hindered motion of the ferrocene side group. Substituent effects on the redox potential and Mossbauer spectra of a series of ketoferrocenes have C. R. Johnson and R. E. Shepherd, Znorg. Chem., 1983, 22, 3506. S. Wadja and W. Kielbur. Radiochem. Radioanal. Lerr., 1983, 55, 195. 238 S. Decurtins, C. B. Shoemaker, and H. H. Wickman, Acta Crysr., 1983, C39,1218. 43B T. Birchall and D. Ronald, Spectrosc. Znr. J., 1983, 2, 22. 240 Y. Maeda, K. Don, H. Ohshio, and Y . Takashima, Nipport Kagaku Kaishi, 1983, 195. 241 G. Neshvad, R. M. G. Roberts, and J. Silver, J. Orgunomet. Chem., 1982, 236, 237. 842 G. Neshvad, R. M. G. Roberts, and J. Silver, J . Organomet. Chem., 1982, 236, 349. a43 G. Neshvad, R. M. G. Roberts, and J. Silver, J. Organomet. Chem., 1982, 240, 265. a44 M. Clemance, R. M. G. Roberts, and J. Silver, J . Organornet. Chem., 1983,243 461. 245 M. Clemance, R. M. G. Roberts, and J. Silver, J. Organomet. Chem., 1983, 247, 219. 246 G. C. Corfleld, J. S. Brooks, S. Plimley, and A. V. Cunliffe, Proc. Z.U.P.A.C., I.U.P.A.C. Macromol. Symp., 28rh., 1982, 12. 24t F. J. Litterst, A. Lerf, 0. Nuyken, and H. Alcala, Hyperfine Interact., 1982, 12, 317. p36

237


307

been published.24sWhereas the isomer shifts were the same or slightly higher than that of ferrocene itself, the quadrupole splittings were found to be smaller. These results were interpreted in terms of the effects of the carbonyl group on the populations of the molecular orbitals. The Mossbauer spectra of the monocations of 1',1 "'-dihaloferrocenes (1) (R = CI, Br, or I) have been reported,249and the valences of iron in the bridged biferrocene (2) have been studied for a range of bridging groups and anions.25o

A number of mixed-valence compounds were identified, and the valence of the iron was found to depend on both the counter-ions at the bridge. In a related paper temperature-dependent valence states were observed in monocations of trans-(as-indacene)bis(Cp-iron) and compound (1 ; R = a l k ~ l ) .The ~ ~ ~data showed that the compounds are of the averaged-valencetype above 200 K but of the trapped-valence type at lower temperatures. Mossbauer spectra of cisCp,Fe,(CO),, CplFe,(CO),(CNR) (R = Ph or CH,Ph), and [Cp,Fe,(CO),(CNHPh)]+PF,' have been obtained.25':' Elastic neutron-diffraction and Mossbauer spectroscopies have been used to study the structural, orientational disordering transition and melting of an Fe(CO), submonolayer on graphite.254The iron carbonyl carbide and iron carbonyl nitride cluster compounds Fer,(CO)13C and Fe,H(CO),,N255and the products of the reaction between tin(ri) and tin(rv) amides and Fe(CO)j256 have been studied. An it1 situ and ex situ Mossbauer study of iron phthalocyanine At loadings below adsorbed onto high-surface-areacarbon has been described.257 ca. 3.5% a single doublet due to FePc chemically bound to the surface was observed; higher loadings showed two doublets, the second of which was identified with bulk FePc. The relative fraction of the two species was shown to be sensitive to the details of the sample preparation. A. G. Nagy, Hung. Akud. Sci., Cent. Res. Znsr. Phys., KFKI 1983, KFKI-1983-69. I. Motoyama, K. Sato, M. Katada, and H. Sano, Chem. Lett., 1983, 1215. 260 H. H. Wei, C. Y. Lin, and S. J. Chang, Proc. Natl. Sci. Counc., Repub. China. Part B, 1983, 7, 35. 251 S. Iijima, I. Motoyama, H. Sano, and M. Konno in ref. 1, p. 676. 263 H. H. Wei and K. T. Dai, J. Chin. Chem. SOC.(Taipei), 1983, 30, 131. R. Wang, H. Talb, H. Schekter, R. Brener, J. Suzanne, and F. Y. Hansen, Phys. Rev. B. 27, 5864. 265 R. P. Brint, K. O'Cuill, T. R. Spalding, and F. A. Deeney, J. Orgunornet. Chem., 1983. 247, 61. 2m W. Petz and J. Pebler, Znorg. Chim. Actu, 1983, 76, L189. 257 D. A. Sherman, S. B. Yao, E. B. Yeager, J. Eldridge, M. E. Kordesch, and R. W. Hoffman, J . Phys. Chem., 1983,87,932. 248

308


Mixed-valence and Unusual Electronic States. The Mossbauer spectra of Ba,NiFeF,, Ba,FeCrF,, and NaBaFe,F, have been studied as a function of while the two sites in the Ni"Fe"' and Fe"Fe"' compound showed strict structural order. Some low-spin Fe"' has been observed in the one-electron oxidation product of the ferrous complex Na,[(CN),Fe-pyrazine-Fe(CN),I. 8 H ,O.25 The Mossbauer spectrum of a synthetic rasmuthite has shown electron delocalization attributed to an electron density at the iron between pure ionic Fe2+and Fe+.260 Mossbauer spectra for two compounds containing Fe'" have been reported. The Nee1 temperatures of the layer compounds Srg2LatLiaFe4O4, SrtPrqFegO,, and SrlNd3Fe404 were found to be 29.2, 29.2, and 35.2 K, respectively,2e1 and some new [FeIV(Se,CNR,)][BF,] complexes (R = Et, morpholino, piperidino, or benzyl) have been characterized.262The Mossbauer spectrum of the 57Feenriched ethyl derivative gave 6 = 0.87 (relative to sodium nitroprusside) and A = 2.02 mm s-l Spin-crossover Systems and Unusual Spin States. The effects of low pressure on the high-spin to low-spin transition in [Fe,Zn,-,(2-pi~oline)~],.EtOH ( x = 0.5 or 1) have been investigated and compared with The Mossbauer spectra of Fe(o-phen),X, (X = NCSe-, NCS-, or N3-) have been reinvestigated at pressures of 0 . 0 0 1 4 5 kbar.264Large parts of the high-spin to low-spin transition were found to occur abruptly near 9, 13.5, and 24 kbar, respectively. A variable-temperature Mossbauer and X-ray diffraction study of the continuous ST, 'Al transformation in Fe(4-paptH),(C10,)2 - 2H20 and [Fe(4paptH),](BF,), - 2H20 [4-paptH = 2-(4-methyl-2-pyridyl)amino-4-(2-pyridyl)thiazole] has been The transition temperature of the perchlorate complex is given as 185 K and that for the tetrafluoroborate as 220 K. The non-linear temperature dependence of -In(Ct,) and the different temperature factors for the isomer shift are consistent with different Debye-Waller factors. The continuous nature of the transition is interpreted by the assumption of a weak co-operative interaction between the individual complexes and a wide distribution of the nuclei of the minority constituent. A high-spin to low-spin transition has been observed in the linear, binuclear iron@) compound [FeL2(H,0)2],(CF,S0,)e. 266 A high-spin state was found at

+

P. Liu, F. Varret, A. De. Kozak, M. Samouel, M. Leblanc, and G. Ferey, Solid State Commun., 1983,48, 875. K. Rarchlewicz, J. Pietrzyk, and K. Drabent, Znorg. Chim. Acta, 1983, 77, L189. G. Amthauer and K. Bente, Nafurwissenschaften, 1983, 70, 146. *a J. A. Birch and M. F. Thomas, J. Magn. Mugn. Mufer., 1983, 36, 141. P. Deplano, E. F. Trogu, F. Bigoli, E. Lepovati, M. A. Pellinghelli, D. L. Perry, R. J. Saxton, and L. J. Wilson, J . Chem. SOC.,Dalton Trans., 1983, 25. ma E. Meissner, H. Koeppen, H. Spiering, and P. Guetlich, Chem. Phys. Left., 1983, 95, 163. 284 J. Pebler, Znorg. Chem., 1983, 22, 4125. 26S E. Koenig, G. Ritter, S. K. Kulshreshtha, and H. A. Goodwin, Inorg. Chem., 1983, 22. 25*

2518. 268

G. Vos, R. A. Le Febre, R. A. G. De Graaff, J. G. Haasnoot, and J. Reedijk. J. Am. Chern. SOC.,1983, 105, 1682.

Mhsbauer Spectroscopy

309

room temperature, but the spin transition occurs at the phase-transition temperature, 203 K. Mossbauer, magnetic susceptibility, and far4.r. spectroscopy have been used in a detailed characterization of hexa-co-ordinate complexes of The spin transition in the iron(@ with monodentate 1-alkyltetrazole ligand~.~~' n-propyl(ptz) derivative induces a first-order phase transition with a structural reordering in the vicinity of the iron centre, even in the zinc-diluted compound. The methyl, ethyl, and i-propyl complexes, however, exhibit a more gradual and incomplete spin transition and no phase transition. A simulation of the Mossbauer spectra of spin-crossover iron(n1) complexes has been described.2e8The presence of time-dependent electric-field gradients in spin-equilibrium systems between high- and low-spin states of iron(m) was assumed. Results for cases when the principal axis of the e.f.g. of the high-spin state is (i) parallel with and (ii) perpendicular to that of the low-spin state were presented. The application of the model to systems showing fast relaxation is described. Rapid electronic relaxation is described. Rapid electronic relaxation in the 6T e A spin-equilibrium systems [Fe(acen)(dpp)][BPh,] and [Fe(acen)(pic)2][BPhJ [acen = N,N'-bis-( 1-methyl-3-0x0butylidene)ethylenediamine, dpp = 1,3-di-4-pyridylpropane,pic = 4-methylpyridine] has been studied.%O The temperature-dependent Mossbauer spectra of the complexes demonstrate the rapid relaxation (Figure 4), and from the temperature dependence of the quadrupole splittings the separation energies between the two spin states were calculated as 330 and 339 cm-l, respectively.

+

.- 0 . 4 ,

I

I

I

3.00 v,

ul

0 .I

I

,

,

100

200

16gl 300''~

Temperature / K

F m e 4 Temperature dependence of the isomer shgt ( 0 )and quadrupole splitting (0) for [Fe(acen)(~ic)~l(BPhr) (Reproduced with permission from Inorg. Chem., 1983, 22, 2684)

Mossbauer spectra have been obtained for Fe(p-MeC,H,SO,), at 2.3-300 K in zero field and at 2 . U . 2 K in an applied field of 1.1-5.6T.270 The complex

'*'

E. W. Mueller, J. Ensling, H. Spiering, and P. Guetlich, Znorg. Chem., 1983, 22, 2074. Y. Maeda and Y. Takashima, Mem. Fac. Sci., Kyushu Univ., Ser. C, 1983,14, 107. sm H. Ohshio and Y. Maeda, Inorg. Chem., 1983, 22, 2684. *'O J. S. Haynes, A. R. Hume, J. R. Sams, and R. C. Thompson, Chem. Phys., 1983,78, 127.

310

Spectroscopic Properties of Inorganic and Organometaliic Compounds

behaved as a fast-relaxing paramagnet under all conditions, and the magnetic properties were interrupted by treating the ground state as a non-Kramers doublet with fictitious spin S = +.Iron(1r) complexes of N-substituted thiosalicylideneimines have been prepared by the reaction of bis(thiosalicy1dehydrato)iron(n) with primary amines.271p272 While the bidentate complexes show S = 2 spin states, a number of the tetradentate compounds have the S = 1 state. Biological Systems and Related Compounds. A series of papers has been published Mossbauer spectroon the reactions between protoporphyrin 1X and iron.273-27s scopic, magnetic-susceptibility, and i.r. data were reported for a series of metal protoporphyrin-iron(m) complexes.273Studies on frozen aqueous solutions containing Fe"' and protoporphyrin IX have revealed two forms of the complex, monomeric and p-0x0-oligomeric, the latter complex being formed at high pH,274 and they also gave some evidence for an interaction between alkali metals and the propionate groups of the protoporphyrin-iron complex.275Three different iron(@ species were identified in frozen solutions containing protoporphyrin TX and iron(@ (Figure 5).276Over the range pH 7-13 a polymeric species containing Fe" in the S = 1 spin state was found, while above pH 13 a high-spin iron(@ species with 6 = 4.1 1 mm s-l was observed. A second, minority high-spin iron(n) site was also found in all the spectra. The Mossbauer spectra of a series of 14 highly oxidized iron porphyrins have been The authors found that the nature of the porphyrin complexes is extremely sensitive to the nature of the axial co-ordination. As the bridging atom in (tetra-ary1porphyrin)iron complexes was changed from carbon or nitrogen to oxygen, the Mossbauer spectra showed clear changes in the oxidation site from metal-based orbitals to those of the porphyrin. Several other groups have reported work on tetraphenylporphyrinato (TPP) iron complexes and their derivatives. Electrochemical and emission Mossbauer data have been reported for cobalt tetramethoxyphenyl porphyrin,gi8and e.s.c.a. and Mossbauer spectra fot (TPP)iron chloride have been published.279The Mossbauer spectra of a polycrystalline form of the six-co-ordinate high-spin compound (meso-TPP)iron(I1) were recorded over the temperature range 4.2-195 K in magnetic fields of 0-6.0 T and compared with crystal-field calculations.280The results gave an octahedral crystal field around the iron, trigonally distorted in the (111) direction, with a prolate dz2 orbital as the ground state. P. J. Marini, K. S. Murray, and B. 0. West, J . Chem. SOC.,Dalton Trans., 1983, 143. P. J. Marini, K. J. Berry, K . S. Murray, B. 0. West, M. Irving, and P. E. Clark, J. Chem. SOC.,Dalton Trans., 1983, 819. 273 B. Lukas, J. Silver, I. E. G . Morrison, and P. W. C. Barnard., Inorg. Chim. Acta, 1983.78, 205. 274 J. Silver and B. Lukas. Inorg. Chim. Acta, 1983, 78, 219. 275 B. Lukas, J. Peterson, J. Silver, and M. T. Wilson, Znorg. Chim. Acta, 1983,80, 245. J. Silver and B. Lukas, Znorg. Chim. Acta, 1983, 80, 107. 277 D. R. English, D. N. Hendrickson, and K. S. Suslick, Znorg. Chem., 1983, 22, 367. D. A. Scherson, S. H. Gupta, C. Fierro, E. B. Yeager, M. E. Kosdesch, J. Eldridge, R. W. Hoffman, and J. Blue, Electrochim. Acta, 1983, 28, 1205. 270 R. Larrson, J. Blomquist, U. Helgeson, L. C. Moberg, and B. Folkesson, Inorg. Chim. Acta, 1983, 69, 17. 280 B. BOSO, G . Long, and C. A. Reed, J. Chem. Phys., 1983, 78, 2561. 271 272

31 1


I t

-10

I

L

-5

l

I

0

1

L

'

l

10

Veioci t y /mm 5-1

-10

-5

0

10 Velocity / m m s-'

Figure 5 Mossbauer spectra of protoporphyrin I X iron(@ (a) frozen solution from p H 11.95, (b) frozen solution from pH greater than 14 using Me4NOH as base (Reproduced with permission from Inorg. Chim. Acfa, 1983, 80, 107)

The electric-field gradients in dicarbonyl complexes of (TPP)iron(rr) and (octamethyltetrabenzoporphyrinato)iron(rr) have been discussed,281 and the

spin states in bis-(3-chloropyridine)(octaethylporphinato)iron(rr1) have been investigated.282A quantum-admixed intermediate-spin state was stabilized in the latter compound and characterized by a number of techniques, including Mossbauer spectroscopy. The data from a Mossbauer spectral study of oxidiad chloro-5,10,15,20-tetra(mesityl)porphyrinatoiron(111) have been interpreted using a spin-Hamiltonian model in which the central FeIV complex, with S = 1, is tightly coupled to a S = 9 system of the oxidized porphyrin to yield a net S = 8 system.283 The synthesis and spectroscopic properties of a five-co-ordinate picket-fence porphyrin complex and synthetic analogues for the active site in cytochrome P450 have been d e ~ c r i b e d . ~The ~ ~preparation -~~~ and Mossbauer properties of a

2eo

K. J. Reimer, C. A. Sibley, and J. R. Sams, J . Am. Chem. SOC.,1983, 105, 5147. W. R. Scheridt, D. K. George, R. G. Hayes, and G. Long, J. Am. Chem. SOC.,1983,105, 2625.

B. Boso, G. Lang, T. J. McMurry, and J. T. Groves, J. Chem. Phys., 1983, 79, 1122. R. Monteil-Montoya, E. Bill, U. Gonser, S. Lauer, A. X. Trautwein, M. Schappacher, L. Ricard, and R. Weiss, NATO Adv. Study Znst. Ser., Ser. C, 1983, 100, 363. 285 M. Schappacher, L. Ricard, R. Weiss, A. Trautwein, R. Monteil-Montoya, U. Gonser, and E. Bill, Inorg. Chim. Acta, 1983,78, L9. 284

286

L. Ricard, M. Schappacher, R. Weiss, R. Monteil-Montoya, E. Bill, U. Gonser, and A. Trautwein, Nuuv. J . Chim., 1983, 7, 405.

312


series of peptides derived from horse-heart cytochrome c have been and a comparative Mossbauer study of bovine-heart cytochrome oxidase and cyctochrome C1aa3from Thermus thermophifus has been described.288 The influence of protein dynamics on Mossbauer spectra has been The Mossbauer spectra of 57Fe-containingdeoxymyoglobin crystals were analysed using a minimum of three Brownian oscillator modes to account for protein specific motions of affecting the iron nuclei. It was concluded that anomalies in the Mossbauer spectra of protein crystals originated from protein dynamics. Other workers have obtained good results by using a bounded diffusion model to fit the Mossbauer spectra of a variety of biological Mossbauer spectra of human deoxyhaemoglobin and haemochrome frozen solutions, selectively enriched with 57Fein either the ct- or the @-chains,have been measured from 4.2 to 250 K.291The structural dynamics of the haem atoms were determined from the Lamb-Mossbauer factors calculated from these spectra. Comparison of the motions of the two haemoglobins studied showed that molecular diffusion can be neglected in the analysis of the dynamics below ca. 250 K. The orientational dependence of the Mossbauer spectra of a metmyoglobin single crystal in a weak magnetic field has been investigated at 4.2 K.292 The haem normal was detected with respect to the orientation of the myoglobin crystal. The effects of microwave radiation on rat h a e m ~ g l o b i nand ~ ~an ~ anomaly in the temperature dependence of the quadrupole splitting of m e t h a e m ~ g l o b i n ~ ~ ~ have been studied. The temperature-dependent Mossbauer spectra of oxyhaemoglobin have been investigated over the temperature range 9-170 K.295 A previously reported mechanism for the reduction of iron(rr1) to iron@) in microbial iron-transport compounds has been modified by evidence for the monoprotonation of the monocatecholo acid-stable iron complex.2g6The monoprotonated catechol species was identified as the electron donor to Fe"', and protonation of the iron-containing siderophore was considered essential for the reduction. The pH-dependent Mossbauer spectra of ferric enterobactin and some synthetic analogues have been reported,297and Mossbauer data for an important iron-transport protein, human transferrin, have been The ferric and J. Peterson, M. M. M. Saleem, J. Silver, M. T. Wilson, and I. E. G. Morrison, J. Inorg. Biochem., 1983,19, 165. z88 T. A. Kent, L. J. Young, G. Palmer, J. A. Fee, and E. Munck, J . Biol. Chem., 1983, 258, 267

8543. aoo

E. W. Knapp, S. F. Fischer, and F. Parak, J. Chem. Phys., 1983,78,4701. L. Nowick, S. G. Cohen, E. R. Bauminger, and S. Ofer, Phys. Rev. Lett., 1983, 50, 1528. K. H. Mayo, D. Kuchieda, F. Parak, and J. C. W. Chien, Proc. Natl. Acad. Sci. U.S.A.,

a*2

S.S. Yakimov, V. M. Cherpanov, M. A. Chuev, A. M. Afanas'ev, and F.Parak, Hyperfine

1983,80,5294.

Interact., 1983, 14, 1. N. Devyathov, N. D. Didenko, V. I. Zelenstov, S. V. Zololov, V. F. Tsarik, and V. A. Cha, Radiobiologiya, 1983.23, 80. 294 N. P. Didenko, V. I. Zelentsov, V. S. Kositsyn, V. A. Cha, and E. M. Chuprikova. Pis'ma Zh. Tekh. Fiz., 1983, 9, 332. 2os L. Fiesdi, M. Mancini, G. Spina, and L. Gianchi in ref. 1, p. 971. 206 R. C. Hider, B. Howlin, J. R. Miller, A. R. Mohd-Nor, and J. Silver, Inorg. Chim. Acta, z93 N.

1983, 80, 51. *07

V. L. Pecoraro, G. B. Wong, T. A. Kent, and K. N. Raymond, J . Am. Chem. SOC.,1983, 105,4617. S. Adelski, H. Appel, H. Haffner, Th. Kriger, and D. M. Taylor in ref. 1, p. 663.


313

ferrous oxygenated bleomycin complexes were ~ t u d i e d The . ~ former ~ ~ ~ ~ study ~ ~ found a single pH-dependent paramagnetic site in the ferrous complex, while the ferric compound showed an additional pH-dependent site that converted to Fez+ above pH 0.5. The latter investigation showed the iron to be diamagnetic, and the Mossbauer parameters ( 6 = -0.16 and A = -2.96 mm s-l at 4.2 K) were attributed to low-spin Fe"' bound to superoxide anion. Evidence has been presented for the formation of an S = Q spin-coupled pair of high-spin Fe"' in the major reaction product of sulphide with methaemerythrin of Phasholopsis go~ldi.~Ol A novel high-spin Fe" site has been identified in protocatechuate 4,Sdioxygenase from Pseudomonas testosteroni.302The Mossbauer parameters A = 2.22 mm s-l and 6 = 1.28 mm s-l (relative to a-Fe) are unique for enzymes but similar to those of the reaction centre in Rhodopseudomonas spheroides R-26. Mossbauer data for the hydrogenase from Desulfovibrio desulfuricans,303 nitrogenase from Xanthobactor autoropicus GZ29,3w and pig allantoic acid have been reported, and the state of iron in subchromophore fragments of Rhodopseudomonas sphaeroides has been investigated.30s A series of papers on the reaction of iron with glutathiones and related thiols has been p ~ b l i s h e d . ~A~Mossbauer ~ - ~ ~ ~ study of putidamono-oxin has been reported.310Three iron atoms were identified in its activation of oxygen; two were identified with a [2Fe-2S] ferredoxin-type chromophore and the third was identified with a mononuclear non-haem iron. Mossbauer evidence has been presented for exchange-coupled sirohaem and [4Fe4S] prosthetic groups in Escherichia coli sulphite r e d ~ c t a s e . ~An ~ l analogue ~ ~ l ~ for the [4Fe4S]+ sites of reduced ferredoxins (Et4N)3[Fe4S4(S-p-C8H4Br)4] has been characterized, and its crystal structure and Mossbauer spectra were studied.s13Experimental and

B. Balko and G. W. Liesegang, Biochem. Biophys. Res. Commun., 1983,110, 827. R. M.Burger, T. A. Kent, S. B. Horwitz, E. Muenck, and J. Peisach, J. Biol. Chem. 1983, 258, 1559. D. M. Kurlz, jun., T. J. Sage, M. Hendrich, P. G. Debrunner, and G. S . Lukat, J. Biof. Chem., 1983,258,2115, w1 D. M. Aciero, J. D. Lipscomb, H. B. Huynh, T. A. Kent, and E. Muenck, J. Biol. Chem., 1983, 258, 14 981. S. H. Bell, D. P.E.Dickson, C. E.Johnson, R. Cammach, D. 0.Hall, W. V. Lallamahajajh, and K. K. Rao in ref. 1, p. 654. K. A. D. Rottergarat, GSF-Ber. BT, 1983, 789. P. G. Debrunner, M. P. Hendrich, J. De Jersey, D. T. Keough, J. T. Sage, and B. Zerner, Biochem. Biophys. A d a , 1983,745,103. N. Ya. Uspenskaya, A. A. Novakova, A. Yu Aleksandrov, R. N. Kuzmin, A. A. Kononenko, and A. B. Rubin, Biojizika, 1 9 8 3 , s . 376. M.Y.Hamed, J. Silver, and M. T. Wilson, Inorg. Chim. Acfa, 1983, 78, 1. M. Y.Hamed and J. Silver, Znorg. Chim. A d a , 1983, 80, 115. M.Y. Hamed, J. Silver, and M.T. Wilson, Inorg. Chim. Acfu, 1983,80,237. alo E. Bill, F. H. Bernhardt, and A. X . Trautwein, NATO Adv. Study Insf. Ser., Ser. C, 1983, 100,259. 311 J. A. Christner, E. Muenck, P. A. Janick, and L. M. Siegel, J. Biof. Chem., 1983, 258, 11 147. 31a J. A. Christner, P. A. Janick, L. M. Siegel, and E. Muenck, J . Biol. Chem., 1983, 258, 11 157. 303

81a

D. W. Stephon, G. C. Papaefthymiou, R. B. Frankel, and R. H. Holm, Inorg. Chem., 1983,22, 1550.

314


theoretical Mossbauer parameters of the octahedral iron cluster compound Fee(p3-S)s(PEt3)e(BPh4)2have been The syntheses, Mossbauer spectra, and crystal structures of the Ph4P+ and Et4N+ salts of the anions [(PhS)2FeS2MS2]2-and [(S3)FeS2MS2I2-(M = Mo or W) have been described,315 and a new anionic complex [CI,F~S,MOO(S,)]~has been ~ h a r a c t e r i z e d . ~ ~ ~ The Mossbauer spectra of synthetic melanins from L-dopa, dopamine, and diethylamine-dopamine have been reported. 317 A polynuclear mixed-ligand complex Fe8L2D2AcO(OH)lg(L = lactabionate, D = one glucopyranose of dextrose, Ac = acetate), for use in parenteral iron therapy, has been characterized318and a single high-spin Fe"' site identified.31gThe reduction of Fe"' to Fe" and of Vv to V" by polygalacturonic acid32oand the iron location in humanplacental membranes have been studied. 821 --

Oxide and Chalcogenide Systems Containing Iron.-Simple Oxides and Hydroxides. The hyperhe splitting parameters of Fe203 have been measured over the temperature range 130-955 K, without finding any temperature dependence of the electric-field gradient at the iron nuclei.322The magnetic and Mossbauer properties of a-Fe2O3coated with 57Fe323 and 57C0adsorbed on y-Fe20s324 have been investigated. The Mossbauer spectrum of haematite has been studied at pressures up to 53 kbar and at temperatures in the range 77-340 K.325An anomalous reduction in the quadrupole splitting in conditions near the Morin transition was observed, and precise data on the atomic positions were obtained. Mossbauer data for some aluminium-substituted haematites have been rep~rted.~~~~~~~ Features attributed to quasi-particle behaviour have been observed in the Mossbauer spectra of magnetite.328The magnetite-maghaemite and the magnetic and Mossbauer properties of 60 A particles of Fe304330have been

F. Del Giallo, F. Pieralli, L. Fiesoli, and G. Spina, Phys. Lett. A , 1983, 96, 1411. D. Coucouvanis, P. Stremple, E. D. Simnon, D. Swenson, N. G. Baenziger, M. Draganjac, L. T. Chan, A. Simopoulas, V. Papalefthymiou, A. Kostikas, and V. Petrouleas. Znorg. Chem., 1983, 22, 293. 31e A. Mueller, S. Sarhar, H. Boegge, R. Jostes, A. Trautwein, and U. Lauer, Angew. Chem., 314

315

1983, 95, 574.

M. Carbucicchio and P. R. Crippa in ref. 1, p. 661. 318 L. Burger, I. Zay, and G. T. Nagy, Inorg. Chim. Acta, 1983, 80, 231. 31D C. Gessa, M. L. De Cherchi, A. Dessi, S. Deiana, and G. Micera, Inorg. Chim. Acta, 1983, 80, L53. 320 M. Tronkovic, 0. Hadzija, and I. Naggy-Czako, Inorg. Chim. Acta, 1983, 80, 257. 321 S. H. Bell, P. J. Brown, D. P. E. Dickson, and P. M. Johnson, Biochem. Biophys. Acra, 317

1983,75,250.

D. A. Khramov and A. V. Polosin, Fiz. Tverd. Tela, 1983, 25, 2769. sa3 T. Shinjo, M. Kiyama, N. Sugita, K. Watanabe, and T. Takada, J. Magn. Magn. Muter., 322

1983, 35, 133. 324

T. Okada, H. Sekizawa, F. Ambe, S. Ambe, and T. Yamadaya, J. Magn. Magn. Muter., 1983,31-34,

903.

C . L. Bruzzone and R. Ingals, Phys. Rev. B, 1983, 28, 2430. 326 E. De Grave, L. H. Bowen, and G. G. Robbrecht, Stud. Inorg. Chem., 1983,3, 571. s27 E. De Grave, D. Chabaere, and L. H. Bowen, J . Magn. Magn. Muter., 1983, 30, 349. s28 A. A. Hirsch, Valence Znstab., Proc. Int. Conf., 1982, 569. 320 A. Gedikoghi, Scr. Metall., 1983, 17, 45. s30 S. Morup and H. Topsoe, J . Magn. Magn. Mater., 1983, 31-34, 953. 3a6

MGssbauer Spectroscopy

315

studied. Magnetic-susceptibility and Mossbauer data for three ferrofluids have been reported. 331 The ferrofluids, suspensions of 100-200 A Fe304 particles, were found to display the properties of spin glasses. The products of the disproportionation of ferrous hydroxide in an argon atmosphere have been studied using Mossbauer spectroscopy.332 The temperature dependence of the magnetic-hyperfine field of microcrystalline wFe00H has ~ ~ found been compared with the behaviour of well crystallized g ~ e t h i t eIt. ~was that the magnetic properties could not be described by existing theories for collective magnetic excitations and superparamagnetic relaxation. A model was proposed which takes into account the magnetic interaction among the particles and uses a modified Weiss mean-field theory. This 'superferromagnetic' model was found to give a significantly better fit than a 'super-spin-glass' model. The transformation of a-FeOOH into magnetite, zinc, and molybdenum ferrites by the air oxidation of aqueous suspensions in the presence of Fe", Zn", and Mo"' has been described and studied by methods including Mossbauer spectroscopy.334- 3 36 Spinels and Related Oxides. The temperature dependences of the Mossbauer linewidths and their variation with the cell parameter in a series of ferrite spinels have been A series of papers has appeared on the Mossbauer spectra of mechanically activated ferrite spinels,339-343 and some ultrafine spinel ferrites have been c h a r a c t e r i ~ e d .A~ ~Verwey ~ transition has been observed in Li,Fe,-,O, (0.025 < x < 0.03),344and a variable-temperature study has shown that the Co2+ions occupy the octahedral B sites in Co,Fe,-,04 (x < 0.4).346 Two studies on zinc-substituted magnetite346i347 and others on copper magneA. Tari, J. Popplewell, S. W. Charles, D. S. Dunbury, and K. M . Alves. J . A p p l . Phvs.. 1983,54, 3351. 332 J. Zhang, Y. Ni, Y . Xia, and S. Qi, Kexue, Tongbao, 1983, 28, 91. 'ws S. Morup, M. B. Modsen, J. Franck. J. Villadsen. and C. J. W. Koch, J . Mngn. M t r w . Mater., 1983, 40,163. Y. Tamaura, K. Ito, and T. Katsura, J . Chem. Soc., Dalton Trans., 1983, 189. 38b K. Ito, Y. Tamaura, and T. Katsura, J . Chem. SOC.,Daltori Trans., 1983, 987. 336 T. Kanzaki, H. Funikawa, and T. Katsura, J. Chern. Soc., Dalton Trans., 1983, 987. 337 V. I. Nikolaev, M. M. Guseinov, V. V. Korchazhkin, N. N. Oleinikov, V. S. Rusakov, and A. M. Shipilin, VINITI, 51 17-82. V. 1. Nikolaev, V. S. Rusakov, and N. I. Christyakova, Vestn. Mosk. Univ. Ser. 3, Fiz., Astron., 1983, 24, 74. 339

Yu. T. Pavlyukhin, Ya. Ya. Medikov, and V. V. Boldyrev, Dokl. Akad. Nauk SSSR, 1982, 266, 1920.

Yu. T. Pavlyukhin, Ya. Ya. Medikov, and V. V. Boldyrev, Fiz. Tverd. Tela, 1983, 25. 630. 841 Yu. T. Pavlyukhin, Ya. Ya. Medikov, and V. V. Boldyrev, Mater. Res. Bull., 1983, 18, 340

1317.

342Yu. T. Pavlyukhin, Ya. Ya. Medikov, and V. V. Boldyrev, Izv. Sib. Otd. Akad. Nard SSSR, Ser. Khim. Nauk, 1983, 8. 343 R. E. Vandenberghe, R. Vanleerberghe, and G. G . Robbrecht, Stud. fnorg. Chem., 1983. 3, 395.

T . Merceron, C. Djega-Mariadassou, and J. L. Dormann, J . Magn. Magn. Muter., 1983. 31-34,78 345

1.

E. De Grave, R. Leyman, and R. Vanleerberghe, Phys. Lett. A, 1983,97, 354. S. Ligenza, M. Lukasiak, Z. Kucharski, and J. Suwalski. Phys. Starus Solidi B, 1983, 117, 465. C. E. Deshpande, S. K. Date, P. M. Gupta. and M. N. S. Murthy. Proc. Indian Acad. Sci.. Ser. Chem. Sci.. 1982,91,377.

316


tite348and on a germanium-substituted magnetite349have been reported. A highfield Mossbauer study on small NiFeO, particles has found an anomalous cation distribution attributed to a collective magnetic-excitation Bancroft and his co-workers have investigated the Mossbauer spectra of Al-, Mg-, and Zn-substituted chromium Whereas the spectra of the Fe(Cr,Al)O, spinels were interpreted using partial quadrupole splittings, the other spinels gave only a singlet for compositions with less than half the iron replaced by the divalent ions. Mossbauer studies on nickel-substituted magn e s i ~ mcopper,354 , ~ ~ ~ and cadmium365ferrospinels have been described, and work on NiAlo.31n,Fel.,-,0,35s and Nil-,-yZnySn,Fe2-2x04357 systems has been reported. Cationic distributions in (Co,Mn,Fe)O,, (Ni,Mn,Fe)0,,368 (Zn,Co)FeMn0,,359(Ni,Zn,Sn,Fe)0,,360and (In,Mn,Zn,Fe)043s1have been determined. The Mossbauer spectra of CoGaFeO, have been measured over the temperature range 5-325 K.362It was found to contain only Fe3+in both the octahedral and the tetrahedral sites. An investigation of the Cd,Mgl-,Fe204 system (x = 0 4 . 8 ) at 4.2 K has identified two hyperfme fields.363The variations in isomer shift as a function of cadmium content were found to be consistent with the changes in the F e - 0 internuclear distances. Evidence has been obtained for a fast electronic exchange between Fe2+and Fe3+in rhombohedra1 The variation in NCel temperature in the ironrare-earth layer compounds Sro.5M1.5Lil.5Feo.504(M = La, Pr, or Nd) has been studied and discussed in terms of interlayer separations and the magnetic natures of the r a r e - e a r t h ~ . Magnetic ~~~ relaxation rates in Y 3Al,Fe,-,0,2 (x = 0 or 1.25) have been and low-temperature transitions have been observed in RFe20, (R = Y-Lu, Y-Dy, Er, or Tm).367Ferrite spinels containing

B. Hannoyer and M. Langlet, Stud. Inorg. Chem., 1983, 3,617. G.K. Jung, Sae Mulli, 1982, 22, 364. 350 K. Haneda, W. Kojima, and A. H. Morrish, J . Magn. Magn. Mater., 1983, 31-34, 951. 361 G.M. Bancroft, M. D. Osborne, and M. E. Fleet, Solid State Commun., 1983, 47, 623. 36a M.D. Osborne, M. E. Fleet, and G . M. Bancroft, Solid State Commun., 1983,48,663. 313 K. Seshan, A. S. Bommannavar, and D. K. Chakrabarty, J . Solid State Chem., 1983, 47. 348

a49

107.

3 S P AS.. Bommannaver, D. K . Chakrabarty, and A. B. Biswas, J . Indian Chem. Soc.. 1982. 59, 1310.

Sh. M. Aliev, I. K. Kamilov, and A. S. Batymurzaev, Fiz. Tverd. Tela, 1983, 25, 1539. J. D. Bakuma, E. A. Zhurakovskii, G . S. Podval'nykh. and A. I . Antoshchuk. Metnllnfizika, 1983, 5, 25. 357 U. Varshney, R. K. Puri, and R. G . Mendiratta in ref. I , p. 190. g58 V. K. Singh and S. Lokanathan, Pramana, 1983, 20, I . S6Q P. S. Jain and V. S. Darshane, Pramana, 1983, 20, 7. 360 R. K. Puri and U . Varshey, J . Phys. Chem. Solids, 1983, 44, 655. K. H. Rao and R. G . Mendiratta, J . Appl. Phys., 1983, 54, 1795. G. D. Sultanov and S. G . Ibrayimov, Tr. Vses. Konf. Fir. Polirprov., 1982, 279. 363 R. V. Upadhyay and R. G . Kulkarni, Solid State Commun., 1983, 48, 691. 381 R. Gerardin and D. Everard, J. Phys. Chem. Solids, 1983, 44, 423. 385 J. A. Birch and M. F. Thomas, J . Magn. Magn. Mater., 1983, 36, 141. as6T. M. Uen, D. E. Chen, C. C. Dai, and P. K. Tseung, J . Magn. Magn. Mater., 1983. 855

356

31-34, 367

789.

M. Kishi, Y. Nakagawa, M. Tanaka, N. Kimizuka, and I. Shindo, J. Magn. Magn. Mater., 1983, 31-34, 807.

Mhbauer Spectroscopy

31 7

Ge4+and Sn4+,3esCo2+ and Ti4+,3697370 and Li+, Ti4+,or Ge4+371 have been reported. The 67Feand lZISb Mossbauer spectra of LiSbo.5Fel.504have been

Other Oxides. The lSIEuand 67FeMossbauer resonances have been used to study magnetic exchange interactions in the orthorhombic perovskite solid solutions (0 -c x -el). Replacement of a neighE u F ~ , - , C O , O ~and ~ ~ ~EuF,-,C~,O,~~~ bouring Fe3+ion by diamagnetic Co3+373 was found to result in a reduction in the flux density of the supertransferred hyperfine field at the 67Fenucleus of 1.02 T extrapolated to 0 K,while the corresponding value for Cr3+substitution was 0.82 T. Several groups have published work on yttrium iron garnets (YIG). Pure nuclear reflexes and combined hyperfine interactions in pure YIG,376domainwall pinning in silicon-doped YIG,376and broad magnetic transitions in cobaltsubstituted YIG377have been investigated. The Mossbauer spectra of YIG containing large amounts of Sc3+and Zr4+substituted for Fe3+ions (with the latter ions compensated for by Ca2+) have confirmed that the Zr4+ and Hf4+ ions exclusively occupy octahedral sites. Very small amounts of Sc3+,0.03 ions at a level of one Sc3+per formula unit, were found to occupy tetrahedral A Mossbauer study of bismuth-doped YIG single crystals has also been reporThe cationic distribution of Fe3+and Ga3+in Ga-YIG has been studied after heating to temperaturesin the range 1 ~ 1 5 0 0C.380 0 The Ga3+showed a preference for the tetrahedral sites whereas the Fe3+preferred the octahedral sites. A more disordered distribution was observed at higher temperatures. The magnetic properties of amorphous rare-earth iron and an yttriumcalcium-indium-germanium-iron garnet382 have been described. Electricquadrupole interactions at the octahedral, tetrahedral, and dodecahedral sites in E U , + S C ~ + ~ F ~(0 , OG~ x, < 0.5) have been probed by lSIEu and a7FeMossbauer and the e.f.g. tensor at the three sites was calculated using a monopole-point-dipolemodel. K. Melzer, S. Mueller, J. Suwalski, and Z. Kucharski, Cryst. Res. Technol.. 1983. 18. K101. Y .Abbas and A. Adam, J . Magn. Magn. Mater., 1983,31-34,635. 370 J. L. Dorman, T. Merceras, and M. Nogues in ref. 1, p. 193. 371 A. Watanabe, H. Yamamura, Y . Moriyoshi, and S. Shirasaki Fevites. Proc. ICF, 3rd. 1980, 1982, 170. G. Dehe and J. Suwalski, Phys. Status Solidi B, 1983, 119. K155. a73 T. C. Gibb, J. Chem. SOC.,Dalron Trans., 1983, 873. s74 T. C. Gibb, J. Chem. SOC.,Dalton Trans., 1983, 2031. a7s W. Winkler, R. Eiskerg, E. Alp, R. Rueffer, E. Gerdau, S. Lauer, A. Trautwein, M . Grodzicki, and A. Vera, 2.Phys. B, 1983,49, 331. a76N.A. Artem’ev, V. E. Makhotkin, A. V. Myagkov, and V. A. Ruban, Tr. Fir. Inst. Im. P. N . Lebedeva, Akad. Nauk SSSR, 1983, 139, 93. 377 S. Geller, G. Balestrino, A. K. Ray, and A. Tucciavone, Phys. Rev. B, 1983. 27, 326. a78 G. Balestrino and S. Geller, Phys. Rev. B, 1983, 27, 5807. s7@Q. Ling, X. Xu, and C. Lin, Wuli Xuebao, 1982, 31, 1680. 380 G. Amthauer, V. Guenzler, S. S. Hafner, and D. Reinen, 2.Krist., 1982, 161, 167. a81 N. Schultes, H. Schieder, F. J. Litterst, and G. M. Kalvius, J . Magn. Magn. Mnter.. 1983. 31-34, 1507. 381 M. Lin, S. Li, and G. Li, Qinghua Daxue Xuebao, 1982, 22, 1. Z. M. Stadnik and B. F. Otterloo, J . Solid State Chem., 1983, 48, 133. 36*

318


The Mossbauer spectrum of microcrystalline YFeO, has been reported,384 and two-dimensional magnetic ordering has been observed in L u ~ FThe~ ~ magnetic properties and Mossbauer spectra of the hexagonal ferrites La,Ba,-,ZnxOlg,386Ba(Znl-xMnx)zFels0271,387 BaZnFe16-,Mx027 (M = In or S C ) , ~ ~ * and Ba2Fe22+Fe283+04638g have been studied. A large quadrupole splitting in the cubic pyrochlores Bi,-,Y,FeSbO, (x = 0, 1, or 2) has been attributed to a highly disordered MOB A Mossbauer singlet resonance observed by progressively reducing preoxidized P-Ca2Si04containing 10 wt. % FeO has been attributed to finely particulate iron metal in an insulating matrix.3g1 Studies on iron-doped potassium molybdenum and V02,393 the , ~ the~surface ~ oxidation of M,FeMoO, interaction of iron oxides with O S O ~and ceramics (M = Ba, Sr, or Ca)3g6have been described.

Inorganic Oxide Glasses Containing Iron. 57FeMossbauer studies of borate, borosilicate, and vanadate glasses through their glass-transition temperatures, T . , have shown that the recoil-free fraction decreases with temperature, particularly around Tg.3g6 An attempt to explain the results using the cluster model suggested that soft modes were associated with the glass transition. The effect of iron concentration on the Fe2+/FeS+ratio in Si02-Fe20, glasses obtained by the sol-gel method has been investigated3g7and a relationship found. In a separate study on sol-gel-prepared glass the iron in the silicate lattice was found to have Mossbauer parameters corresponding to tetrahedral Fe3+.3g8Mossbauer spectroscopy has been used to study the crystallization kinetics and mechanism of borosilicate glasses399and the properties of iron-containing aluminosilicate Several borate glasses have been studied using Mossbauer method^,^^^-^^^ and f l u o r o p h ~ s p h a t eb, ~o ~r o~p h o ~ p h a t e and , ~ ~ ~t e l l u r o p h ~ s p h a t eglasses ~ ~ ~ have been 3e4P. Ayyub, M. S. Multani, and A. Gurjar, Muter. Lett., 1983, 2, 122. M. Tanaka, N. Kimizuka, J. Akimitsu. S. Funahashi, and K. Siratori, J . Mugn. Mugn. Muter., 1983,31-34, 769. 386 Y . Du, H. Lu, Y. Zhang, L. Hui, and T. Wang, Wuli Xuebuo, 1983,32, 168. T. Besagni, A. Deriu, F. Licci, and S. Rinaldi, J. Mugn. Mugn. Mater., 1983, 31-34, 791. M. Carbucicchio, L. Paretijad, and S. Rinaldi, Phys. Status Solidi A , 1982,73, K193-Kl97. B. X. Gu, H. X. Lu, and Y. W. Du, J . Mugn. Mugn. Muter., 1983, 31-34, 803. 390 M. D. Sundararajan, A. Narayanasamy, T. Nagnarjan, G. V. Subba-Rao. A. K. Singh, and L. Haeggstroem, Solid State Commun., 1983, 48, 657. 391 K. J. D. Mackenzie and M. E. Bowder, J. Muter. Sci. Lett.. 1983, 2, 317. 302 J. Dumas, E. Bervas, J. Marcus, D. Salomon, C. Schlenker. and G. Fillion. J. Mugit. Magn. Mater., 1983, 31-34, 535. 3g3 J. Pelder, Phys. Status Solidi A , 1983, 78, 589. 3g4 L. L. Tokar, V. N. Bruek, and Yu. V. Permyakov, Tsvetri. Met., 1983,29. 3Db K. Shono, M. Abe, M. Gomi, and S. Namura, Jpn. J. Appl. Phys., 1982, 21, 1720. S. Bharati, R. Parthasarathy, K. J. Rao, and C. N. R. Rao, Solid State Commun., 1983, 46, 451. 3g7 M. Guyielmi, A. Maddalena, and G. Principi, J. Muter. Sci. Lett., 1983, 3, 467. N. Uetake and M. Kikuchi, Chern. Lett., 1983,229. 309 T. Nishida, T. Hirai, and Y. Takashima, Phys. Chem. Glasses, 1983, 24. 1 1 3. 400 F. D. Doenitz, C. Russ, and W. Vogel, Silikuttechnik, 1983, 34, 155. 401 A. Schnell, J. C. Berner, and J. P. Sanchez, Muter. Res. Bull., 1983, 18, 251. 402 E. BUTZO, D. Ungur, and I. Ardelean, J. Mugn. Mugn. Muter., 1983, 31-34, 1509. 403 T. Nishida, T. Nonaka, T. Isobe, and Y . Takashima, Phys. Chem. Glasses, 1983, 24, 88. 404 R. Kamal, S. S. Sekhon, N. Kishore. and R. G. Mendiratta, J. Non-Cryst. Solids. 1982. 53, 227. 385

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319

investigated. The potassium borophosphate glasses showed a decrease in the Mossbauer isomer shifts of both Fe2+ and Fe3+ with increasing alkali-metal content and also a linear decrease in the relative absorption area of Fe2+due to shorter Fe-0 distances. Magnetic properties of a Iead-boron-aluminium-ironyttrium oxide glass ceramic have been Interactions between iron and vanadium ions in semiconducting barium vanadate glasses have been studied using e.p.r., magnetic susceptibility, d.c. conductivity, and the Mossbauer The iron was found to enter the lattice as Fes+ and form associations with both V4+ and other Fe3+ions.

Minerals. Mossbauer spectra of pyroxenes from two meteorites (achondrites) have been compared with those of selected terrestrial and lunar The results show the highly oxidized state of Earth's mantle, and the significance of Mossbauer spectroscopy in the study of the evolution of the planets was discussed. Data for the iron minerals found in two chrondrites have also been reported.41fFour different magnetic species have been identified in the Mossbauer spectra of two Soviet lunar regolith rock The cation distributions in three standard samples of amphibole asbestos (amosite, crocidolite, and anthophyllite) have been determined from their Mossbauer and the magnetic properties of two samples of crocidolite (blue asbestos) have been examined.424 A Mossbauer study on oriented micas with normal and reverse pleochoisms has been d e s ~ r i b e d , ~and l ~ - the ~ ~ ~origins of reverse pleochoism have been discussed. The cationic distribution418and the effects of heat treatment on biotite micas419~420 have been studied. Other iron silicates that have received attention are h ~ r n i t e ,pyroxenes,422 ~~' clin~pyroxene,~~:~ g r ~ n e r i t e and , ~ ~n~~ n t r o n i t e . ~ ~ ~ J. J. Videau, J. Porter, B. Tanguay, and S. Slevic, Cluss Techno/., 1983, 24, 171. Nishida, Y . Miyamoto, and Y. Takashima, Bull. Chem. Soc. Jpn.. 1983, 56, 439. 40' V. T. Shipatov and V. S. Minaev, Fiz. Khim. Sreklo, 1982, 8. 739. 408 D. Bahadur, D. Chakravorty, A. Prasad. and R . M . Singru. J. Mugn. Magn. Moter.. 1983,31-34, 1513. 409 L. D. Bogomolova, M. P. Glasova, 0. C. Dubsatovka. S. I . Reiman, and S. N . Spasibkina. J . Non-Cryst. Solids, 1983,58, 71. 410 V. W. A. Vieira, J. M. Knudsen, N. 0. Roy-Poulsen, and J. Campsie. Plips. Scr.. 1983. 21, 437. 411 T. V. Malysheva, A. V. Polosin, and E. P. Smirnova. Meteoritika, 1982. 109. 412 T. Zemcik and A. Cimbalnikova in ref. 1, p. 844. 413 M. J. Luys, G. L. De Roy. F. Adams, and E. F. Vansant, J. Chent. Soc.. Foraday Trans. /. 1983,79, 1451. 414 A. Moukarika, J. M. D. Coey, and N. V. Dang, Phys. Chem. Miner., 1983, 9, 269. 415 I. Shinno, Kyushu Daiguku Kyoyobu Chigaku Kenkyrc Hokoku, 1983. 3 5 . 416 I. Shinno, Prelim. Rep. Afr. Stud, (Nagoya Univ.), 1982, 6, 151. 417 G. Smith, U. Haalenius, H. Annersten, and L. Ackerman, Am. Mineral., 1983, 68. 759. 418 G. Radukic, J. Slivka. and L. Marinkov, Glos. Priv. Miiz. Beogmdu. Ser. A, 1980, 1981. 35, 13. J. S a m , T. Gonzalez-Carveno, and R. Gancedo. Phys. Chem. Mincr.. 1983. 9. 14. 4a0 V. Chandra and S. Lokanthan, J . Phys. D , 1982, 15. 2331. 481 B. J. Reddy and K. B. N. Sarma in ref. 1. p. 883. V. M. Khomenko, E. V. Pol'shin, A. N . Platanov. and N. 1. Buchinskaya. Mineml. Zh.. 1983,5, 47. 423 M. Akasaka, Phys. Chem. Miner., 1983, 9, 205. 4B4 J. Linares, J. R. Reynard, and N. Van Dang, J . Mugrt. Mugn. Muter., 1983, 31-34. 715. 425 G. Besson, A. S. Bukin, L. G. Dainyak, M . Rautureau. S. I . Tsipurskii, C. Tchoubar. and V. A. Drits, J . Appl. Crystallogr.. 1983. 16, 374. 405

4ae T.

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The transformation of ferrihydrite to haematite by ageing has been studied in aqueous media at 92 0C.426 Mossbauer studies of aluminous haematite427s428 and g ~ e t h i t have e ~ ~ been ~ described, and the degree of isomorphous substitution of iron by aluminium in goethites of bauxite and red mud has been determined.429 Mossbauer spectroscopy has been used to date Western Australian laterites (haematites and goethites) and gave good agreement with other Thermal-decompositionand Mossbauer studies on amesite have been described.431 Two dehydroxylation stages were identified culminating in the formation of spinel, sapphirine, and forsterite. Iron-rich f a y a l i t e ~and ~ ~ ~s m e t i t e ~and ~~~ montniorillite and l e ~ t o r i t have e ~ ~ received ~ attention. Two studies on kaolinites have been d e ~ c r i b e d . ~ ~ ~ ~ * ~ ~ Several chlorites and their oxidation products have been the cation populations in ferruginous uvite have been determined,438and the presence of Fe3+ in a Cuban clinoptilolite-mordenite has been A series of Bulgarian spinels has been characterized into three classes from their Mossbauer spectra.44oThe spectra of chromium-containingmagnetites or ferroan chromites were particularly complex when the Cr3+/Fe3+ratio exceded 1 : 3. Cuban chromites have also been and the complex magnetic behaviour of some titanomagnetites has been investigated.442A synthetic manganoan lipscombite has been studied by methods including Mossbauer Pentlandite samples with metal-to-sulphur ratios of 0.90-1.23 have been examined.444The poorly resolved asymmetric doublet obtained was explained by the nonequivalence of the tetrahedral and octahedral sites. Pyrrhotites in an Indian ore deposit have been studied by methods including Mossbauer spectroscopy.446 Chalcogenides. A series of room-temperature Mossbauer spectra obtained on J. H. Johnson and D. G. Lewis, Geochim. Cosmocliim. Acra, 1983, 47. 1823. S. A. Fysh and P. E. Clark, Phys. Chem. Miner., 1982, 8, 257. 428 T. V. Tkacheva and E. G. Umnova, Nov. Dannve Miner., 1982. 30, 200. 429 A. G. Suss, V. I. Kosneev. F. K. Egorov, and I. B. Firfarova. Zli. Prikl. Khim. (Lenirrgrad), 1983, 56, 1877. 430T.Hastein, U. Hauser, F. Mbesherubusa. W. Neuwirth. and H. Spaetl. 2. Geomorphol. 426

427

1983,27, 171.

K. J. D. Mackenzie and M. E. Bowden, Ttiermochim. Acra. 1983. 64. 83. 432 M. W. Schaefer, Nature (London), 1983, 303, 325. 433 M. F. Bugatti, Cfay Miner., 1983, 18, 177. 434 J. A. Helsen and B. A. Goodman, Clay Miner., 1983, 18, 117. 436 D. Bonnin, S. Muller, and G. Galos, Bull. Minernl.. 1982, 105, 467. 436 L. Jun in ref. 1, p. 877. 487 H. Kodama, G. Longworth, and M. G. Townsend, Can. Mineral., 1982, 20, 585. 43aZ.P. Razmanova, V. A. Kornetova, M. N. Shopko. and N. V. Belov. Nov. Dannw Miner., 1983, 31, 108. 43e C . Diaz and A. Picart, Rev, Cubana Fis.. 1983. 3. 47. 940 B. Genov, I. Vergilov, M. Zhelyazkova-Panaiotova, and I. Plyusnina. God. Sofii Univ.. Geo1.-Geogr. Fak. 1979-1980, 1982, 72, 199. N. Suarez, C. Diaz, and S . Garcia, Rev. Cubana Fiz., 1983,3,39. C . Radhokvishnamurty, S. D. Likhiete, E. R. Deutsch, and G. S. Murthy, Phys. Earth Planet. Inter., 1982, 30, 281. R. Vochten, P. Van Acker, and E. De Grave, Phys. Chem. Miner., 1983, 9, 263. a44 A. G. Bobkovskii, P. A. Ioffe, and L. Sh. Tsemekhman, Geohkimiya, 1983, 1212. 445 V. P. Gupta, A. K. Singh, K. Chandra, and S. K. Jaireth in ref. 1, p. 863. 431


32 I

samples of natural pyrite has been used to determine a value for the LambMossbauer factor of 0.545.446The effects of a cobalt impurity on the crystallographic and magnetic transitions of FeS have been investigated.447 The Mossbauer measurements showed that the superexchange interactions are unaffected by the cobalt impurity, while the a-transition temperature decreased considerably. Two independent low-temperature Mossbauer studies on 57Fe-dopeda-MnS have been d e s ~ r i b e d .Iron ~ ~ ~incorporated ,~~~ into CuTnS, has been found in the copper and indium sites in a concentration ratio of 3 : 1.450$4s1 Mossbauer measurements of single-crystal and quasi-single-crystal samples of AFeS, (A = K, Rb, or Cs) show no evidence for any variation of the hyperfme field with applied fields up to 10 T.4s2This is consistent with a quasi-one-dimensional system with relatively high anisotropy. Other workers have discovered a sudden first-order magnetic and structural phase transition in CsFeS, at 77 K.4s:s The 4.2 K Mossbauer spectrum is consistent with strong covalent Fe"'-S bonds. Amorphous RbFeS, has been prepared and its Mossbauer spectra have been The room-temperature spectrum is described as a broad singlet made up of several resonances arising from a local distribution of the tetrahedral environment of the Fe3+ ions. Mossbauer studies of Fe,NbS, ( x = 0.25, 0.33, or 0.5) have been carried out at 4.2-715 K.4s5The iron existed as Fe2+ at all temperatures and reversible phase transition was identified at 600 K for x = 0.25 and at 490 K for x = 0.5. Electron exchange in amorphous GeS films doped with 57Fe4sB and the ironcation distribution in Fe,ZrSe, ( x -= 0.25)457have shown that the Fe3+ ions occupy the metal layers that are without vacancies.458The quadrupole splitting, 0.45 mm s-* at 84 K, decreases linearly with increasing temperature. Magneticsusceptibility and Mossbauer-effect measurements on Fel + xNbs-xSel, (0.25 Q x < 0.4) are dominated by Fe-Nb disorder on the zigzag octahedral chains.4sg

Applications of 57FeMiissbauer Spectroscopy.-Corrosion Studies and Steel. The products of the atmospheric corrosion of steel panels have been investigated.460 E. Fritzch and C. Pietzsch, Phys. Status. Solidi A, 1983, 79,KI 13. K. S. Baek, J . Y . Park, and H. N. Ok, Sue Mulli, 1983, 23, 88. 448 A. Tomas, L. Brossard, J. L. Dormann. and M. Guittard, J. Magn. Mugn. Mntw . 1983 31-34,755. R. J. Pollard, V. H. McCann, and J. B. Ward, J . Phys. C, 1983, 16,345. 450 J. J. M. Binsma, L. J. Giling, and J. Bloem, Stud. Inorg. Chem., 1983,3. 3 3 1 J. J. M. Binsma, J. Phys. Chem. Solids, 1983, 44,237. D. M. Cooper, D. P. E. Dickson, P. H. Domingues, G. P. Gupta, C. E. Johnson. M F . Thomas, C. A. Taft, and P. J. Walker, J. Magn. Magn. Muter., 1983. 36. 171, *j3 M. Nishi, Y . Ito, and A. Ito, J . Phys. SOC. Jpn., 1983,52,3602. G. A. Petrakovskii, K. A. Sablina, and V. Pikonnikov, Phys. Status Solidi A, 1983. 7S, K165. q55 M. D. Sundararajam, A. Narayanasary, T. Nagarajan, C. Sunandana. G. V. S. Rao. D. Niarchos, and G. K. Shenoy, J . Phys. Chem. Solids, 1983,44,773. ls6 F. S. Nasredinov, P. P. Seregin, A. A. Andreev, A. V. Ermolaev, H. Stoetzel, and A . Kollwitz, Fiz. Tverd. Telu, 1983,25, 1528. p57 M. A. Buhannic, A. Ahouandjinou, M. Danot, and J. Rouxel, J . Solid State Chem. 1983. 49,77. 458 C.S. Lee, Pusan Susan Taehak Yongu Pogo, Chayon Kwahak, 1982, 22, 37. 458 R. J. Cava, F. J. Di Salvo, M. Eibshutz, and J. V. Waszczak, Phys. Rev. B, 1983, 27, 7412. H. Leidheiser, jun. and S. Music, Corros. Sci., 1982,22, 1089. 4p6 147

322


y-FeOOH was found to be the initial product, which transformed into a mixture of a-FeOOH and y-Fe,O,, while a panel exposed for ca. 25 years was found to be covered with y-Fe,03. Similar results have been obtained by workers in Latvia4s1 and India.462The latter group has also shown that Mossbauer spectroscopy can detect the onset of corrosion underneath painted Mossbauer spectroscopy has also been used to identify the corrosion products found on an ionexchange resin from a water-softening ion-exchange plant.464Examples of the ise of Mossbauer spectroscopy in the analysis of steels have been And the Mossbauer method has been found to be more reliable than XRF and magnetic measurements for the determination of the residual austentite in highspeed A molecular-orbital calculation of the local electronic state of carbon in steel martensite has given good agreement with Mossbauer data,36i and the effects of carbon and nitrogen on the Mossbauer spectra of some austentitic chrome steels have been An investigation of the effects of annealing on tempered tool steel has described the changes in the paramagnetic and ferromagnetic phases as a function of the annealing parameter.46Q Iron-containing Cutalysts. The formation of iron carbides on Fe/AI,O, and Fe(Cr)/Al,O, Fischer-Tropsch synthesis catalysts has been Carbides with compositions in the range Fe,C-Fe,.,C were identified, and the variation of rhe magnetic-hyperfme field at the iron nuclei with the number of carbon nearest neighbours was described. The bulk composition of a reduced 10% Fe/Al,O, Fischer-Tropsch catalyst has been studied by in situ Mossbauer As the reaction progressed the degree of carburization and the proportions of the carbides formed were followed. Other workers have studied the Mossbauer spectra of Fischer-Tropsch iron catalysts containing mangane~e~ and ~ , copper and magnesium.473Other Fischer-Tropsch catalysts have been prepared by reduction of Fe2+-exchangedY zeolite and (NH4)4Fe(CN)s.474 Mossbauer results have shown that the iron is in particles of > 10 nm diameter and therefore lies outside the zeolite cages. The Mossbauer spectra of sputtered Fe-N phases have been The films, which are active as FischerTropsch catalysts, were shown to be mixed phases, with y'-Fe4N the only pure phase obtained. l';

I. Kina, R. Avotina, 0. Kukurs. and Z. Konstants, Latv. P S R Zinat. Akad. Vestis, Kim. Ser., 1983, 281.

R. K. Nigam, U. S. Mehrotra, S. Varma, and S. N. Pandey in ref. 1, p. 299. JR3R.K. Nigam, S. Varma, G . P. Sharma, K. Mukundam, G . K . Sinphania. and S. N. Pandey, Fundam. Appl. Electrochem., Proc. Symp., 1982,243. T. Peev and A. Vertes, Radiochem. Radioanal. Left., 1983, 57, 3 1 I . J6.i F. I. Wei, Chi Shi Yu Hsun Lien, 1982, 7 , 60. IR6 A. Ikhlef, T. Vieira, R. Vilar, and G. Cizeron. Mem. Etud. Sci. Rev. Metall.. 1983, 80. 377. 4A7 F. E. Fujita, S. Nasn, and A. Adachi, J . Phys. Colloq., 1982, C-4, 103. 468 Ts. Kamenova and R. Banov, Eulg. J . Phys., 1982, 9, 138. 469 S. Nagy, K. Ramanyi, A. Vertes, E. Kuzmann, and Z. Hegedus, Acta Metall.. 1983. 31. 529. 470 M. Pijolat, G . Le Caer, V. Perrichon, and P. Bussiere in ref. 1, p. 431. '71 D. Bianchi, S. Borcar, F. Teule-gay, and C. 0. Bennett, J . Catal., 1983, 82, 442. 472 W. Podetta, W. Gunsser, and M. Ralek, Chem.-hg.-Tech., 1983, 55, 631. 473 P. S. M. Tripathi, B. K. Sharma, V. A. Krisnamurthy, and S. K. Date in ref. 1, p. 974. 174 J. Scherzer, J . Catal., 1983, 80, 465. l i 5 L. N. Mulay, S. V. Krishnaswamy, C. Lo, K.R.P.M. Rao, and R. Messier in ref. 1, p. 460.

Mdssbauer Spectroscopy

323

The effectsof preparation method of monomeric FePc catalysts on Mossbauer parameters and transformations have been investigated.476The form of FePc was found to influence its reactivity and stability against oxidative destruction. Mossbauer spectra of mixed Cu,Fepoly(Pc) catalysts have shown that the presence of copper in the poly(Pc) core influences the distribution of the iron species and their ability to undergo oxidation to iron oxides during cumene oxidation.477The Mossbauer spectra of FePc catalyst used in the electrochemical reduction of oxygen have been rep~rted."~ / n situ Mossbauer spectroscopy has been used to study the reduction behaviour of FeRh/SiO, The spectra showed that co-clustering of iron and rhodium occurred and the increased reducibility of iron in the presence of rhodium. Two papers have been published on the use of Mossbauer spectroscopy as a tool to study the reduction of an iron ammonia synthesis ~atalyst.~ 809481

Coal and Related Topics. Mossbauer parameters for 15 Indian coals482and one African c o a F have been presented. The decomposition of coal and mineral pyrites of various particle sizes in hydrogen and oxygen flows has been studied using in situ Mossbauer In hydrogen the pyrite converted to pyrrhotites, while the products formed in oxygen depended on the reaction temperature. A comparison of microwave and radiofrequency methods for the low-temperature ashing of coal has been made using the Mossbauer spectra of A value of 0.55 was obtained for the recoil-free the Fe-S fraction ratiof(su1phate) :f(pyrite). The effects of additives on the stoicheiometry of iron sulphides formed during coal liquefaction have been described,48oand the effects of acid treatment on coal subject to low-temperature carbonization have been in~estigated.~~' The iron content of minerals taken from the North Sea oil fields has been Iron was found in clay minerals, pyrite, haematite, and carbonates, and the results suggest that the presence of ankerite [(Fe,Mg,Ca)CO,] is related to the maturity of the source rock. Ores, Slags, Soils, and Sediments. The nature of the iron oxides formed in the autoclave oxidative-leaching pyrrhotite concentrates has been and a detailed Mossbauer analysis of the phase changes of roasted iron-containing M. Hronec and J. Sitek, React. Kinet. Catal. Lett., 1982, 21, 351. M. Hronec, G. Kiss, and J. Sitek, J . Chem. SOC.,Faraday Trans. I , 1983, 79. 1091. 478 J. V. Johansson, Diss. Abstr. Znt. C , 1983, 44, 620. 47s J. W. Niemantsverdriet, A. M. Van der Kraan, J. J. Loef, and W. N. Delgass. J. P h w . Chem., 1983, 87, 1292. 4R0 A. Pattek-Janczyk and A. 2. Hrynkiewicz, Appl. Catal., 1983, 6, 27. 4u1 A. Pattek-Janczyk, A. Z. Hrynkiewicz, J. Kraczka. and D. Kulgawczuk. Appl. Card.. 476

477

1983, 6, 35.

C. Bhan, D. Raj, and N. Nath in ref. 1, p. 278. 483 V. Mudago, H. Pollak, and A. Blondin in ref. 1, p. 325. 481 P. A. Montano and P. P. Vaishnava in ref. 1, p. 281. 485 J. L. Guilianelli and D. L. Williamson, Fuel, 1982, 61, 1267. 486 A. Bommannavar and P. A. Montano, Fuel, 1982,61. 1288. 487 M. Valentine and P. G. Debrunner in ref. 1, p. 316. 488 S. Moerup and H. Lindgreen in ref. 1, p. 290. 489 A. G. Bobkovskii and Ya. M. Shneerson, Kompleksn. Ispol'z Miner. Syr'ya, 1983, 5, 3. 482

324


minerals has been published.400A Mossbauer study of acid-leached bauxite has been made at 4.2 and 300 K,401and the iron minerals present before and after HCl leaching were identified. A quantitative phase analysis of red muds containing iron hydrogarnets has been made using Mossbauer s p e c t r o ~ c o p yThe .~~~ distribution of iron between the phases present in two steelmaking slags has been i n v e ~ t i g a t e d . ~ ~ ~ ~ ~ ~ ~ A study of two Indian clay soils has found a correlation between the Mossbauer parameters, weathering, and natural vegetation found in the soils.495Another study, of some Indian alluvial deposits, has also revealed a connection between the Mossbauer spectra and the weathering and mode of deposition of the A method of absolute dating of sediments using Mossbauer spectroscopy has been Mossbauer spectroscopy has also been used to study the formation of viviantite in sediments from Lago Maggiore (Italy)408 and to investigate the form of iron in sediment from Lake Ontario (Canada).400 Other Applications. Three studies on cements have been described. A study of the hydration of blast-furnace slag cement and Portland cement has revealed a relationship between the fraction of Fe3+in tetrahedral sites and the compressive strength of the hardened cement.500The states of iron in sulphate-resisting Portland cement and Portland slag cernent5O1and the Mossbauer spectra of grey high-alumina cement502have been examined. A Mossbauer study of ancient pottery from the Greek colony of Pithekoussai has differentiated between local and Corinthian pottery and specified the firing conditions for the local pottery.503The Mossbauer spectra of ferro-gallic inks from the twelfth and fifteenth centuries have shown the presence of large amounts of ferrous ~ x a l a t e Superparamagnetic .~~~ or amorphous phases containing Fe3' were also observed and related to the black colour of the ink. The influence of meteorological conditions on the iron concentration in the atmosphere has been The concentration of iron in the atmosphere (at Saarbriicken in West Germany) was found to be three times higher on J. Zheng, M. Niu, G. Dai, S. Liu, H. Zhang, Q. Zhang, K. Chen. and X. Yuan, Nucl. Tech., 1982, 7. 491 S. A. Fysh and P. E. Clark, Hydrometallurgy, 1983,10,285. 402 K. Jonas, J. Zoldi, A. Vertes, and 1. Nagy-Czako, Trav. Corn. Znt. Etude Bauxites. Alumine Alum., 1982 17,223. 4Q3 C. Gohy, A. Gerard, and F. Grandjean, Muter. Res. Bull., 1983, 18, 275. *04 E. Ramous, G. Principi, M. Magini, A. Tiziani, and L. Giordano in ref. 1, p. 274. 4Q5 U. K. Makeshwari, J. S. Samra, A. K. Singh, and K. Chandra in ref. 1, p. 866. 4Q6 S. M. Kanetkar, S. M. Bendre, S. N. Rajguru, and Arunkumar in ref. 1, p. 880. 497 H. Spaeth and F. Mbesherubasa, Z. Geomorphol., Suppl., 1982, 203. 4g8 G. P. Nembrini, J. A. Capobianco, M. Viel, and A. F. Williams, Geochim. Cosmochim. Actu, 1983, 47, 1459. P. G. Manning, K. R. Lum, and T. Birchall, Can. Mineral., 1983, 21, 121. -ioo N. A. Gissa, M. Y. Hassan, H. A. Sallam, S. H. Salah, and S. A. Abo El-Enein in ref. 1. 4g0

p. 293.

K. S. Harchand, R. Kumar, Vishwamittar, and K. Chandra in ref. 1. p. 296. C. L. Honeybourne in ref. 1, p. 319. jo3 A. Deriu in ref. 1, p. 838. J. Danon, M. Darbour, F. Flieder, N. Genand-Riondet, P. Imbert. G. Jehanno. Y. Roussel in ref. 1, p. 841. jo5B. Kopcewicz, M. Kopcewicz, and V. Gonser in ref. 1, p. 287.


325

rainless days than on days with heavy rainfall. No iron sulphur compounds were detected in the Mossbauer spectra. The use of iron compounds as agents for smoke reduction in PVC combustion has been investigated using coulometry and Mossbauer spectroscopy.5 Tin-119

General Topics.-llOSn has been used in a coincidence Mossbauer experiment to study the time distribution of resonantly filtered y-radiation."' Resonance detectorswere used to measure very small chemical-isomer shifts in tin-containing materials.04An inversion of the composite line resulting from experiments with a fixed sample placed in front of a resonance detector was observed at high effective thickness. The asymmetry parameter of the composite line was said to be a sensitive linear function of the shift between the sample and detector lines. An isomer shift of +0.028 k 0.0024 mm s-l of CaSnO, relative to the unresolved SnO, doublet was claimed following measurements by temperatureshift compensation. A method of analysing magnetically split llOSnspectra using a hyperfine-field distribution function has been tested on data for Zn,Sn,.,FG.~-,O~spinels.lo6 Tin-119 data were included in a review of implanted sources. A method of tin analysis using a source of y-resonance quanta has been described.m* A large number of papers published during the review year were concerned with the use of the Mossbauer effect to study materials doped with tin or with isotopes that produce llOSnas a daughter nucleus. Radioactive llOSb has been implanted into SnO,, CaSnO,, SnCI,, and SnI, and into the corroded surface of P-Sn by means of an isotope separator. The nature of the impurity-atom bonding was then studied by emission Mossbauer spectroscopy using CaSnO, as absorber at 80 KSo0 The emission spectra from "OSb adsorbed on a-Fe203have also been studied.610The spectra obtained from SbV solutions dispersed with haematite have isomer shifts in the Sn"' region of the emission spectra. The spectra were, however, very broad, and this was attributed to magnetic interactions on the impurity nuclei from the magnetically ordered haematite lattice. Mossbauer studies on ll%n impurities dissolved in the superionic conductor Ag,Se showedh1' that there was a decrease in resonance absorption intensity 56K below the normal superionic transition temperature at 406 K. This effect was independent of the impurity concentration in the range 0.5-2 atom % and was shown to be reversible with temperature. The mechanism suggested to explain the effect T. V. Hoang and P. Bussiere in ref. 1, p. 303. E. Vapirev, P. Kamenov, D. Balabanski, S. Ormandzhiev, and K. Yanakiev, J . Phys., 1983,44,657. A. V. Dolenko, L. A. Zemlerub, V. P. Korneev, L. A. Korytko, and E. M. Raikhman. Otkrytiya Izobret, Prom. Obraztsy, Touarnye Znaki, 1982,34, 302. 5oQ H. Muramatsu, T. Miura, N. Nakahara, and M. Fujicka, Radiochem. Radoanal. Lett., 1983,55, 169. 610 T. Okada, H. Sekizawa, F. Ambe, and S. Ambe in ref. 1, p. 450. 611 M. Pasternak, N. Benczer-Koller, Y. Yang, R. Ruel, and R. H. Herber, Phys. Rev. B. 1983,27, 2055. 608

326


involved a local order-disorder phase transition brought about by the fast hopping of Ag' ions surrounding the Sn impurity atom. The local disorder induced by the impurity atom was presumed to co-exist with the bulk-ordered phase at temperatures well below 406 K. The effects of both ll9Sn and 57Fe impurities on As,Se, glasses were determined,512and it was found that Sn impurities have no effect on the conductivity of the glasses or on their activation energy. The Mossbauer effect has also been used in a study51Yof photostructural transformations in Sn-doped arsenic selenide glassy semiconductors. The data show that consecutive annealing at 190 "C and irradiation with polychromatic light induced the formation of Sn" species that disappear again during thermal treatment. The mechanism suggested to explain this effect involves light-induced polymerization destruction processes that lead to a breakdown of the Sn-Se bonds. The Mossbauer spectra of the initial samples provided evidence for the presence of Sn'" in interstitial positions in which they would be co-ordinated to six Se atoms, three from the layer above and three from the layer below the impurity. Tin was included514with a number of elements in a Mossbauer study of the local H distribution around substitutional impurities in P-PdH,. A model for the description of the resonance line positions and intensities was derived from the data. The Sn impurity in P-PdH, repels hydrogen atoms, and the energy required to bring the first H atom into the nearest-neighbour environment of Sn was calculated as at least 150 meV. For higher numbers of nearest-neighbour H atoms the repulsive interaction of H becomes weaker. The effects of impurities in tin508 and have been studied by the ll9Sn Mossbauer effect. An investigation on ll9Sn implanted in Si provided information on thermal and radiation annealing515 and showed that high-intensity sub-threshold-energy electron irradiation leads to disintegration of the Si-Sn solid solution in a similar manner to the thermal disintegration of the material. The spectrum of ll9Snin Si is a singlet with a shift that is independent of the doping concentration Isomer-shift and Debye-temperature data for and is due to substitutional tin.516-517 substitutional l19Sn impurities in the face-centred cubic metals Al, Ag, Au, Cu, Pb, Pd, Pt, and Rh have been obtained519by Mossbauer emission measurements after ion implantation of or l19Sb isotopes into single crystals or high-purity foils of the metals. Isomer-shift data are correlated with the electronic properties of the host metals including the Fermi-level free-electron density and the cellboundary electron density, while the Debye temperatures are interpreted in terms of the Einstein-Debye and Mannheim models for impurity-lattice vibrations.

j12

514

617

G18

V. L. Aver'yanov, V. M. Lyubin, F. S. Nasredinov, 0. Prikhod'ko, and P. P. Seregin, Proc. Znt. Conf. 'Amorphous Semicond.', 1982, 160. S . S. Lantratova, V. Lyubin, and P. P. Seregin, Fiz. Tverd. Tela, 1983, 25, 2494. F. E. Wagner, M. Karger, F. Proebst, and B. Schuettler, NATO Conf. Ser., [Ser.] 6, 1983. 6 . A. M. Oak, V. S. Vavilov, M. Chukichev, and V. S. Shpinel, Radiat. Eff.Lett. Sect., 1983, 86, 1. G. J. Kemerink, H. De Waard, L. Niesen, and D . 0. Boerma, Hyperfine Interact., 1983, 14, 37. G. J. Kemerink, H. De Waard, L. Niesen, and D. 0. Boerma in ref. 1, p. 412. H. D e Waard and G. Kemerink, Physica B, 1983, 116, 210. H. Andreasen, S. Damgaard, J. W. Petersen, and G. Weyer, J. Phys. F, 1983,13.2077.


327

The ratio of impurity-host to host-host force constants has also been for lleSn in Cu, Pd, and Au. Emission studies on lleSn after low-temperature implantation of lleSb in Pt trapping of vacancy-type defects after annealing at 250-450 K. Two distinct steps due to different atomic-migration mechanismswere observed. At higher annealing temperaturesevidence was found for detrapping of defects at 550 K and of additional trapping at 850-1500 K. The probabilities of obtaining recoil-less resonant absorption from lleSn in host lattices of C, Pt, and Nb were for 80-400 K and found to be in good agreement with the experimental data. of a conversion-electron study of lleSn nuclei in Ni metal are described in Section 7 of this chapter. The temperature dependence of the hyperfine field and chemical-isomer shift of 1 ll%n face-centred-cubic and hexagonal Co was measured in the temperature range 83-754 K.524The hyperfine fields in the two modifications of Co at 83 K were 18.5 and 50.8 kOe, respectively; the corresponding values at 673 K were 3 and 9.5 kOe. The dependence of the field on temperature in both modifications is anomalous and is attributed to formation of localized moments at the Sn atoms. Four papers published during the year dealt with results from studies on llgSn-doped 111-V compound semiconductors. Site-selective implantation techniques were used to incorporate amphoteric Sn impurities on the two inequivalent lattice sites in 111-V compounds. The shift data for the products showedsa5that the electronic configuration of the Sn atoms depended upon dehybridization of covalent bonds with increasing bond length and of the fractional ionicity of the host bonding. Below a fractional ionicity of 0.3, the host electrons have no effect on the Sn-donor and Sn-acceptor sites, and the tin atoms on both sites retain a configuration similar to that which would be found for a homopolar compound with equivalent bond length. For hosts with higher fractional ionicities, positive and negative charges accumulate on the Sn-donor and Sn-acceptor sites, respectively. Debye temperatures obtained from the Mossbauer emission spectra have been compared with values calculated using the mass-defect model with different Debye temperatures for the donor and acceptor ~ i t e ~Lattice . ~ ~force ~ tconstants ~ ~ ~ calculated from the data were found to be bigger for Sn on (V) sites in Ga-containing compounds but bigger on (111) sites for In-containing semiconductors. The host-lattice semiconductors studied in these experiments were Gap, GaAs, GaSb, InP, InAs, and InSb. Mossbauer shift data for lleSn impurities in 111-V compounds have been interpreteds28,s29 in terms of the bond structure of the host lattice and the electronic structure of R. K. Puri and L. R. Gupta in ref. I , p. 625. L. Niesen and H. De Waard, Nucl. Instrum. Methods, 1983, 209-210, 441. s22 R. B. Yadav, Solid State Commun., 1983, 47, 267. 623 K. G. Prasad in ref. 1, p. 420. B24 I. B. Kim, Taehan Kumsok Hakhoe Chi, 1982, 20, 975. s2G G. Weyer, J. W. Petersen, and S. Damgaard, Physica B C (Amsterdam), 1983,116,470. sa6 G. Weyer, J. W. Petersen, and S. Damgaard, Physica B C (Amsterdam), 1983, 147, 620

521

+

1, 523,

+

0. H. Nielsen, F. K. Larsen, S. Damgaard, J. W. Petersen, and G. Weyer. Z . Phys. B, Condens. Matter, 1983, 52, 99. G28 E. Antoncik and B. L. Gu, Physica B C, 1983,116,127. 520 E. Antoncik and B. L. Gu, Physica B -t- C , 1983, 117-118, 69. 527

+

328


the Sn implants. A Green-function perturbation based on the tight-binding method was used to determine the electronic configurations of ionized donor and acceptor Sn implants and to calculate their chemical-isomer shifts. It is suggested that for n acceptors the impurity consists of a small cluster of neutral Sn atoms rather an discrete negative Sn ions but that discrete positive Sn ions are the dominant species at donor sites. The hyperfine interactions at Sn impurity sites in the ferromagnetic GdAl, intermetallic and in the Heusler alloys Co,MnZ (Z = Al, Ga, Si, Ge, or Sn)531have been studied. In the intermetallic compound the Sn atoms are localized in the A1 sites, and at 6 K the hyperfine field at Sn is 29.3 T. As the temperature rises the hyperfine field decreases more rapidly than the matrix magnetization, and evidence is found for strong radial dependence of the partial contributions to the field. The hyperfine fields found at Sn atoms in the Heusler +6.2, and f 1 0 2 kOe for alloys C O ~ M ~ Z ~were . ~ +40.5, ~ S ~+35.3, ~ . ~ -15.6, ~ alloys with Z = Al, Ga, Si, Ge, or Sn, respectively. The hyperfine fields at l19Sn in the Heusler alloys Rh,MnGe and Ni,MnGa have also been measured.632A comparison of y-resonance results for Sn impurity atoms at the 0.5 atom % level in Pd,,Ni,, and Ni,,Rh,, alloys has been The temperature dependenceof the spectra showed that the oscillating behaviour of the shift was sensitive to the alloy composition and probably also to the distribution of magnetic moments. In the range 361-371 K the chemical-isomer shifts for the NislRhlo phase show abrupt variations with an amplitude of about 15 x mm s-l. The value of lleSn y-resonance spectroscopy in studies of a number of tincontaining systems has been discussed. The uses of the technique in investigations of the bonding in and phase transformations of tin chalcogenide IV-VI semiconductors18and were reviewed. A Green-function procedure based on a modified tight-binding method was used628to evaluate the electronic configurations and isomer-shift values for Sn present in AN-B8-Nsemiconducting materials either as one of the components or as an impurity. The influence of non-cubic Te substrates on thin films of cubic Sn has been studied using lleSn Mossbauer The spectra for Sn films on Te substrates of thickness 860 A, showed a quadrupole doublet. The s-electron density at the Sn sites of the deposit appears to increase with Te thickness, and the influence of non-cubic Te on the deposit of cubic Sn disappears for sufficiently high deposit thickness. The phase composition of the tin component of a number of solders and coatings in printed circuit boards subjected to ageing in air at 70 "C for one year was also studied using the ll9Sn effect.636The results of studies on the y-resonance

th"

N. N. Delyagin, V. I. Nesterov, and S. I. Reiman, Zh. Eksp. Teor. Fiz., 1983, 84, 1580. R. A. Dunlap and D. F. Jones, Phys. Rev. B, 1982, 11, 6013. 5srG. M. Julian, J. W. Blue, G. K. Shenoy, S. Tha, H. M. Seyoum, M. De Marco, and M. El Fazani in ref. 1, p. 491. 63s N. N. Delyagin, V. I. Nesterov, and S. I. Semenov, Phys. Status Solidi 8, 1983, 1, K27. T. E. Cranshaw in ref. 4, p. 217. 6ss R. G. Mendiratta, J. S. Baijal, K. Aggarwall, and G. L. Sawhney in ref. 1, p. 466. V. V. Igrushin, A. M. Kapustina, V. G. Kinrichenko. D. I. Novikova, and V. V. Chekin. Deposited Doc., 1982, VINITI 3158-82. 5s0

631

Mijssbauer Spectroscopy

329

spectra of solutions of different Sn-containing compounds in nematic and smectic glasses have been published in a Two papers described the results of studies on Pt-Sn-Al,03 catalysts. One was concerned with the problems of fitting the complex spectra obtained, while the other dealt with the changes in the nature of the tin species present after calcination, reduction, or reforming reactions with the catalyst.s338 An example of the use of llsSn Mossbauer spectroscopy to study the fate of tin-containing moieties in biological systems is provided by the of the distribution of Sn injected as SnCl, into mice. The nature of the Sn in liver and bone samples of mice injected with 24-36 mg of Sn over 30 days was determined by the Mossbauer effect in samples 87 mg cm-, in thickness. The ll9Sn Mossbauer spectra of various Nb-Sn layers prepared by different methods have been reporteds40in studies of superconducting layer materials. Three different phases, Nb3Sn, Nb,Sn,, and NbSn,, were identified in some layers, but pure Nb3Sn layers were obtained by heating the samples to 1253 K for 11 minutes or to 1203 K for 22 minutes. The presence of two Fe sites and one Sn site in the solid solutions (Fel.22Sb)1-,(Fel.68Sn), (0 < x < 0.5) has been inferred from the room-temperature y-resonance data for the alloys.s41Mossbauer data obtained on P-MnSnS4,on the phases RIn3-,Sn (R = Ce or Pr)s43and on the Heusler alloys C U ~ Mand ~ Rh,MnSnS3, S ~ ~ ~ have ~ also been discussed. Ti@) Compounds.-The lattice dynamics of tetragonal SnO have been studied in the temperature range 78-300 K by variable-temperature lleSn Mossbauer spectroscopy.s4sThe lattice temperature calculated from the temperature dependence of the recoil-free fraction was 229 K, but that calculated from the temperature dependence of the isomer shift is lower (193 K). The values reported for the shifts at 78 and 300 K are 2.697 and 2.641 mm s-l, respectively; therecoil-free fraction at 295 K is said to be 0.35 5 0.02. The quadrupole-coupling parameter in SnO was found to be only weakly temperature dependent in the range studied, and no evidence was found for a vibrational anisotropy parallel with and perpendicular to the four-fold axis through the Sn atom. The tetragonal phase of PbO is isostructural with SnO, and the tetragonal-to-orthorhombic phase transition in lead oxide was studied by lloSn y-resonance in samples of PbO containing Sn. Quadrupole coupling was found only in the orthorhombic phase, and the transition was shown to be an orderdisorder In an attempt to understand the electrical properties of semiconducting glasses containing tin the D. G. Todoroff, Diss. Abstr. Int. B, 1983,44, 1170. Y. F. Hsai and Y. X. Li in ref. 1, p. 438. J. Akashi, M. Chiba, and H. Sano, Bunseki Kagaku, 1983,32,E123. s40 B. Glowacki and J. Chojoan, Phys. Status Solidi A, 1983,80, K93. M1 E. A. Vasilev and V. A. Virchanko, Phys. Status Solidi A, 1983,80,K41. Ma J. M.Williams and I. J. May in ref. 1, p. 500. P. N. Tandon, L. C. Gupta, R. G. Pillay, E. V. Sampathumaran, and H. G. Devare in ref. 1, p. 608 6u R. A. Dunlap, S. P. Ritcey, G. Stroink, and D. Hutt, Solid State Commun., 1983,45, 67. Ms R. H. Herber, Phys. Rev. B, 1983,27, 4013. u6V. A. Izvozchikov, V. S. Zagrai, and V. V. Laptev, Izv. Akad. Nauk SSSR, Neorg. Muter., 1983, 19, 501. b87

330


ratios of the element in its I1 + and IV + oxidation states have been determined by Mossbauer The method used to obtain an accurate ratio from the recoil-free fraction data is described, and results for a series of barium aluminoborate glasses are given. The &values of the Sn" and Sn'" sites have different temperature dependences; the results were obtained by using both the Einstein and Debye modes.548A similar method was used to determine the Sn" : SnIV ratio in A1203-B203-Si02-Sn02 and A1203-B203-P205-Sn02 systems with a claimed accuracy of about 5%.549 Both 57Feand l19Sn spectra have been obtained for the interchelation compound Fe&Sn+NbS,.The lloSn data ( 6 = 3.65 mm s-l) are consistent with the presence of Sn" in the comMossbauer data on the solid solutions Pb,_,Sn,Se have been interpreted in terms of two-electron exchange between neutral and ionized centres in the solids.561Solid samples of SnTe of two different compositions, the eutectic composition and Sn,,Te,,, were obtained by ultrafast cooling with different initial temperatures to start the cooling. The dependence of the Mossbauer spectrum on the initial temperature from which the melt is cooled suggeststhat the fast-cooled solids retain the liquid-state Samples of Pb,_,Sn,Te ( x = 0.21,0.25,0.55, or 0.75) with thickness of less than 15 pm were studied by the temperature-dependent Mossbauer effect.The Sn atoms are in cubic-lattice sites, and there is no evidence for transitions to low-temperature orthorhombic or high-temperature cubic phases such as have been reported for SnTe itself over this temperature range. The lattice temperatures calculated from area data for the phases are independent of x and are similar to that of SnTe. Radiation damage produced by 2 MeV proton irradiation to a total flux of about 1017 cm-2 at liquid-nitrogen temperature does not have any effect on the Mossbauer parameters, possibly because the major damage is annealed at temperatures below 150 K.553 A number of new compounds of the type Sn(R1CHOCHCOCHCOR2)and Sn(R1COCH2COCHCOR2)2 (R1 = R2 = Ph or Me; R1 = Ph, R2 = Me) have been synthesized and The Mossbauer spectra for the first series of new compounds are quadrupole-split doublets with shifts and splittings in the ranges 3.17-3.23 mm s-l and 1.97-1.99 mm s-l, respectively. These have been interpreted in terms of trigonal-pyramidal tin environments similar to those found in many tin@) carboxylates. A four-co-ordinated tin environment was, however, suggested for compounds 3f the type Sn(R1COCH2COCHCOR2)2. Both the absorption and emission spectra of frozen solutions of SnCl, in a

J. M. Williams, S. D. Forder, and J. 0. Isard, Struct. Non-Cryst. Mater., Prbc. Int. Conf., 2nd, 1982, 1983, 221. 548 J. M. Williams and S. D. Forder in ref. 1, p. 341. 549 A. I. Ovchinnikov and A. D. Mokrushin, Deposited Doc., 1982, VINITI 4476-82. 55O M. Katada, K. Sato, Y. Hirasawa, and H. Sano, Radiochem. Radioanal. Lett., 1982,54293. 351 F. S. Nasredinov, L. V. Prokorieva, S. V. Zarubo. A. N. Kurmantaev. and P. P. Seregin, Pis'ma Zh. Eksp. Teor. Fiz., 1983, 38, 20. G. Quintana, H. Sirkin, and B. Arcondo in ref. I , p. 536. .m R. H. Herber and R. Kalish, Solid State Chent.. 1983, 47, 284. .x,4B. P. Bachlas, H. Sharma, J. C. Maire, and J. J. Zuckerman. ltiorg. Chin?.Actn. 1983. 71. 647

227.


33 1

series of donor solvents were reported555as part of a study of the after-effects of the converted isomeric transitions in ll9Sn. The higher shift values for the frozen solutions compared to those for solid adducts of SnCI, with the donor solvent molecules were said to be compatible with the presence of discrete SnCl, molecules in the frozen solutions. A yield of about 30% of the aliovalent Sn'" species was observed in the emission spectra of the frozen solutions. This compares with yields of 48 % and zero for ll9Sn in the solid adducts SnCl,(dmso), and SnCl,(py),, respectively. A mechanism was proposed for the stabilization of the aliovalent species based on the capture of Auger electrons by the organic medium. In the dmso adduct, for example, it was suggested that the charged hot-atoms Sn"+, created by the Auger process, relaxed rapidly to Sn4+ by recapturing electrons from their surroundings. Further electron capture by Sn4+ to give the original Sn2+valence state could not then take place because the Auger electrons would be trapped in the glassy matrix. Methyl radicals generated by dissociative electron capture by the ligands could, however, result in the reduction of some of the Sn4+to Sn2+.Such a mechanism would explain the lower yield of aliovalent species for "*Sn decay in SnCl,(dmso), compared to that in SnCl,(dpso), because the phenyl groups involved in the dpso ligand are stable in radiolysis. The lleSn emission spectra for SnCI, adducts with pyridine N-oxide and picoline N-oxide can be explained in the same way. In these compounds methyl radicals would be formed, and the increasing closeness to the tin atom for radicals formed in the a-, p-, and y-positions is paralleled by a decreasing yield of SntV.The emission spectra of SnBr,(dmso), and SnBr4(dpso), show the presence of reduced aliovalent species.555The authors suggest that the formation of methyl radicals by dissociative electron capture in the y-irradiated crystalline solids is responsible for the reduction of some of the tetravalent Sn to Sn". They also reported that it seemed that the autoradiolysis by Auger electrons could only be effective with the closest ligands in the crystalline solids because reduction by methyl radicals is not observed in solutions said to contain discrete tincontaining molecules rather than adducts. Two new compounds Cs,SnBr, and Cs4SnC1, have been prepared,666and the CsBr-SnBr, phase diagram has been described. Phases of the type Cs,Sn,-,Pb,Br,-,CI, (n = 0 - 1 , .Y = 0 - 6 ) have been examined by X-ray diffraction, electrical conductivity, Mossbauer spectroscopy, and optical reflectance. When first prepared from the melt or from solution, Cs,SnBr, is black with a metallic lustre, but it rapidly turns first yellow then white in the presence of moist air. This process can be reversed by standing the compound over a suitable desiccant or by gentle heating. Chemical analysis shows that the black compound is CslSnBr, and that the yellow form contains variable amounts of water. Freshly prepared samples of Cs,SnBr, gradually lose their colour after exposure to the atmosphere for a period of about 1 week, but samples stored over the desiccant retain their black colour longer and deteriorate only after a period of 6 months. These observations suggest that the presence of water plays a major role in the process causing the loss of the intense black colour of S. Ichiba and M. Yamada, Polyhedron, 1983, 2, 499. a5sR. H. Andrews, S. J. Clark, J. D. Donaldson, J. C. Dewan. and J. Silver, J. Chem. SOC.. Dalton Trans., 1983. 767. 56s

332


freshly prepared Cs,SnBr,. The X-ray powder patterns of both the white and the black phases are found to be identical, showing that the two forms have identical bulk structures. The ll9Sn Mossbauer data show behaviour very similar to that of the system CsSnBr,-,Cl,--CsPbBr,_,CI, previously reported. The Cs,SnBr, phase has the high chemical shift and narrow linewidth consistent with an Oh symmetry environment around the Sn" and a stereochemically inactive lone pair. As Sn" is replaced by Pb" there is no substantial change in the chemical shift, while the replacement of Br and C1 leads to a smaller shift. In both cases the site symmetry, as reflected in the linewidth and quadrupole splitting, is reduced. This would arise from the electric-field gradient produced by an increasing imbalance in the p-electron density around the Sn". Similar changes are also observed in the white form of Cs,SnBr,. As the changes in the Mossbauer parameters are observed, the optical band gap (absorption edge) and the electrical band gap (as related to the electrical conductivity of the samples) both increase significantly (Table 1). This is particularly noticeable in the absorption edges of Cs,PbCl, (2.37 eV), Cs,PbBr, (2.34 eV), and Cs4SnBr, (1.79 eV). These compounds are isostructural, but replacement of Pb by Sn in Cs4PbBr, produces a rapid decrease in absorption edge before levelling off at ca. 20% Sn". More striking is the change in the absorption edge between the black and white forms of Cs4SnBr6.The presence of only small amounts of water has very little effect on the tin(@ electronic environment, as shown from the Mossbauer data, and none on the crystal structure, but it produces large changes in the electronic band structure, almost doubling the optical band gap. Table 1 Reflectance, electrical, and Mossbauer data for Cs,MBr,-,Cl,

phases

Electrical Mossbauer parameterslmm s-' at 80 K Absorption conductivity1 a (k0.01) A (k0.01) r (k0.01) edgelev lo6i2-l cm-' Compound Cs$nBr, (black) I .79 0.04 4.09 0 0.9 (white) 3.40 3.95 0 I .05 1.87 Cs,SnBr,CI, 0.05 4.01 0 1.35 Cs,SnCI, 2.70 0.02 3.85 0.89 1.60 CsSnBr, 1.80 9.00 3.98 0 0.84 0.1 4.03 C S ~ S ~ ~ . &r6 , , P ~ ~ . ~I .82 0 1.24 1.84 0.09 4.08 0 1.32 Cs,Sno.,Pbo.,Br6 2.19 4.05 0 t .32 Cs4Sno.,Pbo.,Br,Cl, 0.02 3.95 0.68 I .46 Cs,Sno.,Pbo.,Br,CI, 2.57 3.89 0.77 1.55 Cs4Sno.,Pbo. ,Br2C14 2.7 I 0.001 3.82 0.87 Cs,Sno.6Pbb.6C16 2.80

The electrical conductivity and optical properties of the phases are explained in terms of the population of solid-state bands by the non-bonding electron pairs of the Group IV atoms. The poorer semiconducting properties of the lead(& rich phases result from the reduced overlap between the Sn 5s-orbitals and the Br d-orbitals arising from the presence of the larger Pb2+ ions, whereas the Pb 6s-electrons are more tightly bound to the Pb2+ion than is the case with Sn. Similarly, the smaller C1 3d-orbitals will overlap with each other, and with the


333

s-orbitals, less than do the larger Br 4d-orbitals. Also the presence of water molecules in Cs,SnBr, serves to disrupt the electronic structure by reducing halogen-halogen overlaps. The interaction between Sn" compounds with methyl 4,6-o-benzylidenea-D-ghcopyranoside and related molecules has been studied by the Mossbauer effect. The low values for the shift of the products are consistent with the extensive use of tin s-electron density in bonding to the oxygen molecules of the organic Palladium dichloride reacts with solutions of Sn" in hydrochloric acid containing [Me4N]+ions to give complexes of the types [Me,N],[Pd(SnCI,),Cl,], [Me4N13Pd(SnC1d2C131, [Me4NI3[Pd(SnC1dsl, [Me4N161Pd4Sn1oClae1, and [Me4N],[Pd4Sn,Cll8], which have been characterized using a number of techniques including y-resonance spectroscopy.668 Papers containing Mossbauer data of tin-containing materials with shifts in the tin@) region discussed earlier in this chapter include those dealing with tin(@ halides,60earsenic selenide glasses,s13c h a l c ~ g e n i d e s and , ~ ~ SnCl, ~ ~ ~ ~in~

mice.638 Inorganic Tin(rv) Compounds.-Both the Mossbauer effect and n.m.r. have been used in a study of the structure of stannate Parameters were reported for stannate solutions with SnO, : M 2 0 ratios of 0.5-1.7 and M = Na or K. A detailed study has been madeM0of supertransferred hyperfine-field effects at ll*Sn doped into various perovskites with the formula (Ao.e6cao.56)(Fe,,.86Mo.loSno.06)Os(A = La, Eu, or Lu, M = Al, Ga, Sc, Cr, Mn, Co, or Ni). The solid solutions of AFeOS(A = La, Eu, or Lu) were prepared and they contained 10 mol % of AMOS and 5 mol % of CaSnO, with the dual aim of giving a strong llQSnMossbauer resonance and an easily observable fine structure. In a random solid solution at these concentrations, 27% have five Fe and one M cation and 13 % have five Fe and one Sn cation. In total there are eight different new-neighbour environments that contribute more than 1 % to the spectrum (but only five more that contribute 2%). All eight of these were included in the computed data analysis by assuming that each cation contributed a flux density characteristic of the cation, so that the total flux density Beffat the Sn nucleus was given by the equation Bcff = nlB(Fe) n2B(M) n,B(Sn) where nl n, n, = 6, and each six-line hyperfme pattern contributing to the actual spectrum was weighted according to the binomial probability. In retrospect it would have been possible to reduce the tin content to ca. 2 mol % and thereby reduce the importance of B(Sn). However, the spectra were clearly dominated

+ +

+

+

J. Blunden, P. A. Cusack, P. J. Smith, and P. W. C. Barnard, Itinrg. Chirn. A d a , 1983, 72, 217. 588 P. G. Antonov, Yu. N. Kukushkin, R. Kh. Karymova. V. Strele. and Yu. P. Kostikov, Zh. Obshch. Khim., 1983,53,858. 5ss G. M. Barvinok, S. R. Kasabyan. M. K. Khripun, M. M. Sychev, and V. B. Lebedev, Zh. Prikl. Khim. (Leningr.), 1983, 56, 1238. sM) T. C. Gibb, J. Chem. SOC.,Dalton Trans., 1983, 9, 2035. 5ri7S.

334


by B(Fe) and B(M), and these parameters were easily determined. l n the event the values for B(Sn) were obtained separately from solid solutions of AFeO, with 10 mol % of CaSnO, and were then kept as fixed parameters for the ternary solid solutions. Only one value each was specified for the chemical shift and linewidth, and any quadrupole interactions were assumed to be negligible. The supertransferred hyperfine field at the l19Sn nuclei provides information on the magneticexchange interactions on the perovskites. The field at l19Snwith an environment of six Fe3+ nearest-neighbour cations was shown to be almost independent of the other substituent cation (M) but to be very strongly dependent on the rareearth-metal cation. However, the field at l19Sn with an environment of five Fe3+and one M3+nearest-neighbour cations is also dependent on the radius of the Ms+cation and on any intrinsic supertransformed hyperfine fields that it may produce. Thus it has been possible to show that Cr3+,Mn3+,and Ni3+substituents in rare-earth-metal orthoferrites produce a field contribution at ll0Sn that has the same sign as the one produced by the Fe3+ cations of the host, and any supertransformed hyperfine field produced by more distant neighbouring cations has been shown to be negligible. The Mossbauer spectra for Sn and Sb nuclei in the perovskite superconductors BaPb,-,Bi,O, in which Sn was substituted for Pb have also been and data for l19Sn in BaTiO, and PbZrO, have been included in a review.562An anomalous dependence of the l19Sn chemical-isomer shift on x was found in a study of BaPb,-,Bi,0,.5s3 The shift value was found to be highest at x z 0.22, that is in the composition region where the phases have the largest values for the superconduction critical temperature and for the concentration of free current carrier. The data are said to suggest that the origin of superconductivity in these phases cannot be attributed to any anomalies in the lattice dynamics. The value of the quadrupole-splitting parameter was found to increase with decreasing Pb0-B1203 ratios in the compounds Pb2Bi205,Pb5Bi801,,Pb$i@11, PbBil8OI3, and PbBil2OlQcontaining l19Sn and was attributed to an axial perturbation of the unit cell with increasing Bi203content.564The effects of the method of preparation of the lead bismuth oxides on the Mossbauer parameters of Sn atoms present were also studied, and it was shown, for example, that two crystalline modifications of Pb5Bi,01, could be prepared depending on the annealing temperature used. The Mossbauer spectra of electrodeposited tin on aluminium at room temperature showed the presence of both ?-Sn and SnO,. At 80 K, however, the spectra also contained a doublet with 6 -= 0.9 mm s-l and A = 2.14 mm s-l that was attributed to the presence of a non-stoicheiometric phase AI,Sn,O,+,, saturated with lattice imperfection^.^^^ The absence of lines due to this phase at room temperature was explained in terms of the low Debye-Waller factor that it must C. W. Kimball, A. E. Dwight, S. K. Farrah, T. F. Karlov, D. J. McDowell, and S. P. Taneja, Supercond. d-f-Band Met., Proc. Conf., 4th, 1982,409. .jBa D. K. Date and U. Gonser in ref. 4, p. 882. M. V. Plotnikova. S. I. Reiman, V. V. Bogatko, and Yu. N. Venertsev. Fiz. Tverd. Teln. 1983,2!5,2508. B64 G. A. Bordovskii and A. B. Zharkoi, Fiz. Tverd. Tela, 1983,25, 251 1. .x5H. Mehner, J. Juhasz, M. Suba, and A. Vertes, Radiochern. Radionnal. Lett.. 1983, 56, 57. jsl


335

have, and the negative shift value from SnO, was taken as evidence that the C1203 environment caused a decrease in the s-electron density at Sn. Mossbauer spectroscopy has also been used in studies on the use of tin(rv) phosphates in silk weightingM6and on the propene oxidation catalysts SnSbO and SnSbFeO in which no evidence for the presence of Sn2 was found.567 A number of papers published during the review year were concerned with llPSn Mossbauer studies on ternary and other phases containing sulphide, selenide, and t e l l ~ r i d e . The ~ ~ ~spectra - ~ ~ ~for SnSe,, TI2SnSe3,Tl,SnSe,, TlSnS,, and TI,Sn,S, were all fitted568to quadrupole doublets and showed the presence of only one tin site in each compound. In an attempt to explain the quadrupole splitting of the spectrum for SnMo,S,, Nefedovbsgcalculated the e.f.g. on the Sn nucleus in the cluster [Sn(M O , S , ) ~ ] ~ ~The - . estimated valence and lattice contributions to the field gradient at the cluster Sn atom were 0.57 and 0.03 mm s-l, respectively. The external vibrational modes of the Chevral phase Sn,Mo,S, were also investigated by measuring the temperature dependence of the Debye Waller factor of 110Sn.570 An evaluation of the mean-square displacement of Sn atoms parallel (uIl2)and perpendicular (uL2)to the rhombohedra1 axis (ullB) clearly showed harmonic behaviour with a Debye temperature varying between 160 and 250 K, depending on the stoicheiometry, and (uL2)could only be described by a quasi-harmonic model with a linear temperature dependence of O,, which is consistent with the phonon softening already known from inelastic neutron scattering. In addition, a step in the temperature dependence of B,(T) was observed between 120 and 200 K for high-Tc, Sn-rich samples, indicating the occurrence of a structural instability in this temperature regime. A linear increase in the y-resonance chemical-isomer shift with .Y has been found for the phases Cu,CdSn(S,-,Sex), and Cu,CdSn(Sel-,Te,), ( x = 0, 0.25, 0.5, 0.75, or l), and a comparison of the shifts for Cu,Sn(S,-,Sex), and AgCrSn(S,-,Sex), revealed the existence of two correlations between the shift data and interatomic distances.571The shift and the interatomic distances both increase on replacing S with Se. The broad asymmetric lines found in the Mossbauer spectra of the compounds Cu,SnY, (Y = S, Se, or Te) have been resolved into subspectra from two Sn'" sites with parameters 6 = I .43, A = 0.77 and 6 = 1.57, A = 3.14 mm s-,, respectively.572 The Mossbauer spectra of solutions of SnCI, and SnT, in porous glasseslloJIL were discussed earlier in this chapter (p. 294). The data for reduction products of graphite laminar compounds with SnCI, obtained by a number of techniques including llOSn Mossbauer spectroscopy were not consistent with charge-transfer effects. The reduction products can therefore only be described as containing

Ts. Busova and D. Khristov, Textilveredlung, 1982. 17, 446. B. Benaichouba. P. Bussiere, J. M. Friedt, and J. P. Scanchel, Appl. Catal., 1983, 8, 237. 5clR P. Houenou, A . L. Ajavon, and G . A . Fatseas. C. R . Scanrev Acnd. Sci.. SPY.2, 1982. 56(1 547

295,455.

V. S. Nefedov, Fiz. Tverd. Tela. 1983, 25, 291. H. A. Wagner and H. C. Freyhardt, Supercond. d-f-Band Met., Proc. Conf., 4th, 1982, 197. 571 A. Dramas, K. Makariunas, and M. Balciuniene, Phys. S?atus Solidi A, 1983, 77, 463. 572 M. P. Gupta, S. K. Date, and A. P. B. Sinha in ref. 1, p. 700. 560

570

336


dimeric Sn clusters not interacting with the graphite lattice and not as laminar graphite The configurations of hexahalogenostannate(rv) complexes in glassy aqueous mixed-halide solutions were determined by l19Sn y-resonance spectroscopy and Raman The resonance lines for mixed-halide complexes are broader than those of the monohalide SnX,?- species, and it was found that trans-(SnF,C1,)z-, (SnCI,Br)'-, and trans-(SnF,Br,)?- were the main complexes Sn"-HCI-HBr, and in the glassy states of the systems Sn"-HF-HCI, Sn"-HF-HBr, respectively. There also appears to be a reasonable direct relationship between the shift and the average electronegativity of the halide ions. The temperature dependence of the isomer-shift data for CuSnF,H,O in the region of a phase transition was shown to be non-monotonic at temperatures just below the dehydration temperat~re.~'~ Adducts of SnCI, and SnBr, with crown ethers have been prepared and characterized by their Mossbauer data,576 which are consistent with adduct formation involving oxygen donors from the crown ether. The low values for the shift were taken to mean that the Sn-0 interactions were strong. The reactions between Sn'" chloride and methyl 4,6-o-benzylidene-a-~-glucopyranoside and related molecules have been in the solid state and in solution. The single-line resonance spectra of the products are considered with the presence of cis-octahedral SnCI,L, environments. New complexes of the type CI,Sn( R1COCHCOCHCOR2)and Sn(RlC0CHCOCHCOR2), have been prepared.554The spectrum ( 6 = 0.17, A = 0.57 mm s-l) of the chloride compound at 77 K is a narrow doublet corresponding to Sn in a site highly co-ordinated by electronegative atoms. Compounds with shifts in the tin(rv) region of the spectrum discussed earlier in this chapter include CaSn0,,509 spinels,511 arsenic selenide c h a l c ~ g e n i d e s platinum , ~ ~ ~ ~ ~ tin ~ ~ aluminate catalysts,538 oxide glasses,5471548 and aliovalent halide species formed in the course of l19Sn emission in tin(1r) halide

Organotin(1v) Compounds.-A point-charge model for the quadrupole splitting of the y-resonance spectra of organotin halides containing phosphorus ligands was The hexa- and penta-co-ordinated compounds L,SnR,X,-, and LSnR,X,-, were considered, and it was found that the calculated values generally agreed with those obtained experimentally, although the method did not unambiguously determine the sign of the quadrupole splitting in trans-L2SnX, compounds or establish unambiguous structures of the compounds L2SnR,,X,-, (n = 1 or 2). The chemistry and ll9Sn Mossbauer spectroscopy of some 3-thienyl halides V. L. Solozhenko, I . V. Arkhangel'skii. A. M. Gas'kov, Ya. A. Kalashnikov. and M . V . Pletneva, Zh. Fiz. Khim., 1983, 57, 2265. .ji4 M. Katada, H. Kanno, and H. Sano. PoIJhedron, 1983. 2, 104. ".' B. Ya. Sukharevskii. V. G. Ksenofontov. A. N . Ul'yanov. and I. V. Vilkova. Ukr. N:. %/I.. 1983, 28, 720. ,-#76P. A. Cusack, B. Patel, and P. J . Smith, Inorg. Chirn. Actn. 1983, 76. L21. i77 A. S. Khramov, 1. Ya. Kurawshin, and A. N. Pudovik. Koord. Khim., 1982. 8, 1638. .i3

-.I-


337

R,Sn,-, (R = 3-thienyl, n = 2 or 3, X = CI, Br, or 1) and some of their complexes have been The Mossbauer parameters for the R,SnX,-, compounds were said to be consistent with unassociated tetrahedral structures. The related 2-thienyl and 2-fury1 derivatives were developed and characterized by their y-resonance data, but they are much less stable materials. The crystal structure of bis(triphenyltin)telluride was determined by Einstein et al.,57b and the result was used in the interpretation of the y-resonance data and n.m.r. for bis(tripheny1tin) and bis(trimethy1tin) chalcogenides. The data shown in Table 2 suggest that there is a correlation between the Mossbauer splitting parameters and the llOSnn.m.r. chemical shifts. Table 2 ll9Sn Mossbuuer and n.m.r. data for R,Sn,E compounds R Me Me Me Ph Ph Ph

E S Se Te S Se Te

Mossbauer 8/mm s-l A/mm s-' 1.26 1.68 1.29 1.59 1.32 1.49 1.20 1.46 1.32 1.40 1.33 1.23

N.m.r. 8

+93.9, +84.9

+50.7, +44.5 -59.3, -66.8 -48.7 -76 - 143.2

The crystal structure of the triorganotin arylazobenzoate SnPh JO2CC6H4(N,R)-o] (R = 2-hydroxy-5-methylphenyl) has been determined.580The crystals consist of independent non-interacting molecules (3) in which the carboxylate groups chelate the Sn atom with Sn-0 distances of 2.07 and 2.46 A, resulting in a distorted cis-SnC,O, five-co-ordinated geometry at Sn. The structure of this

(3)

compound is the first characterized example of a truly monomeric triorganotin carboxylate, and it is interesting to note that in spite of the bulky phenyl groups attached to the Sn and the very large steric effectsof the arylazobenzoate group the carboxylate prefers to function as a chelating ligand rather than as a unidentate ligand. A knowledge of the structure of this compound permits an assessment of the structures of similar compounds from an analysis of their ll9Sn Mossbauer shift, splitting, and. recoil-free fraction data. SnPh,[O,CC,H,(NR)-o] (R = 2hydroxy-5-methylphenyl) has 6 -= 1.285, 1 = 2.356 mm s-l and a = d[f(T)J/ dT = - 1.528 mm s-l K-l. The data for the compounds SnRZ,[OBCC6H4(NR2)-o] (R1 = Ph, R2 = 4-dimethylaminophenyl or 2-hydroxynaphthyl) are 6 = 1.296, D. W. Allen, J. D. Derbyshire, J. S. Brooks, and P. J. Smith, J . Organomat. Chem., 1983. 251, 45. .xHF. W. B. Einstein, C. H. W. Jones, T. Jones, and R. D. Sharma, Caw. J . Chem.. 1983,61. 2611. jeo P. G. Harrison, K. Lambert, T. J. King, and B. Majee, J . Chem. SOC.,Dalton Trans., 1983, .i7R

363.

338


A = 2.383 mm s-l, a = - 1.590 mm s-l K-l and 6 = 1.297, A = 2.312 mm s-l, a = 1.596 mm s-l K-l, respectively, which are similar to those of the 2-hydroxy5-methylphenyl compound, and the compounds must have a structure similar to that of compounds (3). The parameters ( 6 = 1.455, A = 3.349 mm s-l, a = - 1.299 mm s-l K-l) for tricyclohexyltin 0-(2-hydroxy-5-methylphenylazo)benzoate are quite different, indicating a gross change from the structure of its triphenyltin homologue. The increase in isomer shift is as expected for a change from an electron-withdrawing phenyl group to an electron-donating cyclohexyl group. The quadrupole splitting is much higher and the value of a increases, both of which are consistent with the weakly bridged chain structure exhibited by both tricyclohexyltin acetate and trifluoroacetate, which have quadrupole splittings of 3.33 and 3.78 mm s-l, respectively. The value of a for the compound is comparable with the values of the weakly bridged chain structures proposed for triethyl- and tripropyl-tin cyclohexanone oximate (- 1.16 x and -1.43 x lo-, K-l, respectively), but it is higher than that observed for the trimethyltin homologue (-0.97 x lo-* K-l) and trimethyltin glycinate (-1.15 x lo-? K-l), both of which have strongly bridged one-dimensional structures. The quadrupole splitting and a values for the compound trimethyltin 0-(4-hydroxynapht hy1azo)benzoate represent somewhat of a paradox. The increase in quadrupole splitting of 3.059 mm s-l could similarly indicate a distortion towards a trans-SnC,O, geometry at tin, implicit in which is the occurrence of some weak intermolecular interactions. However, the decrease of a to - 1.710 x K-l is inconsistent with this argument and suggests a molecular solid more loosely packed than the other three triphenyltin arylazobenzoates. An alternative rationalization of these Mossbauer data is that in this case the arylazobenzoato ligand chelates the tin atom not as an O,O-chelating carboxyl ligand as in compound (3), giving a distorted cis-SnC302geometry, but rather as an 0,N-chelate where the larger ligand-bite requirement allows a preference for the meridional-SnC,ON geometry, for which a quadrupole splitting much greater than 2.3 mm s-l would be expected. If indeed this is adopted by the compound it is not readily apparent why it should be preferred, and it suggests that rather subtle factors affect the structure. No examples of triorganotin compounds possessing the mer-SnC,X, geometry have as yet been characterized by structural techniques. Nevertheless, this geometry has been proposed for the

cationic species [SnPh,(opoj] diphoso

+

and [SnPh,(diphoso)]

= OPh261pPh20),which

+

(opo

= OPh2PqPh20,

exhibit quadrupole splittings of 3.52 and 3.56

mm s-l, respectively. Variable-temperature Mossbauer data have been obtained on the compounds Ph,SnSCH,CH,CO,SnPh, and Bu,SnSCH2CH,C02SnBu,, both of which contain four- and five-co-ordinated tin sites. The relative areas under the resonance lines were measured, and the Debye model of solids was used to fit the experimental data and to give the Debye temperature associated with each site.681Twenty-four N,N-disubstituted hydroxylamines of the formula R,SnL, (R = Bun or Ph, LH = N,N-disubstituted hydroxylaminesj and Ph,SnL J. S. Brooks, R. W. Clarkson, and J. M. Williams, J . Organomet. Chem., 1983, 251, 63.

Miissbauer Spectroscopy

339

were synthesized by the reaction of organotin(1v) chlorides and hydroxylamines in the presence of NEt3 in C6H6 medium. The Mossbauer spectra of the compounds were recorded and are typically 6 = 0.80-1.60 mm s-l and A = 1.683.53 mm s-l. Results indicate that the di-n-butyltin derivatives have distorted trans-octahedral structures, whereas the diphenyltin and the triphenyltin derivatives are &-octahedral and trigonal bipyramidal with equatorial p henyl groups, respectively.68* lroSn Mossbauer data have been obtained for the triorganotin compounds MesSnL and Ph,SnL (L = AcGlyO, AcAlaO, or AcMetO) and BunaSnL (L = AcGlyO or AcAlaO). The shifts and splittings are in the narrow ranges 1.26-1.46 mm s-l and 3.12-3.65 mm s-l, respectively, and these data taken with other information were interpreted in terms of five-co-ordinated tin environments with equatorial R groups and axial oxygen-ligand moieties.68s The y-resonance spectra of five disulphoxide complexes of Ph,SnCl were and discussed in terms of the structures of the complexes, the nature of the bonding of the tin atoms, and the changes in the electronic environment about Sn induced by complex formation. The shifts and splittings for monoPh,SnC1 complexes lie in the ranges 1.37-1.46 mm s-’ and 3.06-3.36 mm s-l, respectively, while the corresponding parameters for (Ph3SnC1), (PI-SOCH~)~ are 1.22 and 3.06 mm s-l. The llsSn data for some alkyltin trifluoroacetates have also been published.68sBoth l1@Sn and 67FeMossbauer effects were used to study the crystalline phase of a liquid crystal.6MSolutions of Me,Sn4methoxybenzylidene4-aminocinnmte (4.3% by weight) in the crystalline phase of the liquidcrystal material 4-pentylphenylheptyloxythiobenzoate(%) were studied by the llOSneffect. A pronounced deviation from Debye-like behaviour was observed at 80 K in the temperature variation of the recoil-free fraction data. This was interpreted as being due to a crystakrystal phase transition occurring in the liquid crystal at 183 K. Other systems studied were of tetrabutyltin and triethyltin palminate in 4-n-methoxybenzylidene-4‘-nt-butylaniline, in 4-n-trimethyltinbenzylidene4’-n’-butylaniIine (Sn-BBA), in 4-n-butoxybenzylidene-4’-ntoctylaniline, in 4-n-hexyloxybenzylidene-4’-n’-propylaniline, in trimethyltin-4-nmethoxybenzylidene-aminocinnamate,and in trimethyltin-4-n-methoxybenzylidene-aminocinnamate, and of Sn-BBA in ’iS5. The lloSn Mossbauer parameters of five tetrahedral organotin compounds of formula R1ReR3SnMn(CO)6(R1, R*, R3 = Ph, Me, or C1) have been obtained. The data combined with earlier results provide information on the series of jmmpounds where three R1 groups are progressively replaced with three R3 groups, and the changes in the shifts and splittings are discussed in terms of the effects caused by the s u b s t i t ~ t i o n s The . ~ ~ ~67Feand ll0Sn Mksbauer data for

-

M. K. Das, M. Nath, and J. J. Zuckerman, Znorg. Chim. Acta, 1983, 71, 49. Huber, H. Preut, A. Silvestri, and R. Barbieri, J . Chem. Soc., Dalton Trans., 1983, 595. A. Abras, F. J. Berry, J. G. Holden, and C. A. L. Filgueiras, Inorg. Chim. Actu, 1983,74, G. Roge, F.

135. *mA. Midha. R. D. Verma, K. Brown, and R. V. Parish, Indian J. Chem., Sect. A , 1983.22, 211. 6811

D. G. Todoroff, R. Marande, D. Boyd, and D. L. Uhrich, Mol. Cryst. Liq. Crysr., 1983, 95,367. B. Mahieu, D. Apers, E. 1. Vanden, and M. Gielen. J. Organoniet. Chem.. 1983,246.49.

340


some stannylene and tin ylid complexes of iron carbonyl derivatives have also been reported.688 The crystal structure of 1,lo-phenanthroline dichlorodi-n-butyltin has been determined. The tin environment in the crystals is a distorted octahedral (1,lO-phen)BuSnCl, unit. The Mossbauer data for the compound have been compared with the parameters obtained from similar The synthesis of diorganotin oxycarbonate (R,Sn),0C03 - nHzO has been described, and the llsSn Mossbauer and i.r. spectra of the compounds have been The oxycarbonates with R = Me, Et, Pr, Bu, or octyl have shifts in the range 1.12-1.24 mm s-l and splittings of 3.02-3.32 mm s-' at 80 K, while the corresponding parameters for (Ph,Sn),OCO, are 0.93 mm s-l and 1.97 mm s-l. The compounds display room-temperature spectra indicative of polymeric structures in the solid state for the high-melting insoluble oxycarbonates. The similarity of the Mossbauer parameters for the dialkyltin oxycarbonates suggests that they all adopt the same structure in the solid state, and the quadrupolesplitting values are typical of those associated with a trigonal-bipyramidal tinatom geometry, in which the two alkyl groups are occupying equatorial positions. Hence, the compounds probably possess a polymeric structure as in compound (4), containing intermolecularly bridging carbonate groups and four-membered Sn,O, rings. The Mossbauer parameters for diphenyltin oxycarbonate are also consistent with equatorial R groups and trigonal-bipyramidal co-ordination at tin, as in structure (4), for example in comparison with Ph2Sn(sal-N-2-OC,H,), which shows 6 = 0.99, A = 2.19 mm s-l, which is known to have Sn in trigonalbipyramidal co-ordination. A previous report on the Mossbauer spectrum of (Ph,Sn),OCO, suggested that it consisted of four lines with the inner doublet having parameters similar to those now reported for the compound. It has now been shown that, if the product is not washed effectively with water after precipitation from methanol, it shows a four-line spectrum ( 6 = 1.00, A = 2.26 mm s-l; 6 = 1.16, A = 3.82 mm s-l), and it is therefore likely that the larger quadrupolesplit doublet is due to an ionic diphenyltin impurity, in which the tin atom is occupying an octahedral trans-R,SnX, geometry. The phenylphosphonate and phenylarsonates Me,Sn [PhPO ,I, M e,Sn [PhA s 0 J, and Bu",Sn [PhA s 0 3] were prepared as their a-modifications by the reaction of dialkyltin dichlorides with the monosodium salt of the appropriate acid. The P-modifications of the compounds were obtained by dehydrating the monohydrates prepared by the reaction of dialkyltin dichlorides with the disodium salt of the appropriate acid. Only the p-form of Ph,Sn[PhP03] was isolated. Direct reaction of diorganotin dichlorides with the acids gave Me,Sn[PhAs(OH)O,],, Bu"Sn[PhAs(OH)O,],, and Me,Sn[PhP(OH)O,],. Cunningham et reported that the most illuminating structural data that they obtained on these phosphonates and arsonates were derived from llOSny-resonance data. The large values of A (3.79-4.34 mm s-l) for W. Petz and J. Pebler, Inorg. Chim. Acta, 1983, 76, L18Y. P. Ganis, V. Peruzzo, and G . Valle, J . Organomet. Chem., 1983, 256, 245. jSo P. J. Smith, R. Hill, A. Nicolaides. and J . D. Donaldson, J . Orgonornet. Chern., 1983. 252. 588

*jBS

149. 3Q1

D. Cunningham, P. Firtear, K. C. Molloy, and J . J . Zuckerman. J . Cltem. SOC.. Dnltort Trans., 1983, 1523.

34 I


R2Sn[PhE(OH)0,J2(E = As, R = Me; E = P or As, R = Bun), the asymmetry of the spectra that appears to be due to the Goldanskii-Karyagin effect, and the ease of accumulation of a spectrum for the methyl derivative at room temperature were taken as evidence for infinite chain structures with Sn atoms in octahedral sites with trans-alkyl groups and hydrogen bonding linking the chains. The a-modifications of the compounds R2Sn[PhE03] differ from the B-forms in the following respects: (a) they have higher chemical-isomer shifts, (6) they have larger quadrupole splittings, and (c) they have different slopes for the graphs of In(A) against temperature. The temperature dependence of the total areas under the resonance peaks suggests that the Sn atoms are more rigidly bound in the lattices of the a-forms. These data were interpreted in terms of two-dimensional sheet structures for the a-R2SnphE03Jcompounds with Sn in four co-ordination and infinite chain structures for the @-modificationswith Sn in five co-ordination. The data for the hydrates R,Sn[PhEO,] - H,O suggest that they have similar backbone structures to the @-formsof R,Sn[PhE03], for which they are the precursors. The parameters for a-Me,Sn[PhPO,] do differ from those of the other a-modifications and do not preclude the possibility that it has a different structure with a more associated network and Sn in highly distorted octahedral sites. \

0 f

-0

0 I

The co-ordination of some N- and 0-donor ligands with di-n-butyltin glycolate succinate and o-phthalate was characterized by the y-resonance data of the comp l e x e ~ The . ~ ~complex ~ with dmso has parameters of 8 = 1.32, A = 3.10 mm s-l, compared to 8 = 1.18, A = 3.15 mm s-l for the parent di-n-butyltin ethyleneglycolate.Davies and Price603reported that the dioxastannolans Bu,Sn(OCR,) react with ligands such as pyridine, dmf, dmso, sulpholane, and thf to form a series of complexes Bu,Sn(OCR,),L. They recorded the ll@SnMossbauer and n.m.r. data for the complexes, and the y-resonance data (shifts in the range 0.91-1.25 mm s-l, splittings in the range 2.1 1-2.82 mm s-l) were reported as being compatible with trigonal-bipyramidal structures with equatorial Bu groups and 598

S. P. Narula, R. K. Sharma, S. Lata, N. Kapur. and R. Seth, Indinn J. Chern., Sect. 1983, 22, 248.

593

A. G . Davies and A. I. Price. J . Organomet. Chem., 1983, 258, 7.

A.

342


axial-ligand donor atoms. Harrison et al. published two papers describing investigations into diphosphine oxide ligands in complex formation with diorganotin(1v) corn pound^.^^^^^^^ They recorded the spectra of three SnR,Cl,L complexes [L = 1,2-bis(diphenylphosphoryl)ethane (dppoe)] in the temperature range 77-150 K and of (SnPh,Cl),(dppoe) at 77 K. The value of A for (SnPh,Cl),(dppoe) is in the range expected for trans-SnR,X, geometry. In the case of the SnR,Cl,(dppoe) complexes the splittings with values greater than 4 mm s-l suggest a trans-SnR,X4 arrangement of atoms around the Sn. This observation is consistent with the X-ray structure found for SnBu,Cl,(dppoe), although in which the Sn atom is in a severely distorted octahedral site. Graphs of lnA(T) versus Tfor the complexes and the least-squares computed values for the temperature coefficients, a, were found to be -0.758 x lo-, K-l, - 1.231 x lo-, K-l, and -1.041 x lo-, K-l for R = Pr", Bun, or Ph, respectively. These values of a lie in the range expected for compounds with strong associated lattices and are in accord with the known one-dimensional chain structure for the dibutyltin complex. The ambient-temperature and crystallographic-temperature factors were used to calculate values for the root-mean square amplitudes of vibration < x > and for the absolute recoil-free fraction, f, at various temperatures from the equation f ( T ) = exp[- < x ( T ) > 2A2], where A is the wavelength of the . values of < x > and f for SnBun,y-resonance transition divided by 2 ~ ; The SnCl,(dppoe) vary from 0.146 A at 77.3 K to 0.198 8, at 290 K and from 0.438 at 77.3 K to 0.0032 at 290 K, respectively. The authors also used llsSn Mossbauer data along with crystal-structure determination to characterize the cis-l,2-bis(diphenylphosphory1)ethylene (dppoet) complexes SnR,Cl,(dppoet) (R = Bun or Pr"). The crystal structures show that the complexes have Sn in distorted octahedral sites with trans-R groups. The Mossbauer shift and splitting parameters for the two complexes do not change significantly over the temperature range 80-150 K : the shifts and splittings for the Pr" derivative have values between 1.53 and 1.64 mm s-l and 3.82 and 4.00 mm s-l, respectively, with the corresponding values for the Bun derivative being 1.52 and 1.56 mm sdl and 4.07 and 4.11 mm s-l. The values of A of about 4 are consistent with the transalkyl groups in the distorted octahedral tin environments. Although the shifts and the splittings do not vary with temperature, both complexes do show a rapid decrease in resonance area with increasing temperature.The slopes of the linear portions of the semi-logarithmic plots of the relative resonance areas against temperature were found to be - 1.76 x lo-, K-' and - 1.56 x lo-, K-l for the Pr" and Bun derivatives, respectively. These values are characteristic of molecular lattices, with the lower value for the butyl derivative being attributed to the more open co-ordination found for Sn in this complex. Two papers published during the year were concerned with the spectra of

P. G. Harrison, N. W. Sharpe, C. Pelizzi, G. Pelizzi, and P. Tarasconi, J . Chem. SOC., Dalton Trans., 1983,921. 5s6 P. G. Harrison, N. W. Sharpe, C. Pelizzi, G. Pelizzi, and P. Tarasconi. J. Chem. Soc., Dalton Trans., 1983, 1687.

6s4


343

tin-containing materials in p o l y r n e r ~ .Incorporation ~ ~ ~ ~ ~ ~ ~of Bu2SnC1, into a polyvinyl chloride matrix resulted in a decrease in A from 3.45 mm s-l for the pure compound to 3.09 mm s-l when it is dispersed at 1.2 weight % in the polymer. The decrease was attributed to the breakdown of the associated sixco-ordinated structure of Bu,SnCl, and the progressive formation of dimeric units involving five-co-ordinated tin.bw The mechanism of plasticization of tin-containing polymers was confirmed by Mossbauer spectroscopy of the waterplasticized polymer from resorcinoldiglycidylether and Bu,Sn(OBz),. The Mihbauer spectrum of the polymer is an asymmetric doublet that was interpreted in terms of the presence of two tin sites. 6 Other Elements

This section reviews the data for elements other than iron and tin. In each of three main subsections (main-group elements, transition-metal elements, and lanthanide and actinide elements) the isotopes are treated in order of increasing atomic number. Main-group Elements.-The isotopes 83Kr, llgSn, 121Sb, 126mTe,lagmXe,and lS3Xewere included in a survey of the sensitivity of Mossbauer spectroscopy in ion-implanted samples.6g8 Germanium (73Ge).Pfeiffer et aZ.6gareported the first use of the 13.3 keV 73Ge Mossbauer effect to study Ge nuclei at substitutional sites in single crystals of Si. M h b a u e r sources were made by using laser melting to incorporate volatile 7 3 Aradioactive ~ parent nuclei into crystals of Si or Ge. This method of incorporation of the active nuclei was found to be much more efficient than conventional thermal diffusion. The Mossbauer resonance lines obtained with the the 73AsSisource are broadened to 118 pm s-l at half-height, of which about 106 pm s-l can be accounted for by the broadening effects due to laser processing of the Si. The data suggest that the observed broadening is not due to a distribution of isomer shifts but to an e.f.g. at the Ge daughter nuclei by bulk strain. Bond-orbital calculations of the e.f.g. induced at the Ge nuclei by deforming the host lattice in uniform tension in the place of the (1 11) surface are reported and discpssed. Transmission electron-microscope data in agreement with the conclusions from the Mossbauer experiments do reveal a high density of dislocations. Antimuny (la1Sb). The use has been described of the lPISb effect to check the accuracy of the wavefunctions applicable to the electronic structure of semiconductors and obtained from either band-structure calculations or from the J. S. Brooks, R. W. Clarkson, and D. W. Allen, J. Organornet. Chem., 1983,243,411. V. A. Lagunov, V. I. Polozenko, A. B. Sinani, and V. A. Stepanov. Fiz. Tverd. Tda, 1983.

U,1816. me I.

Dezsi in ref. 1, p. 141. L. Pfeiffer, T. Kovacs, C. K. Celler, V. M. Gibson, and M. E. Lines, Phy,s. Rev. B. 1983,

27,4018.

344


solution of the impurity problem. A Green function based on a modified tight-binding method was used to evaluate the shift data and the electronic structures of 121Sb either as a main component or as an impurity atom in AN-BB-N~ e m i c ~ n d ~ c t o r ~ . ~ ~ ~ A method has been described to obtain the spectral parameters from poorly resolved lZISbspectra where it has been shown that, even for samples of moderate thickness, analysis with a sum of Lorentzians instead of with a complete transmission integral can induce significant errors in fitting. Graphs of the relative deviations for purely magnetic-quadrupolar interactions were constructed and used to determine the parameters when use of the complete transmission integral is required.600 Friedt and his co-workers601~so2 have shown that intense electronic-charge and spin-density perturbations occur at Sb-Fe interfaces with Sb. In one paper they found evidence for a large hyperfine field that was transferred from the magnetic layer at Fe-Sb to the non-magnetic Sb layer.6a1The value of the transferred field at 350 kOe is found to be larger than the field (235 kOe) at Sb diluted in a-Fe. In the second papersoZthe authors describe studies on multi-layered structures with an artificial superstructure consisting of Fe and Sb layers prepared by ultra-high vacuum deposition. The thickness of the individual layers varied from 2 to 42 and from 8 to 41 A, respectively. Both the 57Feand 131SbMossbauer effects were used with other techniques to obtain information on the interface magnetism. Evidence was found to suggest that the spin polarization penetrating into the Sb layer was large and long-range. The syntheses, i.r. spectra, and lZISbMossbauer parameters for the complexes of 1,lO-phenanthroline (L) with SbX, (X = F, CI, or Br) and PhSbI, have been describedsa3 along with the data for the 1 : 1 adduct of 2,2”-bipyridine with PhSb12.The data suggested that SbF, - L contains a stereochemically active lone-pair orbital with high p-character, while those for the PhSbIz complexes are consistent with a pseudo-octahedral distribution of electron pairs around Sb with the Ph groups trans to the lone-pair orbital. A non-empirical Hartree-Fock-Slater ( Xx)-LCAO study was made of the Mossbauer parameters of thirteen Sb compounds, viz. SbX3 ( X = F, CI, Br, or I), Me,,SbCl,_,, (n = 1, 2, or 3), SbX, ( X = F or CI), and Me,SbX, (X := F, CI, Br, and I).s04The calculated isomer shifts for all of the compounds are found tobeingoodagreement withtheexperimentalvalues,withAR/R = -1.08 x The calculated quadrupole-splitting values are, however, consistently smaller than the experimental values, and in the case of Sb” compounds there is a great deal of scatter in the graph of the observed against the calculated splittings. The authors suggested that these differences could be accounted for either by uncertainty in the 121Sb nuclear-quadrupole moment or by the neglect of the effects of core electrons. Surprisingly they do not consider the effects of the nature of the distributions of bonding electrons among the bonds and, in the case of 6oo

D. Gryffroy and R. E. Vandenberghe, Nucl. Instrum. Methods, 1983,207,455. J. M. Friedt, N. Hosoito, K. Kawaguchi, and T. Shinjo, J . Mugn. Mugn. Muter., 1983.35, 136.

eosT.Shinjo, N. Hosoito, K. Kawaguchi, T. Takada, Y. Endoh, A. Yoshitami. and J. M. Friedt, J . Phys. Soc.Jpn., 1983,52, 3154. N. Bertazzi. G. Alonzo, and T.C. Gibb, Znorg. Chim. Actu, 1983,73, 121. so4 W. Ravenek, J. W. M. Jacobs, and A. Van der Aoird, Chem. Phys., 1983,78,391.


345

SbI1', the non-bonding orbitals, but they do conclude that the structures of Sb compounds might be different from what has previously been suggested. Rubidium oxalate reacts with antimony(ni) fluoride in aqueous solution to give the products RbSb,(C,O,)F, and RbaSbn(Ce04)Fg, which were characterized by their i.r. and 121SbMijssbauer The y-resonance spectra have also been recorded for some lithium thioantimonites at 4.2 K. The chemical isomers for the ternary sulphides isolated from the Li,S-Sb,S, system are in the range -6.22 to -3.50 mm s-l from InSb and are characteristic of Sb"' compounds. The data are discussed in terms of the stereochemical activity of the lone pair of electrons on Sb.60gA detailed study of the propene oxidation catalysts SnSbO and SnSbFeO included lZISbMossbauer data that were used to confirm that the Sb was present in the TI1 oxidation state. The problems encountered when using y-resonance methods for quick Sb assays on minerals and samples obtained at various stages of the industrial production of antimony metal have been described.6n7Data from thirty assays showed that the Sb is usually present as a mixture of three phases SbY03,Sbz05,or Sb2S3.The concentrations obtained from the Mossbauer assays were found to be close to tho& obtained by chemical analyses. The i.r. and Mossbauer data for (ReCI,(NO)y[SbPh3]2)have been used to show that the NO groups are in cis positions and that the SbPh, moiety is a strong a-donor to Re. The complex has a structure containing octahedrally co-ordinated ligands with the two SbPh, moieties in trans positions.6o* Antimony-121 y-resonance studies have been carried out on the compounds SbF, and MeNO,SbF, intercalated in graphite. Stage-two samples of the graphite-SbF, intercalation compound were prepared by reactions at 200 "Cfor five days. The 121SbMossbauer spectra obtained at 4.2 K showed the presence of a broad resonance in the Sb"' region.6n0!' The spectra of the intercalation compounds C,,,SbF,(MeNO,) (n = I or 2) also showed a narrow band in the SbV region of the shift spectrum but in these cases there was no evidence for spectral lines attributable to Sb1".610The data for all of these intercalated compounds were discussed in terms of the likely chemical species formed on intercalation. The data for the SbV species in the intercalate layers are consistent with the presence of SbF,- ions. The antimony-121 y-resonance effect was also used to show the presence of three Sb species in samples of SbF,-doped polyacetylene with dopant levels of 0.1-8.4 mol %. The three species identified were SbF3, SbF,, and SbF,-, and the spectra were sufficientlywell resolved to permit the determination of the relative amounts of the three species present.e11

+

aos R. L. Davidovich, L. A. Zemnukhova, A. A. Udovenko, and N. I. Sigula, Koord. Khini.. 1983, 9, 787. J. C. James, J. Oliver-Fourcade, E. Philippot, and M. Maurin. J. Solid State Chem.. 19113. 49, 6.

B. G. Zemskov and Yu. V. Permyakov in ref. 1, p. 322. D. Fenske, N. Mronga, and K. Dehnicke, Z.Anorg. Allg. Chem., 1983,498, 131. two D. H. McDaniel, P. Boolchand, W. J. Bresser, and P. C. Eklund, Mater. Res. SOC.S.vmp. Proc., 1983,20,377. ' l o P. Boolchand, W. Bresser, D. McDaniel, P. C. Eklund. D. Bilaud, and J. E. Fischer. Mater. Res. SOC.Symp. Proc., 1983,20,389. F. Godler, B. Perscheid, G. Kaindl, K. Menke, and S. Roth, J . Phys. Colloq., 1983,233.

346


The Mossbauer spectrum of Sb205was shown to have a zero isomer shift from BalB1Sn03suggesting that the SbV-0 bonding in the oxide is similar to that of SnxVin BaSn0,.812 The Mossbauer effect at 121Sbimpurity nuclei in the perovskite superconductorsBaPb,-,Bi,O, with Sb substituted for Bi has been studied. Small quantities of Sb in the lattice extend the range of Bi compositions over which the compounds are superconducting. The Sb y-resonance spectra for the phases are similar for the superconducting and non-superconducting composition and are characteristic of Sbv-oxygen bonding.661Both the 67Feand 121Sbisotopes were used in a study of the Sb-substituted lithium ferrite Lio.s+xSb,Fez.5-2xOa (x=0.05) in a longitudinal magnetic field of 6 T. The unexpectedly small value found for the supertransferred hyperfine field at Sb was interpreted in terms of the indirect effect of B-site occupation on A-0-B spin 121Sb spectra were also recorded on the spinel phases ZnNio.,6FeSbo.3,04and Nio.,,FeSb0.,,O, with and without the application of a transverse magnetic field. The spectra for the Zncontaining spinel were found to contain a contribution arising from covalency mixing by direct cation-cation orbital combinations. A temperature region in the spinels above TN was also found for which the Sb nuclei were affected by a magnetic ordering to which the Fe nuclei were insensiti~e.6'~ Tellurium (lZsTe).Hartmann et aL615reported on a study in which the Xascattered-wave method was used to deduce estimates of the differences in the electron densities at the Te nucleus in some compounds. On the basis of these estimates some assertions were made regarding the calibration problem of the Mossbauer nuclide lZ5Teand the chemical influence on the internal conversion of the 33.5 keV M1 E2 transition in lz5Te. Methods of studying the Mossbauer effect at high pressures on la6Tenuclei have been reported, and the camera and cell have been described.616The spectra of Te and TeO, were recorded at < 110 kbar. No significant change was observed in the shape of the spectrum of TeO,, confirming the absence of a phase transition. The Mossbauer spectrum of Te indicated the phase transition at 40 kbar and 300 K. A source with a natural linewidth and high probability and weak temperature dependence of the Mossbauer effect has been obtaineds1' by irradiating SMgO-TeO, and annealing it at 850-1000 "C for 5-7 hours. Compounds from the Te-Mo-0 and Te-V-0 systems have been studieds18 by e.s.r. and le6Te y-resonance spectroscopy. The Mossbauer spectra are similar, with isomer shifts characteristic of Texv in an oxide environment, typically 6 = 0.6 mm s-l and A = 6.6 mm s-l. The data are further interpreted in terms of the cationic oxidation states and their environments in the mixed-oxide structures. The hyperfine field at the lZ6Tenucleus has been observed61gin Cr0.,Te. It is assumed that this

+

61a

618

610

M. Jansen, J. Pebler, and K. Dehnicke, Z . Anorg. Allg. Chem., 1982. 495. 120. G. Dehe and J. Suwalski, Phys. Status Solidi B, 1983, 119, K155. G. Dehe and U. Behn, Phys. Status Solidi A , 1983. 78, 485. E. Hartmann and M. Rysavy in ref. 5, p. 257. A. A. Kornilova and A. A. Opalenko, Vestn. Mosk. Univ., Ser. 3, Fiz. Astron., 1983,24,85. A. Y u Aleksandrov, Yu. S. Grushko, E. E. Makarov, K. Ya Mishin. and D. 1. Baltrunas. Otkrytiya Izobret. Prom. Obraztsy, Tovarnye Znaki, 1982,48,272. F. J. Berry and M. E. Brett, Inorg. Chim. A m , 1983,68,25. I. Ortalli, A. Vera, E. Maniezzi, and P. Gibart in ref. 1, p. 694.


347

field is compatible with a transferred hyperfine interaction mechanism due to overlap of the Te 5s- with the Cr 3d-orbitals. The magnetic properties of MnTe, have been studiedsz0by the use of thermal expansion, 126TeMossbauer effects, and X-ray diffraction. The Mossbauer spectra show that the Mn spins are noncollinear the angle $ between the spin axis of Mn and the principal axis of the e.f.g. increases from 23" at 4.2 K to 30" at 60 K and decreases to 0" at 70 K. These observationshave been explained by taking the fourth-order spin interaction and anisotropy into consideration. In their study on the Mossbauer isomer shift of the electronic structure of semiconductors, Antoncik and Guszg consider lBSTe,along with ll9Sn and 121Sb,as representing either one of the components or an impurity in various AN-B8-N semiconducting materials. The reaction of NaTeR compounds with organic dihalides generally gives telluronium salts. Table 3 lZ5TeMiissbauer data for the reaction products of NaTe(C,H,OEt-p) with dibromoalkanes Compound [(p-EtOCeH4)Te]&H2CHaBr2 KP-E~OC,I~,)T~(CH,) 8Brl

[(p-EtOC,Ii,)Te(CH,),Brl

s/mm s-1

A / m m s-'

0.53 0.36 0.38

7.58 5.58 5.50

The la6Tedata for the products of the reactions between NaTe(p-EtOC,H,) and three organic dibromides are given in Table 3. The parameters for [(p-EtOC,H,)Te],CH2CH2Br2differ from those of the other two compounds that have shifts and splittings typical of telluronium salts. The mechanism suggestedoz1to explain the shift and splitting for [(p-EtOC6H4)Te]2CH2CH2Brz involves the loss of Sp-electron density from the non-bonding electron-pair orbital by a charge-transfer reaction. Two possible formulations for a charge-transfercomplex of the type suggested are shown in compounds (5) and (6).

Over the past year a number of papers have appeared in the literature concerned with Miissbauer studies of 12"e-doped or -implanted materials. The nature of defects in heavily tellurium-doped gallium arsenide is one of the studies undertaken,bZ2and in another study crystalline Ge and amorphous Ge,Te,-, ( x = 0.8) were implantedsz3with lzamTeions. The Mossbauer spectra were similar e80 681

N. Kasai, Denshi Gijutsu Sogo Kenkyusho Kenkyu Hokoku, 1982, 824, 1. K. G. Karnika De Silva, Z. Monsef-Mirzai, and W. R. McWhinnie, J . Chenr. Soc., Dalton Trans., 1983, 2143. D. L. Williamson, M. Kowalchik, A. Rocher, and P. Gilvert, Rev. Phys. Appl.. 1983. 18, 475. I. Dezsi, M. Van Rossum, R. Coussement, and G. Langouche in ref. 1. p. 360.

348


in the implanted crystalline and amorphous samples, but their annealing behaviour was found to be different. laSI implantation in silicon and germanium has been studied over a wide ] . ~ ~ ~ interaction and channelling dose range [5 x (1012-1015) atom ~ m - ~Hyperfine studies of impurities such as Sn, Te, and I implanted in silicon have been carried outs18to provide insight into the location and electronic states of the impurities implanted in semiconductors. Mossbauer spectroscopy of implanted and laserannealed sources of different Te isotopes was used, and channelling studies were carried out on samples of Si implanted with stable Te and I isotopes. For both Te and I impurities a clear dependence of the Mossbauer isomer shift on semiconductor doping was found. Laser-annealed Te-implanted silicon has been investigated using lleSn and 125TeMossbauer spectroscopy. The 'lQSn Mossbauer spectra consist of a single Lorentzian, known to be due to substantial Sn atoms in Si, independent of the type of doping of the silicon. The 125TeMossbauer spectra taken at 4.2 K from a crystal implanted with 6 x 1014 at P cm-2 (50 keV) and 5 x 1014 at Te cm-2 (120 keV) and subsequently laser annealed have been fitted with a single line, which is slightly broadened compared to the Sn125mTeline [8.6(2) versus 8.1(2) mm s-l]. It has an isomer shift of +0.14(5) mm s-l with respect to SnTe. The spectrum that stems from a crystal implanted with 2 x 1015at B cm-2 (15 keV) and 5 x 1014at Te cm-2 (120 keV) has a linewidth similar to that for the n-type crystal; the isomer shift, however, is different at -0.1 3(5) mm s-l. The spectrum from a crystal implanted with equal doses of B and Te (6 x 1014atom cm-2) is a broadened line with an isomer shift between the two previous values. This spectrum could not satisfactorily be fitted as a combination of the two components. The results on 125Tereveal at least two different components. In heavily doped n-type Si a single-line component is observed with an isomer shift of 0.15(5) mm s-l with respect to SnTe and an effective Debye temperature of 207(3) K. Heavy p-doping leads to another single-line component with an isomer shift of -0.13(5) mm s-' and an effective Debye temperature of 232(3) K. These components are ascribed to the neutral and doubly positive charge state of substitutional Te atoms, respectively. The difference in isomer shift can qualitatively be understood on the basis of an effective mass model. The difference in Debye temperature has been explained as a result of a difference in the number of anti-bonding orbitals associated with the two configurations. The emission Mossbauer spectra of 1251-labellediodobenzene, MeI, and of their dilute solutions in benzene and hexane have been recorded and computer a n a l y ~ e d Two . ~ ~ ~species were observed: in one Te is presumably attached to two organic moieties, and in the other Te is attached to a single organic moiety. Iodine (12'1 and 1291). The lZ7I Mossbauer spectra of a number of iodine(m) cations of the type [IX,][MY,] and related molecules having four ligands and two non-bonding electron pairs about the central iodine have been recorded at 4.2 K.s26 I. Dezsi and R. Coussement, Radiar. E f f . Lett. Sect., 1983, 76, 221. C. Sanes, M . Reiche. A. Halpern, and A. Nath, Chern. Phys. Lett., 1983, 94, 227. 6z6 T. Birchall and R . D. Myers, J . Chem. Soc.. Daltori Trans., 1983, 885. 624 625


349

Agreement with literature data for K[ICI4] and for 12C16,the latter after conversion from 1291data, is good. The Mossbauer parameters are consistent with largely p-character for the ligand-iodine bonds. The central iodine in all of the compounds has a positive quadrupole-coupling constant indicating that the principal component of the electric-field gradient is along an axis perpendicular to the near-planar ligand arrangement. These changes in Mossbauer parameters, dominated by the two primary bonding interactions and the bridging ligands that complete the arrangement about the iodine, have only a minor, although significant, effect on the data. 127T Mossbauer isomer shifts and quadrupole interactionshave been measureds2' to evaluate the charge on the iodine in the Chevral phase compounds Mo,Xs12 (X = S or Te). The analysis yields 22.3 and 28.3 electrons per Mo, cluster in the sulphide and telluride. The quadrupole interactions at the iodine nucleus in Mo,S612and Mo,Te,l, are small but have opposite signs signifying bonding differences between these compounds. Both l2'I and lzeI Mossbauer spectra of PbIz are characterizeds2*by single resonances showing no measurable quadrupole coupling and with chemical-isomer shifts within the range expected for ionic iodides, The 1271 Mossbauer spectrum of Pb2021also shows a single line typical of an ionic iodide. No evidence was found for the presence of intercalated I in Pb"O1 nor for the existence of iodate in [Pb1120]2+OI-I-.The Mossbauer spectrum is consistent with a mixed-valence Pb oxyiodide of composition Pb114-xPb1V,0412x (1 o x < 2) with a Pb,O,Cl,-type structure. Kothekar the CND0/2 computation of the Mossbauer-effect parameters of iodine compounds and their comparison with experimental data. A study of alkali iodides, iodobenzene, monoiodiothyrosine, and diiodothyrosine has shown that the molecular-orbital technique can be applied successfully to iodine compounds. for the x--0 chargeThe lZsI Mossbauer spectra at 16 K were transfer complexes of I2with benzene, coronene, perylene, and poly(p-phenylene). It is suggested that the benzene-I, complex consists of alternate benzene and I, molecules. The Mossbauer spectrum for the coronene-I2 complex ( 1 : 1) shows only one chemical state of I,. In the poly(p-pheny1ene)-I, complex the I, exists as almost a free molecule. indicating that the interaction between the phenylene ring and I, is very weak. A number of papers report the use of lZsIMossbauer spectroscopy in iodinedoping and -implantation studies. Three papers by Matsuyama et al. have appeared reporting studies of iodine doped in poly(pheny1ene s ~ l p h i d e and )~~~ p 0 1 y a c e t y l e n e . ~ The ~ ~ ~ ~Mossbauer ~~ spectrum of the former indicates the G. V. Subba Rao, D. Niarchos, G . K. Shenoy, J . D. Cashion, D. Hinks, A. M. Umarji. and R. Janaki in ref. 1, p. 748. 628 F. Berry, C. H. W. Jones, and M. Domhsky. J . Solid State Chem.. 1983. 46. 41. V. Kothekar in ref. 1 , p. 71 1. 630 H. Sakai, T. Matsuyama, H. Yamaoka. and Y. Maeda. Bull. CIiem. Sor. Jpn., 1983. 56, 627

1016.

H. Sakai, T. Matsuyama, H. Yamaoka, and Y. Maeda, Chem. Phys. Lett., 1983,101,490. 632 T. Matsuyama, H. Sakai, H. Yamaoka, Y. Maeda, and H. Shirakawa, J . Phys. SOC.Jpn., 631

1983,52,2233. 633

T. Matsuyama, H. Yamaoka. and H. Shirakawa, J . Phvs. Chem. Solids, 1983, 11, 1093.

350


presence of two different chemical species, suggesting that the doped I molecule forms an n-a-type charge-transfer complex with the S atom of the polymer. From a series of Mossbauer studies the authors have been able to show quantitatively632ss33 that in iodine-doped polyacetylene the iodines are incorporated in the forms I-, 13-, and 15- in (CH),, where 13- and I,- are linear arrays of three and five iodine atoms, respectively. The variation of electrical conductivity in I-doped polyacetylene is along with the mechanism of charge transfer from the polymer and with the mutual conversion of iodide anions. The Mossbauer In spectra for C~S-(CHI,-,.~~~)~ and trans-(CHIo.156)x have been his review' on the developments in Mossbauer spectroscopy of implanted sources De Waard presents Mossbauer spectra for 129mTe-doped Si single crystals, and in another papers1*he reports on the hyperfine interaction and channelling studies of I implanted in silicon. Laser-annealed 129mTe-implantedsilicon has been investigated using lZ0IMossbauer At least three dope-dependent Mosscharge states of substitutional iodine are found. Figure 6 shows the 1291 bauer spectra of differently doped Si single crystals implanted with 129mTe and subsequently laser annealed. For heavily doped p-type Si a single-linecomponent S1,with isomer shift 6 = 0.96(4) mm s-l with respect to Cu12*Iand an effective Debye temperature 8' = 196(3) K, is observed. This component is attributed to I++. For compensated Si a single-line component S2, assigned to I+, with 6 = 2.39(4) mm s-l and 8' = 170(3) K, is found. For n-type Si, a component S,, characterized at 4.2 K by 6 = 2.15(4) mm s-l and a quadrupole splitting eQV,,/h = 452(8) MHz (x z 0), is observed. At higher temperatures S, shows quadrupole relaxation and its recoil-less fraction becomes strongly anisotropic. This behaviour is explained on the basis of a transition from a static to a dynamic Jahn-Teller distortion. Component S , has been attributed to Io. In the spectra of compensated and n-type Si a less well defined component Q, with parameters resembling those of S3 but showing no quadrupole relaxation, is observed. This component has tentatively also been assigned to Io. The results can be understood qualitatively on the basis of a simple MO model. implanted in a The lzeIMossbauer nuclear-quadrupole interactions for lZemTe series of 111-V semiconductors have been a n a l y ~ e d The . ~ ~ electronic-structure ~ investigations support the conclusion that the impurity centre shows a tendency to relax into a position that makes its distance to the nearest-neighbour host atoms consistent with the normal covalent-bond distance. To verify the existence and investigate the properties of local disorder in the ordered state of the superionic conductor RbAg,15 Pasternak used lZ9I Mossbauer spe~troscopy.8~~ Studies were conducted at 4-180 K and covered the low-temperature y-phase (T < 122 K) and part of the high-conducting disordered P-phase. The absorption spectra at all temperatures were analysed with 21 sites, characterized by their quadrupole splitting and isomer-shift values, and a third site, with a non-split G. J. Kemerink, H. D e Waard, L. Niesen, and D. 0. Boerma, Hyperfine Interact., 1983. 14, 53. 635 M. Van Rossum, G. Langouche, K. C. Mishra, and T. P. Das. Phvs. Rev. B, Condens. Matter, 1983, 28, 6086. 636 M. Pasternak, Phys. Rev. B, Condens. Matter, 1983, 28, 82. R34


0.98

351

I

-10

1

-5

1

1

0

5

1

10 Velocity/rnrn

S-'

Figure 6 laOlMossbauer spectra of diferently doped Si single crystals implanted with leomTe and subsequently laser annealed. Absorber Cul*OI, Tmtas. = 4.2 K. Top: 2 x 1016atom B and 2.2 x 1014atom Te ( p t y p e Si). Middle: 6 x lOI4 atom B and 6 x 1014 atom Te (compensated Si). Bottom: 2 x lo1*atom P cm-* and 1.4 x lo1' atom Te cm-a (n-type Si) (Reproduced with permission from Hyperfine Interact., 1983, 14, 5 3 )

single line. The e.f.g. at the l a Q I nucleus, produced by the neighbouring Ag ions, has a continuous linear temperature dependence down to 4.2 K.The existence of the single line has been attributed to a fast-fluctuating e.f.g. due to local hopping of the Ag ions. The Mossbauer effect in lZQIwas measured in frozen solutions of ~ t a r c h - ~ ~ ~ I and glycogen-12aIat 20 K.637In both cases the measured spectra yielded a set of eight lines and a separate single line. The relative intensities of the octet spectrum to the singlet were approximately 2 : 1. The octet of lines is interpreted as being due to the Mossbauer effect in the two outer atoms of It- and the singlet as being due to recoil-less absorption in the central ion, which is located at a site where there is no e.f.g. This is consistent with the observed 2 : 1 ratio of lines. The Is- system in the two complexes appears to be a resonating system resulting in zero e.f.g. at the central-iodine nucleus. Another paper reports638measurement 687

Y. W. Chow, A. Mukerji, and C. K. Wynter in ref. 1, p. 657. H. Haffner and H. Appel in ref. 1, p. 667.

352


of the first Mossbauer spectrum of a stable sulphenyl iodide bond in cysteine in tobacco mosaic virus. The spectrum recorded at 4.2 K has the following parameters: 6 = 0.54 f. 0.06 mm s-l, A = 1488 & 15 MHz. The evaluation of the resulting line pattern proves that the substitution of H by I in cysteine leads to a stable S-I bond, thus excluding the formation of a disulphide bridge for cysteine in tobacco mosaic virus. An laaI Mossbauer emission study has been reported,63sThe after-effects of Auger ionization in diphenyl [12smTe]telluride,dibenzyl [12smTe]telluride,and their dispersions in a solvent at 4.2 K were compared. Three species were observed in the two compounds, I-, Phl, or PhCH,I, and the third one was tentatively identified as Ph,I+ or (PhCH,),I+. The formation of I- represents complete fragmentation of the molecule. Cuesiurn (133Cs).As a method of studying vacancy migration in metals Verbiest and PattyrPO have used l " T s Mossbauer spectroscopy. The spectra show which fractions of implanted lsaXeatoms have trapped a certain number of vacancies. Changes of these fractions at certain annealing temperatures are due to migrating defects. This method to study damage recovery, and especially vacancy migration, is illustrated for M o and Pt. Transition-metal Elements.-Nickel ( 61 N i). The exper i men tal Mossbauer centre line shift includes contributions from the isomer shift, the second-order Doppler effect, and the zero-point motion shift. For the "Ni Mossbauer effect the isomer shift is very small and consequently is of the same order of magnitude as the second-order Doppler shift, and the data must be corrected for this effect. Shifts corrected for second-order Doppler effects were used along with measurements for a range of nickel compounds of the variations in the electron-capture decay rate of 57Ni nuclei in differential ionization chambers. The results gave a first estimate of the value of A < r2> for 'j1Ni of -(8 k 4) x lo4 fm2.The nickel compounds studied in this work, benzoate, oxalate, and oxide, had shifts of -6 -f. 3, -6 k 3, and - 19 ? 9 ym s-l, respectively, from nickel metal.641 A method of obtaining the Mossbauer parameters of the poorly resolved glNi spectra using complete transmission integral rather than the sum of Lorentzian methods was described, and graphs were produced to show when use of the former method is necessary.6oi'

Zinc ("Zn). The s7Zn Mossbauer effect was the subject of a review article published during the year.642The 67Zneffect has also been used as a sensor probe in measurements of subatomic displacements. The sensor was used to determine the linearity and hysteresis of a piezoelectric PZT-4 transducer at very small displacement amplitudes, and the performance of the transducer at 4.2 K was shown to be adequate for use as a high-precision y-resonance velocity Nath, C. Sauer, and A. Halpern, J . Chem. Ph.vs., 1983, 78, 5125. E. Verbiest and H. Pattyn, Point Defects Defect Interact. Met., 5th, 1981, 1982, 485. 5 2 8 . u4l J. Ladriere, M. Devillers, and A. Meykens in ref. 1 , p. 786. 642 T. Katila and K. Riski in ref. 5, p. 119. 643 E. Ikonen. P. Karp, T. Katila, and K. Riski, J . Phys. E, 1983, 16, 875. 639 A.

640


353

The 93.3 keV Mossbauer transition in 67Znwas used by Potzel et a/.644to investigate the anisotropy of the Lamb Mossbauer factor in hexagonal Zn metal. They found that the mean-square displacements along and perpendicular to the c-axis were 0.0037 and 0.00226 A2, respectively. Vetterling and Candela a recursion method that they used to describe the dynamics of disordered lattices and to calculate the properties of isotopically disordered Zn. They described Mossbauer-effect calculations for the high-resolution s7Zn isotope, including descriptions of the variation in shift with temperature and of the Goldanskii-Karyagin effect. A description of the effect of the zero-point motion on the Mossbauer resonance line-positional and linewidth parameters for isotopically disordered Zn was also presented. Because of the high Q value and narrow natural linewidth, the 93.3 keV s7Zn Mossbauer resonance is the best isotope to use for accurate energy-shift measurements. A liquid He cryostat has been designed646for gravitational redshift experiments, the red shift being measured uni-directionally between the reference absorber close to the source and the main absorber 1 m from the source. The spectra obtained from ZnO absorbers in a red-shift experiment were least-squares fitted to Lorentzian lines with the same linewidth constrained for both spectra. The results obtained from the red-shift measurements were shown to be in accordance with Einstein's equivalence principle. Tantalum (lelTa). Mossbauer experiments were carried out with a protonirradiated lelW (W) source consisting of lS1W implanted in W metal. The implanted metal has a shift of 0.836 k 0.005 mm s-l and a linewidth of 0.091 k 0.005 mm s-l at ambient temperatures when measured against a Tametal absorber.647The source was also used to study the effects of implanted H in the metal by proton irradiation with 90 keV energy. A proton-irradiation dose dependence of line broadening accompanied by a decrease in shift was found up ~~~ to the limiting solubility of H in tungsten; Gonser and his c o - w o r k e r ~have used a quadrupole-relaxation model to explain diffusion of hydrogen. The influence of the irradiation of Ta metal with 10 MeV protons and of the subsequent annealing processes on the Mossbauer parameters of le1Ta in Ta metal have been ~ t u d i e d . ~ ~ ~ degree ~ ~ ~of~disorder T h e of the metal structure near primary knocked-out atoms was higher than throughout the rest of the sample. In the high-resolution Mossbauer resonance of lelTa 6.2 keV y-rays in 2H-TaS2 and 2H-TaSe2 the nuclear transitions k 9 + f and k Q -+ L $ are completely resolved from one another, and this has resulted651in the determination of a new and highly accurate value for the quadrupole-moment ratio W. Potzel, U. Naerger, T. Obenhuber. J . Zaenkert, W. Adlassnig. and G . M. Kalvius. Phys. Lett. A , 1983, 98, 295. 645 W. T. Vetterling and D. Candela, Phys Rev. 8, 1983, 27. 5394. 816 K. Riski, P. Helsito, T. Katila, and J. Yla-Jaaski in ref. 1, p. 783. 847 A. K. Zhetbaev, A. N. Ozernoi, B. G. Akhmetova. and M. K . Akchulakev in ref. 1, p. 386. 648 N. Blaes, A. Blasius, U . Gonser, and R. S. Preston in ref. 1, p. 819. A. K. Zhetbaev and A. N. Ozernoi, Phys. Status Solidi A, 1983,77, 63. 650 A. K. Zhetbaev and A. N. Ozernoi. In. Akad. Nauk Kaz. SSR, Ser. Fiz.-Mater. 1983. 6 . 661 M. Eibschuetz, D. Salomon, and F. J. Disalvo, Phys. Lett. A, 1983.93. 259. 644

354


Q(t)/Q(:)of 1.1315 f 0.0002. The best experimental linewidth obtained in the study was 0.145 k 0.006 mm s-l. The literature discrepancy between Mossbauer and TDPAC measurements of the e.f.g. at Ta in 2H-TaS2 has been The discrepancy was shown to be an artifact of the methods used, and combination of both results gives a new value for the quadrupole moment Q(#) = 2.36 derived. A double nuclear magnetic resonance spectrometer suitable for studying the effect of high-frequency magnetic fields ( 2 . 2 4 . 6 MHz) in the Mossbauer spectra of lelTa was constructed.s63The maximum amplitude of the radiofrequency magnetic field possible was 360 Oe in a sample volume of about 0.5 cms.

+

Osmium (18eOs).The Mossbauer spectrum of an 18 wt. % 0 s in Fe alloy was obtainedss4at 4.2 K using enriched lesOsto permit measurement of the 155 keV lseOs effect. The parameters derived from the spectrum were I? = 0.38 mm s-l, gHhr= (3.90 k 0.33) x lo5 Oe, and Hhf= - 1.33 f 0.14 MOe, using a value of g = 0.28 obtained from angular correlation precession methods. The major source of the hyperfine fields at the 0 s nuclei in iron was said to be conductionelectron polarization, that is a Fermi-contact interaction with spin-polarized conduction electrons. Iridium (lQIIr).The results of Mossbauer-effectstudies on Ir-containing materials have been and the use of the effect to study the interaction of hydrogen with substitutional solute metals is considered.514 Gold (lQ7Au).Gold-197 Mossbauer parameters were obtainedsss for the compounds Z[AuR,] (R = Ph, Z = [NBu,]+, [AgC4H8S]+,[Au(SbPh,),]+, or [Au(pdma),]+ [pdma = o-phenylenebis(dimethylarsine1; R = CsF3H2, Z = [NBu4]+,Ag+, or [Ag(C,H,S)]+}. For derivatives of the same cation the isomer shift and quadrupole splitting are both slightly smaller for R = Ph than for CsF3H2in accordance with their electronegativities. Both [Au(pdma),]+ and [Au(SbPh,),]+ are known to be four-co-ordinate, and the Mossbauer parameters are consistent with this. The isomer shifts are extemely low and lie in the range observed for other four-co-ordinatecomplexes (-0.4 to -2.0 mm s-l). The lack of observable quadrupole splitting indicates structures close to tetrahedral. In [ A ~ ( s b P h & ~the ] + bond angles are regular, but there is some variation in the bond lengths (2.59-2.67 A). Such a slight distortion has no discernible effect on the Mossbauer spectrum, and a single line of normal width is seen. The [Au(pdma),]+ salt gives a much broader line (ca. 2.8 mm s-l), which can be fitted as a doublet with a splitting of about 1.1 mm s-l. In this cation the small

T. Butz and A. Lerf, Phys. Lett. A , 1983, 97, 217. S. M.Cheremisin and A. Yu. Dudkin, Prib. Tekh. Eksp.. 1983, 2, 29. 664 Y. W. Chow and L. Grodzins in ref. 1, p. 598. F. E. Wagner in ref. 5, p. 13. ss6K. Moss, R. V. Parish, A. Laguna, M. Laguna, and R. Uson, J. Chern. SOC., Dalton Trans., 1983, 2071. 6J4

663


355

bite of the chelating ligand gives a distorted tetrahedral geometry with AsAuAs bond angles of 87" and 122" and produces a non-zero electric-field gradient at the gold nucleus. For anions with two-co-ordinate Au there is said to be a well established relationship between the shift and the splitting, both parameters increasing with increasing donor power of the ligands. For a-bonded organic ligands high values of the parameters are expected, and those for the anions in the compounds studied, viz. [Au(C,F,)]-, and [Au(C,F,H,),]-, have shifts in the range 3.98-5.47 mm s-l and splittings of 8.63-10.92 mm s-l. The parameters for the fluoraryl derivatives show a systematic variation with the cation decreasing in the order mBu,]+ > [Ag(C,H,S)]+ > Ag+, which is consistent with previous observations that the parameters for the compounds [Z,Au,(C,H,Y),] decrease in the order Z = Li > Cu > Cu,X (X = I or O,SCF,). Structural information on eleven Au' thiolates and twelve phosphine-coordinated Au' thiolates has been collected using Mossbauer The compounds studied included the injectable anti-arthritic drugs gold sodium thiomalate (7), gold thioglucose (8), and gold sodium thiosulphate (9). The data are listed in Table 4. ROCH, Na0,CCHSAu NaO,CCH,

OR (7)

(9) R

=

0 II MeC

Compounds 1 and 2 in Table 4 are the same chemically as 6 and 7, but both the latter cases are used therapeutically. The observed spectra were all quadrupole doublets, and a linear relationship between the shift and splitting parameters was found. The spectra of compounds 1-9 are typical of Au' thiolates in that they have asymmetric spectra with the high-velocity line being broader and of smaller intensity than the low-velocity line, although the peaks are of approximately equal area. The spectrum of compound 15, auranofin, is typical of that of the other phosphine-co-ordinated Au' thiolates (compounds 12-23). The X-ray structure of bis(ethy1enethiouronium)Au' chloride, compound 24, has the Au atom bound to two S ligands with a considerable deviation from linearity ( LSAuS = 167"). The y-resonance data for the compound in which the Au moiety is cationic ( 6 = 1.52, A = 7.22 mm s-l) fall within the range observed for Aul thiolates. In contrast, the gold portion of compound 11 is anionic and its X-ray structure shows the presence of nearly linear twoco-ordinate Au. The Miissbauer parameters for the compound are, however, also consistent with the other Au' thiolates (compounds 1-10). An example of a neutral complex is 667

D. T. Hill, B. M. Sutton, A. A. Isab, M. T. Razi. P. J. Sadler, J. M. Trooster, and G . H. M. Calis, Inorg. Chcm., 1983, 22, 2936.

356


Table 4 lQ7AuMfisshauer datci Compound no.

8/mm s-'

J/mm s-'

I .74 1.72 I .74 2.10 2.23 I .4

6.5 6.50 6.48 6.78 7.03 6.1

1.40

6.20

8 AUSCK~CH(NH~)CO~H 9 AuSCH,CH(NHAc)CO,Na 0 AuSCMe2CH(NH2)C02H* HCI 1 [Au(S,O,),lNa, 12 Et,PAuSCH(NH,)2+CI 13 Et,PAuSCN 14 Et ,PAuSCOPh 1 5 Et ~PAuSCHOCH(CH~OAC)(CHOAC)~CHOAC

I .58 I .67 I .82 I .92 2.9 3.04 3.51 3.55

6.18 6.33 6.68 6.98 7.6 7.73 8.53 8.64

16 E~~PAuSCHOCH(CH~OH)(CHOH)~CHOH

3.44

8.43

I 7 Ph,PAuSCHOCH(CH2OAc)(CHOAc),CHOAC

3.4

8.4

18 E~~PAuSCH(CO~H)CH~CO~H 19 Et ~PAuSCH~CH(NHAC)CO~H 20 Et,PAuSMe

3.76 3.48 3.41

8.79 8.39 8.23

3.42

8.25

3.18

8.2.

3.26

8.15

Complex

1 AuSCH(C0,-Na+)CH,CO,-Na+ * H 2 0

2 3 4 5 6

AuSCH(C02-Na+)CH2C02-Na+. 2H20.0.3C3H,0, AuSCH(C02-Na+)CH2C02-Na+* NaCl AuSCH(C02-Na+)CH2C02-Na+0.5C4H,0,S AuSCH(C02-Na+)CH2C02-Na+.2C,H,O,S

AuSCHOCH(CH~OH)(CHOH)~YHOH

7 AuSCHOCH(CH,OH)(CHOH)~CHOH * H?O

Et, P(CH,),SAu 21

I I Au S(CH,), PEt,

provided by the dimer Au'dipropyldithiocarbamate [Pr,NCS2AuJ2. Again the bonds and the Mossbauer parameters are again crystal shows linear S-Au-S similar to those for compounds 1-1 1. Co-ordination of a 1 : 1 Au' thulate with phosphine ligands increases substantially the magnitude of both the shift and the splitting (compounds 14-23). This is seen directly in three specific examples where the Au' thulate in each case has been complexed with Et,P. Comparison of the shift and splitting for each pair shows an increase of approximately 2 mm s-l on complexation with the phosphine. These increases are due to the strong c-donor-x-acceptor properties of phosphorus, which lead to higher 6s-electron density at the gold nucleus


357

relative to sulphur. However, the values observed are somewhat higher than might be expected on the basis of an average-environment rule, particularly for auranofin. The shift and splitting values of auranofin (compound 15) (3.55 and 8.64 mm s-l) are closer to the values observed for chlorobis(triethy1phosphine)gold (3.06 and 8.93 mm s-l) than those observed for the polymeric gold(1) thiomalate (compound 1). Again this can be explained partly by the fact that the gold-sulphur bond distances in the polymeric gold@ thiomalates are probably longer than those in the monomeric gold-sulphur species, resulting in the loss of o-donor capacity of the sulphur ligand and a corresponding reduction in the Mossbauer parameters. The increasing shift and splitting values of those compounds with a thiomalate-to-gold ratio higher than 1 (compounds 4 and 5) are further evidence for this effect. The structure of compound 15 shows the Au atom to have a marked preferential orientation toward the pyranose-ring oxygen, suggesting a possible influence of the thioglucose ligand. However, the SAuP bond angle (176") and the AuO distance (3.41 A) both indicate that any gold-oxygen interaction must be negligible. Compound 17 contains the triphenylphoshine ligand, which, because of its larger size, would reduce or preclude Au-0 interaction. However, the Miissbauer parameters of compound 17 do not differ significantly from those of compound 15. Further comparison with compound 20, which has no oxygen atoms, again indicates little difference. Thus, the magnitude of the Mossbauer parameters in compounds 14-23 must be intrinsic to the SAuP linkage. The decrease in the Mossbauer parameters of the thiouronium salt, compound. 12, and the thiocyanate, compound 13, relative to the other two-co-ordinate (phosphine) gold(x) thiolates is noteworthy. In both compounds the sulphur atom is bound directly to an electronegative group that withdraws electrons from sulphur, reducing its donor capability. Consequently, the density of 6s-electrons at the gold nucleus is diminished, resulting in smaller shifts and splittings (Table 4). In compound 14, the S-benzoyl compound, the electronegative effect of the carbonyl is compensated for by the phenyl, which, by virtue of its x-system apparently donates electrons to the carbonyl rather than to the sulphur. Aromatic groups tend to be slightly electronegative, and this is seen in the Mossbauer measurements of compounds 22 and 23, where the magnitudes of the shifts and splittings are reduced compared to those of compounds 15-21. The effect of various substituents on the le7AuMossbauer parameters in this class of compounds deserves further investigation. The large-ring digold compound 21

&

&

was of special interest because it contains two linkages. The bonds are slightly bent (173.5"), and the gold atoms are directed in towards each other. The Au-Au distance of 3 . 1 0 A is considered within the range for Au-Au bonds but is somewhat weak at the distance cited. Because of the increased electronic charge perpendicular to the co-ordination axis arising from a Au-Au bond, the magnitude of the splitting should be reduced compared to that of other compounds in its class. However, the data for compound 21 are typical for phosphine-co-ordinated gold(1) thiolates and differ little from those of compound 20. Therefore, within the sensitivity of the Mossbauer experiment no evidence for Au-Au bonding is observed.

358


The trimeric gold(x) azolates Au,(az), [az = 3,5-Me2-pz (pz = pyrazolato), 3,5-Me2-4-I-pz, or benzo- 1,2,3-triazolato (btaz)] were studied by y-resonance The data for Au,(3,5-Me2-pz),I2, Ph,PAu(btaz), and Ph,PAu(3,5-Me2-pz) were also reported, and the following conclusions were drawn : (i) the chemical state of the three Au atoms in the Au,(az), compounds is identical, and (ii) both Au' and Au"' are present in Au,(az),T,. Both s7Feand le7Au Mossbauer data were obtaineds5, for the series of compounds RAuPPh, and [R(AuPPh,),]BF4 (R = aryl). The parameters for [(C,H,)Fe(C,H,)(AuPPh,),]BF,, were shown to be consistent with the presence of Au' and of ferrocene-like Fe" bonding. The compound [Au,(PP~,)~](NO,),- 2CH2C12has been prepared and characterized by a variety of physical measurements, including a complete X-ray structure analysis.ss0The [Au8(PPh3),l2+cation consists of a central Au atom surrounded by seven peripheral Au-PPh moieties and has Au(centra1)Au(periphera1) bond distances of 2.63-2.72 8, and Au(periphera1)-Au(peripheral) distances of 2.71-2.94 A. This Au skeleton can be described as being derived from the regular A ~ 1 3cluster by removing two and three atoms, respectively, above and below the centred hexagon. The centred hexagon is a common feature of all gold clusters containing 8, 9, 11, or 13 Au atoms and explains the close relationship between Au, and Au, clusters. The similarities in the nature of Au atoms in the Au, and Au, clusters are confirmed by their lo7Au Mossbauer parameters. The spectra for [Au,(PP~~)~](NO,), and [Au8(PPh,),](NO,), consist of quadrupole doublets with shifts from a ls7Pt source of 6.6. and 6.9 mm s-l, respectively; the corresponding splitting parameters are 2.1 and 2.4 mm s-l. In both cases the spectra are said to arise only from peripheral Au atoms with no resolvable contributions from the central atom. The shift and splitting parameters (6.7 and 1.9 mm s-l) for the peripheral Au atoms in [Au,(PPh,),](PF,), - 2CH2C1, are similar to those for other peripheral Au atoms, but in this case a singlet resonance line at 2.4 mm s-l attributed to the central Au atom is also found. The reaction of AU,(PP~,)~(~-I,) with Ph2PCH2PPh2in THF results in the immediate precipitation of A u ~ ( P ~ , P C H , P P ~ , A ) ~crystal-structure I~. determination on the product showed that the Au skeleton was a slightly distorted tetrahedron with Au-Au distances of 2.72-2.95 A. One of the Au atoms is bonded to I at 2.59 A, whereas the other three Au atoms are surrounded by three bridging ligand groups, giving Au-P distances of 2.33-2.39 A, as well as by an I atom at rather long distances (3.13-3.67 8,). The differences in bonding for the two types of Au atom are confirmed by the presence of two sets of subspectra in the lB7AuMossbauer spectrum of the compound.881 Katada, K. Sato, Y . Uchida, S. Iljima, H. Sano, H. H. Wei, H. Sakai, and Y. Maeda. Bull. Chem. SOC.Jpn., 1983, 56, 945. ' I i o M. Katada, Y. Uchida, H . Sano, H. Wei, H. Sakai, and Y. Maeda, Radiochem. Radioanal. Lett., 1982,54, 5 5 . J. W. A. Van der Welden, J. J. Bow, W. P. Bosman, and J. H. Noordik, Inorg. Chem., 1983, 22, 1913. BB1 J. W. A. Van der Welden, J. J. Bour, R. Pet. W. P. Bosman, and J. H. Noordik, in or^. Chem., 1983, 22, 3112. R58 M.


359

The Au-197 spectra of the amorphous alloys Pd,,-,Au,Si,, (x = 5, 10, or 20) and Pdm-,,Au,,,Si, (y = 15, 16, 18, or 20) were fitted to doublets. The shifts varied from 1.80 to 1.06 mm s-l with increasing Au content and from 1.3 to 1.06 mm s-l with increasing Si content and were said to originate partly from the changes in the specific volume of Au but mainly from electron transfer from Si to the d-bonds of Au and Pd.e62 Strict compositional and structural short-range order has been deduced from the analysis of hyperfine interactions in rare-earth-gold albys of composition R E A U , ~ .For Eu&uso and G d d u , , the ls7Au data are consistent with a random orientation between the hyperfine- and quadrupolefield axes. The data for Dy,,,AuZoare similar, but because of the relatively small field acting at the Au nucleus a distribution of hyperfine fields cannot be ruled Lsnthadde and Actinide Elements.-The applications of the Miissbauer effects of isotopes of the lanthanide and actinide elements have been considered in a number of review articles. In a s u r ~ e y 8of~ both ~ experimental and theoretical results of y-resonance studies of the rare-earth elements and their intermetallic compounds the isotopes discussed included lr9Sm, ldlDy, lbeEr, 170Yb, l6Tb, 13?La, lS2Sm, lS1Eu, lSsGd, and l*oTm. A general review article on actinide Miisbauer spectroscopy was published,Bd6 and Friedtddehas discussed the principles and possibilities of using y-resonance spectroscopy to study actinide compounds with the isotopes 232Th, 231Pa,236U,238tj, 237Np,23sPu,,Vu, and 843Am. The uses of these isotopes to elucidate electronic structure and bonding, to study magnetism, and to follow phase changes were described. Other topics reviewed considered (i) lS1Eu and lelDy studies on magnetic interactions in superconductorsbe7and (ii) studies on the lattice dynamics of actinide intermetallic C O ~ ~ O U ~ ~ S ~ ~ ~ Samarium (lroSm). From model calculations carried out on the Sm3+ion under cubic crystal fields it is shown that the hyperfine interactions are fairly anisotropic, so the author has measuredbesthe interactions by laDSmMossbauer spectroscopy to obtain information about crystal-field parameters. Europium (lS1Eu,lS3Eu).lS1Eu Mossbauer experiments on EuCIS-AICl, graphite flakes and graphite samples were performedw0as a function of temperature at 4.2-300 K and indicated the presence of a narrow line characteristic of Eu3+; no evidence of Eu2+ was found. Eu-intercalated graphite EUCe was studiede70 by Mossbauer and L-edge spectroscopy. Results 6f isomer shift and LIII-edge H. Ino, K. Tokumitsu, S. Nanao, H. Sakai, and Y. Maeda in ref. 1. p. 363. J. P. Sanguez, M. Maurer, and J. M. Friedt in ref. 1, p. 353. S. P. Taneja and C. W. Kimball in ref. 4, p. 814. (146 W. Potzel, J. Moser, L. Asch, and G. M. Kalvius in ref. 5. p. 58. MO J. M. Friedt, Radiochim. Acta, 1983. 32. 105. e37 G. K. Shenoy in ref. 4, p. 561. MB P. Raj in ref. 1, p. 605. P. Boolchand, G. Lemon, W. Bresser, D. McDaniel, R. E. Heinz, P. C . Eklund, E. Stumpp. and G. Nietfeld, Mater. Res. SOC.Symp. Proc.. 1983, 20, 393. IJ'II G. Kaindl, J. Feldhans, U . Ladeing, and K. H. Frank, Phys. Rev. Lett., 1983, 50, 123.

Spectroscopic Properties o j Inorganic and Organometallie Compounds

360

position indicate the divalent state for Eu. The large e.f.g. at the Eu site ( - 1 . 4 ~1Ol8 V cm-2), with axis parallel to the c-axis, is consistent with the structure of EuC, and partial charge transfer from Eu to C planes. Several Schiff-base complexes containing 151Eu metal ion have been sythesized,B71and their Mossbauer spectra have been studied. From systematic analysis of the quadrupole-coupling constants and isomer shifts, the co-ordination number of the metal ion in each complex was assigned. The 151Eu isomer shifts found in various divalent Eu compounds were a n a l y ~ e d by , ~ ~means of the model proposed by Miedema and Van der Woude (1980) for the lg7Auisomer shift in Au-base materials. Relative changes of 5d- and 6s-electron occupation numbers due to alloying of divalent Eu with other elements were deduced from this analysis, and lalEu y-resonance spectroscopy has been to study the valence state of Eu in Eu,B, in the pressure range 0-130 kbar. Isomer-shift values indicate that the Eu ions remain in the divalent state under these conditions. There is an increase in isomer shift with pressure, i.e. an increase in s-electron density at the Eu nucleus. From the data at 4.2 and 1.7 K at ambient pressure and at 130 kbar the saturation hyperfine field was found to be -21.4 T and -20.4 T, respectively. Mossbauer measurements were carried on Eu4As3at 300 and 77 K using a la1SmF3source in a study of the crystallographic distortion. The isomer-shift data of $0.5 mm s-l and -10.80 mm s-l (with respect to EuF,) indicate that both Eu2+ and Eu3+ ions are present in Eu,As,. Results of lslEu Mossbauer spectroscopy, magnetization, and resistivity measurements show a competition of long-range ferromagnetic and short-range antiferromagnetic exchange in f.c.c. YbEu alloys, leading to complex magnetic behaviour especially for low Eu concentration^!^^ A Mossbauer spectroscopic study of an anhydrous nonstoicheiometric europium(II1) chloride phase was carried Temperaturedependent spectra provided, for the first time, evidence for electron exchange between neighbouring Eu sites in a non-stoicheiometric Eu compound. The activation-energy value for electron mobility above 200 K is 0.083 f 0.003 eV for EuCI,.,, from electrical-conductivity measurements and is consistent with that derived from the Mossbauer spectra using an electron-hopping model. Chemical-isomer shifts and ratios of recoil-free fractions for Eu" to Ed1'were also derived from the spectra. The magnetic properties of Eu2+-based(4f7 electronic configuration) amorphous alloys Eu,-,X, (X = Mg, Zn, Cd, or Al, x z 0.3) have been investigateda7' by studying local moments from 151EuMossbauer spectroscopy and bulk magnetization in low a.c. and high d.c. fields. The divalent 4f7 state of Eu atoms implies vanishing interactions with crystal fields. The magnetic properties are then assumed to be depicted by localized 4f moments interacting via RKKY

-

671

A. L. Sharma, K. Reddy, A. Rama. and N. Ahmed, J. Phvs. SOC. Jpti., 1983, 52, 81. J. W. C. Vries, R. C. Thiel, and K. H . J. Buschow, Phvsico B ' C (Amsterdnm), 1983. 121,

674 675 676

loo.

M. Abd-Elmeguid. J. P. Sanchez, and H. Micklitz J . Phys. C, 1983, 16, L543. R. Nagarajan, E. V. Sampathkumaran, R. Vijayaraghavan, and R. Bhaktdarshan, Phys. Status Solidi A , 1983, 75, 149. V. Oestreich, G. Czjzek, H. Schmidt, and F. Gotz in ref. 1, p. 485. J. Ball, C. M. Jenden, S. J. Lyle, and W. A. Westall, J . Less-Common Met., 1983, 95, 161. M. Maurer and J . M. Friedt, J . Phys. F, 1983, 13, 2175.

1173M.


361

interactions, in view of the pure s (Mg, Zn, Cd) or sp (A]) character of the valenceelectron shells of the components. In another paper Maurer et al.678 report on the structural short-range order in amorphous rareearth alloys. By combining lelEu Mijssbauer spectroscopy (on the Eu2+S-state ion) and e.x.a.f.s. (extended X-ray-absorption fine structure) measurements in a series of amorphous compounds RE,-,X, (RE = rare-earth, X = 'sp'-metal) the authors have investigated the angular correlations and the radial distribution functions (RDF) of the local atomic arrangement restricted to the first-neighbour shell. The shape of the first peak of the partial RDF centred on the major (RE) and on the minor ( X ) atomic components is asymmetric, with the extent of asymmetry depending upon the element X. No significant structural change is detected as a function of the rare-earth element, including rare-earths with different valence (Eu2+, Gd3+).The degree of structural short-range order is evaluated consistently from the e.f.g. distribution and from the asymmetry of the RDF as determined from e.x.a.f.s. The decrease of the short-range order in the sequence Au, Ga, A1 is correlated with a decreasing enthalpy of formation of the corresponding crystalline compounds. On the other hand, no clear relationship can be established between short-range order in amorphous and crystalline phases. Strict compositional and structural short-range order was deduced from the hyperfine interactions in Eu8o AU,~.The lSIEuspectra above T , show a unique quadrupole pattern with 6 = 9.90 mm s-l from Sn203and eqQ = +17.8 mm s-' at 245 K. At 4.2 K, however, the data are best interpreted in terms of a random orientation between the magnetic-hyperfine axis and the quadrupole a ~ i s . 6 ~ ~ By simultaneously applying pressures of up to 19.6 kbar and magnetic fields of up to 13 T, the magnetic-hyperfine fields of the Eu-monochalcogenides and Eu,Sr,-,S were studied using lalEu Mossbauer ~ p e c t r 0 ~ ~ 0 pThree y . 6 ~papers ~~~~~ report Mossbauer studies of EuFe,PlZBs1and EuX,P, (X = Fe, Co, or Ni)682~eet materials. Both s7Feand lslEu Mossbauer spectroscopieshave been used to study the properties of the two potential origins of magnetism in EuFe,P,,. lS1Eu parameters were obtainedee1in the temperature range 4.2-300 K in an applied field. Unusual (Eu-151)2+hyperfine parameters were reported, the low-temperature saturated hyperfine field ( H = -670 kOe) is large, and an isomer shift (-6.0 mm s-l) indicates a high electron density. The ferromagnetic ordering temperature (100 K) is high in spite of (a) the large Eu2+-Eu2+ distance (6.8 A) and (b) the fact that the Fe has no localized magnetic m0ment.f-d-Band coupling is of importance when explaining the high hyperfine field. From the ~ t ~ d i e s ~ on the compounds Eu2X2P2(X = Fe, Co, or Ni) the Eu ions in EuCo,P, and EuFe2P2are found to be in the divalent state and magnetically ordered at low

...

M. Maurer, J. M. Friedt, and G . Krill, J . Phys. F, 1983, 13, 2389. C. Sauer, A. M. Zaker, and W. Zinn, J . Magn. Magn. Muter., 1983, 31-34, 423. C. Sauer, A. M. Zaker, and W. Zinn, J. Magn. Magn. Muter., 1983,38,225. 481 A. Gerard, F. Grandjean, J. A. Hodges, D. J. Braun, and W. Jeitschko, J . Phvs. C, 1983, 16, 2797. w2 R. Nagarajan, E. V. Sampathkumaran, L. C. Gupta. and R. Vijayaraghavan in ref. I , p. 602. 883 R. Nagarajan, E. V. Sampathkumaran, L. C. Gupta. R. Vijayaraghavan, and G . K . Shenoy, J. Magn. Magn. Muter., 1983, 31-34, 757. 678

+jfg

362

Spectroscopic Properties of Inorganic and Organomefallic Compounds

temperatures, whereas the Eu ions in EuNi,P, are in the intermediate valence state, and the linewidth of the 151Eu Mossbauer spectrum exhibits an unusual temperature dependence. Valence instability in EuPd, caused by Si addition has been followed by These studies show that in Mossbauer and susceptibility E U P ~ , S ~ , ,the . ~ ~Eu ions undergo valence fluctuations. The effects of pressure and temperature on the mean valence of EuPd,Si, have also been investigated.BsS The Mossbauer shifts at T = 4.2-296 K and p = 0-53 kbars were recorded, and the results were used to derive the mean valence of Eu. New alloys of formula EuPd,B, (0 < x < 1) have been prepared.s8sThese alloys are observed to have the same crystal structure as EuPd, but with an expanded cell volume. lSIEu Mossbauer studies on EuPd,B, alloys show that the valence of Eu (which is trivalent in EuPd,) changes as a function of boron concentration. In EuPd,B the temperature dependence of the Mossbauer spectrum suggests that the Eu ions undergo a charge ordering. Mossbauer measurements on EuRh,B, have indicatedss7that Eu is in the trivalent state and therefore non-magnetic. However, the compound EuRh,B, orders magnetically at 40 K, and it is concluded that the magnetic ordering is of the itinerant type and is associated with the Rh d-band. Measurements of lslEu Mossbauer isomer shiftsss8in the alloys La,Eu,-,Pd,Si, ( x = 0.3 or 0.5) suggest the presence of both divalent Eu and Eu ions with fluctuating valence in these alloys. The intensity of the resonance exhibits an unusual temperature dependence in both alloys, and the origin of this anomaly is attributed to the valence-fluctuation phenomenon. The valence state of the Eu (RE = La or Ce) was investigatedsss ions in the compounds through isomer-shift measurements, using the 151Eu Mossbauer effect. The spectra were recorded in the range 80-300 K, and the temperature dependence of the isomer shift (and hence the average valence) was found to be weaker than that observed in EuPd,Si,. A temperature-independent weak line, corresponding to the Eu2+state, was also observed. to study magneticBoth the Fe-57 and Eu-151 effects have been exchange interactions in the orthorhombic perovskite solid solutions EuFe,-,Co,O, (0 G x G 1). The 151Euspectra were broad single lines with linewidths of about 3 mm s-l in samples with x > 0.5. For samples with x = 0.1-4.4 below the Curie temperatures, however, the widths were considerably greater at about 4 mm s-l. In the perovskite lattice each Eu site experiences exchange fields from four equivalent pairs of Fe sites. Exchange interactions can then only take place by direct cation-cation overlap or indirectly via the oxygen. Mossbauer-source experiments on dilute 15aEuand 57Fein SmCo, and on w4 S. K. Dhar, R. Nagarajan, S. K. Malik, D. Rambabu, and R. Vijayaraghavan, J . Magn. Magn. Muter., 1983, 31-34, 393. 686 G. Schmiester, B. Perscheid. G . Kaindl. and J. Zukrowsky, Valence Instub., Proc. Inr.

Conf., 1982,219. S. K. Dhar, R. Nagarajan, S. K . Malik, and R. Vijayaraghavan in ref. 1, p. 595. w7 S. K. Dhar, R. Nagarajan, S. K. Malik. and R. Vijayaraghavan in ref. 1, p. 792. E. V. Sampathkumaran, R. Nagarajan, and R. Vijayaraghavan, J . Less-Commorr Met.. 1983, 94, 195. RRs R. G. Pillay, E. V. Sampathkumaran, H. G. Devare, L. C. Gupta. and R. Vijayaraghavan in ref. 1, p. 592. 680

Mdssbauer Spectroscopy

363

lS3Euin S ~ , ( C O ~ - , F ~ ,and ) ~ , Sm,Co,M, (M = Fe, Cu, Zn, or Zr) at 4.1 K have been performed;eg0from the experimentally measured magnetic-hyperfine fields alone, approximate values for the exchange fields in the mixed systems Sm,Co,M, were determined.

Gadolinium (lSsGd).X-Ray, resistivity, magnetization, and Mossbauer studies691 of dilute probes of Fe-57 and Gd-155 in CeMn6A16have indicated that Ce in CeMn,Al, is in a mixed-valence state. The results are interpreted in terms of interconfigurational fluctuations between Ce4+and Ce3+. Results of Fe-57, Gd-155, and Er-166 Mossbauer-effect measurements have been presentedss2for Gd,Fe,Si, and Er2Fe,Si,. There is no magnetic moment on Fe. The Gd Mossbauer results are used to construct an approximate model of the crystalline electric-field effects in the heavy rare-earth members of the R,Fe3Sis family. This model predicts large magnetic anisotropy in the materials and explains the well developed static-hyperfine interaction Seen in the Er spectra up to 4.2 K. Noakes et al!s3 have also reported the magnetic-transition temperatures and 67Fe, lSsGd, lWEr, and 170Yb Mossbauer data for REFelSia (RE = Gd or Lu). The lSsGd quadrupole interaction in GdFe,Si, is used to derive a crystalline electric model for the magnetic behaviour of the other members of the series and to interpret the 166Erand 170YbMossbauer data. In another papeP4 Miissbauer and magnetization studies on RFe,AI, (R = Y or Sm-Lu) in magnetic fields of up to 50 kOe and over the temperature range 4.1-500 K are described. A laSGdMossbauer study on GdFe6A1, reveals only one Gd sublattice with its magnetization pointing at -40" relative to the tetragonal four-fold axis. At 77 K the parameters are 6 = 0.40 mm s-l, A = -30 mm s-l, and a hyperfine field of 277 kOe. The low-temperature hyperhe parameters of the ferrimagnet Hoo.osCe,Gd0.,,-,Fe, are measured using the 87 keV y-rays of Gd-155 Mossbauer spectros c ~ p yA. linear ~ ~ ~ decrease of the hyperfine field B, is observed with increasing x. The slope of the line is nearly three times greater than that found for Gd-155 in the analogous Ho : (Y,Gd)Fe, systems; this is attributed to the influence of the increased conduction-electron density when GdS+is replaced by Ce4+. The lS5Gddata for GdaoAuzohave been interpreted in terms of a random orientation of the magnetic hyperfine and quadrupole axis, a nearly axial eqQ of 4.65 mm s-l, and a unique shift of -0.23 from a SmPd, source. Dysprosium (181Dy).A study has been made of divalent and trivalent dysprosium halides and oxyhalides using the lalDy Mossbauer effect. A value of A = 1. Nowik, 1. Felner. M. Seh, M . Rakavy, and D. 1. Paul, J . Mugn. M o p . Muter.. 1983. 30,295. I. Felner and I. Nowik, Valence Instub., Proc. Int. Con$, 1982, 489. 69* D. R. Noakes, G . K . Shenoy, D. Niarchos, A. M. Umarji, and A. T. Aldred, Phys. Rev. 8. 1983,27,4317. 693 D. R. Noakes, A. M. Umarji, and G. K. Shenoy, J . Mugn. Magn. Muter., 1983.39, 309. 694 1. Felner, I. Nowik. and M. Seh, J . Mugn. Mugn. Mnter., 1983.38, 172. 0.Prakash, M. A. Chaudhry, J . W. Ross. and M. A. H. McCausland, J . Mqen. Mnyn. Muter., 1983, 36, 271.

364


8.0 x fm2was deduced from a combination of isomer-shift data and free-ion electron-density calculations.696The spectrum for DyBr, at 4.2 K is a single resonance line with a shift (-5.6 mm s-l from DyF3) that is characteristic of Dy2+.At 300 K the spectrum can be fitted to two resonance lines of which one has a shift of -5.6 mm s-l attributed to Dy2+and the other a shift of 0.9 mm s-l due to Dy3+. The spectrum obtained at 77 K can also be fitted to these components. The progressive degree of asymmetry appearing in the spectrum of DyBr, with increasingtemperature is therefore indicative of increasing proportion of Dy3+in the lattice. The spectrum of DyI, at 4.2 K is also a singlet, but it does show a weaker magnetic component. The width and asymmetry of the resonance line do, however, also increase with increasing temperature. The spectra can be fitted to three subspectra arising from Dy2+and from Dy3+in DyOI and Dy13. The parameters for the mixed-valence chloride Dy5Cl11can be interpreted as a superposition of two quadrupole-split spectral components of equal isomer shifts, 6 = -5.8 mm s-l (about 70% of the total resonance area), and of a magnetic-type subspectrum, 6 = 0.8 mm s-l. The unusual isomer shift of -5.8 mm s-l for the quadrupole subspectra is attributed to divalent dysprosium ions; the magnetic contribution arises from slowly relaxing Dy3+ions. At higher temperature (T 2 77 K) a progressively increasing contribution of Dy3+confers overall asymmetry to a broad resonance line. Owing to the relaxation behaviour of the Dy3+ion, the spectral shape at 77 K is complex, and analysis of the data becomes unreliable. The room-temperature spectrum can be satisfactorily represented as a sum of two single Lorentzian lines, the trivalent contribution being predominant and the divalent component appearing as a shoulder of about 42 % relative intensity. According to extensive X-ray diffraction studies Dy,CIll can be classified as a mixed-valencecompound, with Dy2+:Dy3+ = 4 : 1, where Dy2+and Dy3+ ions appear in both seven- and eight-co-ordinate sites. The observation of two subspectra for the Dy2+component is consistent with the crystal structure of Dy5Cl11,which has several crystallographicallynon-equivalent lattice sites. An estimate for the Debye temperatures (0,) of the two valence states in Dy5CIll is available by reference to the europium mixed-valence compound; in Eu,Cl, 151EuMossbauer spectroscopy provided values of 150 and 170 K for OD for the Eu2+ and Eu3+ sites, respectively. Direct application of these 8D values to the two types of ions in DyClll is insufficient to account for the observed temperaturedependenceof the Dy2+: Dy3+spectral-arearatio. However, the results as a whole can only be understood in terms of the impurity phase DyOCl for which OD is estimated to be z 300 K from the temperature dependence of the lslDy spectral area in the pure oxyhalide. The variations in the lslDy Mossbauer spectrum of the DyOX compounds (X = CI, Br, or I) are similar. The 4.2 K data for the chloride reveal well resolved magnetic spectra and are interpreted in terms of combined magnetic and quadrupole interactions. This behaviour is consistent with that expected for the Kramers ion Dy3+for which all crystalline electric-field states are at least doublets. The y-resonance data taken with other results suggest that the oxyhalides are antiferromagnets with transition J. M. Friedt, J. MacCordick, and J . P. Sanchez. friorg. Client.. 1983, 22. 2910.


365

temperatures of 9.5, 7.5, and 9.5 K, respectively, for X = CI, Br, or I. A Hamiltonian including crystal-field and magnetic-exchange effects was used to obtain a theoretical description of the effects producing the observed Mossbauer spectra of the Dy compounds. The magnetic behaviour of the Dy3+ion in single crystals of Dy,(SeO,), - 8H20has been studied.697X-Ray diffraction, magnetic measurements, and Mossbauer effects were used to prove the existence of the DyFe, phase and to characterize its magnetic The 57Feand lelDy studies at 4.2 K showed that there were two hyperfine fields with values of 930 and 827 MHz at the Dy atoms but only one field (214 kOe) at the Fe nuclei. The intermetallic phases DyMn, and Dy,Mn,, and their ternary halides have been studied by Mossbauer ~ p e c t r o ~ c o p y The . ~ ~results ~ showed that for Dy Mn, magnetic ordering disappears after charging with hydrogen gas and that absorption of hydrogen by Dy,Mn,, leads to a strong reduction in bulk magnetization even though the Dy sublattice remains magnetically ordered at low temperatures with magnetic moments on the Dy atoms close to the free-ion values. The following intermetallic and alloy phases have also been studied by lslDy Mossbauer spectroscopy: Dy,Fe,,-,Al, ( x = O-8L7O0 Dyl-xYxA12,701 and Dy80A~20.663

Erbium (lssEr). The lB6Erdata have been obtained for ErFe,Si, at 4.2-1.5 K, using a source of lS6Hoin Y0.6H00.4H2, and interpreted in terms of a model devised to explain the la5Gd data in GdFe2Si2.sg3The 80.56 keV y-rays of leeErwere also used in a study of ErZn.702Although 16,Er is not a suitable probe for obtaining electrical-quadrupole moments, measurements can be made of the magnetic-hyperfine field. The value obtained at 1.4 K was 5940 k 50 kOe, which, neglecting any contribution from conduction electrons, corresponds to g J < J z > = 6.6 pB, which is close to the calculated value of 6.8 pB. Thulium (ls9Tm).The Mossbauer parameters for le9Tmin TmPO, were used by Hodges703to obtain a set of crystal-field parameters for the rare-earth ion in the phosphate, and the results obtained were compared with those for TmVO,. The Mossbauer spectra of lseTm in TmMo,S, recorded between 4.2 and 300 K show a unique quadrupole doublet, which gives support to the fact that the Tm3+ ion occupies a single crystallographic site. The thermal variation of the quadrupolar-splitting and magnetic-susceptibilitymeasurements shows that the overall crystal-field splitting of Tm3+is below about 100 K.704

D. Neogy and J . Nandi, J . Phys. Chem. Solids, 1983. 44.943. Zarek, J . J . Bara, A. T. Pedziwiatr, M. Pardavi-Horvath, Z. Kucharski. and J. Suwalski in ref. 1, p. 947, 542. 6s9 P. C. M. Gubbens, W. Ras, A. M. Van der Kraan, and K . H. J. Buschow, Phys. Smtr4.a Solidi B, 1983. 117, 277. '00 J. Pszczoka, J. Zukrowski, J. Suwalski, Z. Kucharski, and M. Lukasiak, J. M o p ] . Mugn. Muter., 1983, 40, 197. '01 A. Hessel, G . M. Kalvius, G . K. Shenoy. W. Zinn. and W. Wiedemann. J . Magn. Magn. Muter., 1983. 31-34, 751. 70p J. A. Hodges, P. Imbert, G . Jehanno, and A. Schuhl in ref. I , p. 524. '03 J. A. Hodges, J . Phys. (Les Ulis, Fr.), 1983. 44, 833. 7n4 P. Bonville, R. Chevrel, J. A. Hodges, P. Imbert, G . Jehanno, and M . Sergent in ref. 1. p. 171. 697

ti@eW.

3 66


Both the magnetic properties and unit-cell parameters for Tm,Mn,, have been determined7OSbefore and after hydrogen absorption. The intermetallic phase is ferrimagnetic with an ordering temperature of 404 K. After hydrogen absorption there is a strong reduction in the magnetization, but the increasing hyperfine splittings found in the lsgTm spectra for the hydrides below 60 K do suggest that the Tm sublattice does become magnetically ordered in the hydrides.?OSThe intermetallic phase TmFe, readily absorbs hydrogen to form several hydride phases, and these have been studied using a number of techniques including the Tm y-resonance effect.706The spectra for TmFe2H, are consistent with a decrease in the hyperfine field from 720 T at x = 0 to 650 T at x = 3.7. The implied decrease in the Tm magnetic moment indicates a decrease in the ratio of exchange interaction to crystal-field interactions in x . This is also shown from the bulk-magnetization measurements by a decrease in the compensation temperature (the temperature at which Tm and Fe magnetic sublattices cancel each other) from 230 K for x = 0 to 9 K for x = 3.7. The values of the magnetic moments and e.f.g.s in TmNi, and TmCo, have been obtained by MossbauerThe spectra for both samples consist of superpositions effect of two magnetically split subspectra representing different Tm sites. The values of e2qQ in TmCo, obtained were 26.5 and 25.3 cm s-l for sites I and 11, respectively; the corresponding values in TmNi, were 25.8 and 11.3 cm s-l. Ytterbium (170Yb).The 170YbMossbauer spectrum of YbNbF, at 4.2 K consists of a three-line pattern that results from quadrupole interactions only, confirming the absence of magnetic ordering at this temperature.708 The 170Ybspectrum of the Chevral phase YbMo,S, has a shift of -0.19 mm s-l that is characteristic of the presence of Yb2+.The asymmetry of the thermal vibrations obtained from the data was found to be smaller than that obtained from neutron-diffraction data. This suggests that the displacement of Yb from the origin includes a significant static component that persists at low temperat u r e ~ . The ? ~ ~spectra for YbMo,S, and for the neutron-irradiated 1sQTmM~6S8 have been obtained at between 0.1 and 50 K.704The spectra consist of two superimposed patterns of which one is a quadrupole spectrum assigned to Yb2+ with a considerable Goldanskii-Karyagin effect and the other is due to Yb3+. The Yb2+ subspectrum provides the first evidence for a Goldanskii-Karyagin effect reported for 170Yb,the evidence being that the relative intensities of the three lines of the quadrupolar spectrum are 0.8 : 2.0 : 0.9 instead of 1 : 1 : 2. The hyperfine parameters obtained from the Mossbauer spectra of YbPO, and YbVO, have been to obtain information on the electronic properties P. C. M. Gubbens, A. M. Van der Kraan, and K. H. J. Buschow, J . Magn. Mugn. Muter., 1983, 30, 383. ?06 D. Niarchos, C. Meyer, B. Schuttler, G. K. Shenoy, B. D . Dunlap, and A. T. Aldred in ref.I,p.331. '07 D . Niarchos, P. J. Viccaro, G . K. Shenoy, B. D. Dunlap, and J. K . Yakinthos, J. Phys. Chem. Solids, 1983,44,307. 708 S . M.Eicher and J. E. Greedan, J . Less-Common Met., 1983.94,213. '09 J. Jorgensen, D . G. Hinks, D . R. Noakes, P. J. Viccaro. and G . K. Shenoy, Phys. Rev. B. 1983, 27, 1465. '"j

Mfissbauer Spectroscopy

367

of the Yb3+ ion. Evidence for magnetic ordering was found for both YbPO, and YbVO, at temperatures below 0.15 K. Spin-spin relaxation rates were obtained in the paramagnetic forms of the phosphate and vanadate, and the origin of the effect in YbVO, was discussed in detail. The Mossbauer effect has been used to study mixed valence and magnetic ordering in YbBe13 in the temperature range 0.065-81 K. The data obtained above the magnetic-ordering temperature (1.27 K) cannot be explained in terms of the r7 ground state of Yb3+, and this is taken as evidence for the presence of Yb in mixed-valence states with the degree of hybridization being dependent on magnetic ordering. Below 1.27 K the Mossbauer spectra can be explained in terms of the r7ground state of Yb3+alone.71oThe 170Ybeffect has also been used to study magnetic-transition temperatures in YbFe,Si,.6e3 Neptunium(237Np).The 237Npspectra have been measured for a series of NprVcompoundsof generalcomposition NpX,, NpX2,and NpX2YlY2[X= acetylacetonate, bis(pyrazolyl)borate, or tris(pyrazolyl)borate, Yl, Y2 = CI, Cp, or M e C ~ ] . ~ l l Isomer shifts, magnetic-coupling constants, and quadrupole-coupling constants were derived. The spectrum of Np(acac),Cl, was reinterpreted from that previously reported. Two interpretations are possible: (i) 6 = -1.47 cm s-l, gOpNHeff = 7.92 cm s-l, and eqQ/4 = 0.97 cm s-l or (ii) 6 = -0.42 cm s-l, gopNHeff = 8.49 cm s-l, and eqQ/4 = -0.42 cm s-l. In a previous publication the first interpretation was erroneously chosen. Comparison with the isomer shifts of other compounds studied leaves no doubt that the second interpretation is the correct choice. Comparison of the isomer shifts also shows no significant difference in isomer shifts among the 237NpMossbauer spectra of any of the compounds investigated, and the isomer shifts do not differ significantly from that for NpCl,, 6 = -0.35 cm s-l. From the evidence of the 237NpMossbauer spectra none of the ligands involved in the bonding of the compounds measured contributes any appreciable electron density to the Sf-orbitals of the NpIV ion. This is in contrast to the striking covalent effects shown by the isomer shifts of Np(C8H8),( 6 = +1.94 cm s-9, and NpCp,CI ( 6 = +1.4 cm s-l). The Cp and MeCp ligands are ligands that can donate electron density to the Nprv ion. Their failure to make any significant contribution is probably because the Np-Cp bond distance in the compounds studied is too long to allow an appreciable overlap between the ligand and the Sf-orbitals of the NpIVion. The 237NpMossbauer parameters have been measured for BaNpO,, Np(C5H5),, (Et,N),Np(SCN),, and a Np-nitrilotriacetate complex.712The information on chemical bonding obtained from data for the latter complex (6 = 6.90 mm s-l, $eQVzz = 15.13 mm s-l, and 7 = 0.6) was compared with that from perturbed angular correlation studies. The electronic structures of Np impurity ions in Tho,, UOz, Np02, Pu02, and AmO, have been calculated713using a linear

'lo

'11

'I2

G. Von Eynatten, C. F. Wang, N. S. Dixon, L. S. Fritz. and S. S. Hanna. Z . Phvs. B, Condens. Matter, 1983, 51, 37. D. G. Karraker, Inorg. Chem., 1983, 22, 503. T. Krueger, Kernforsch. Karlsruhe, 1982, KFK 3463. V. S. Nefedov and V. M. Filin, Radiokhimiya, 1983, 25. 551.

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M-0-Np-0-M cluster approximation, and the results are shown to be in good agreement with 237Npisomer-shift data. The observed increase in the overlap density in the series Tho, < UO, < NpOz < PuOz < AmO, is in agreement with the bond-strength increase for Np ions in the series. Included in a review article on actinide Mossbauer-effectstudies is a discussion on information obtained on the phase transitions occurring in Np02 at about 25

K.34

Americium (z43Am).The use of the 243Ameffect to study the phase transition in AmO, at about 10 K is included in a discussion of the use of Mossbauer spectro-

scopy in actinide

7 Back-scatter and Conversion-electron Mossbauer Spectroscopy

Over the past year the number of papers dealing with the development and application of the conversion-electron Mossbauer spectroscopy (c.e.m.s.) technique that have appeared in the literature has more than doubled. Details of the theoretical developments and advances in instrumentation and methodology published over the past year are outlined below and are followed by a description of recent applications of the technique. Sawicki and Sawicka714have reviewed the experimental techniques used in c.e.m.s. Recent applications of Mossbauer spectrometry of back-scattering geometry, which has been developed to an attractive technique for studying the solid surface containing iron or tin, have been reviewed with particular attention paid to c.e.m.~.~l~ The chemical and physical state of iron or tin compounds produced at the surface of chemically treated steels, such as hardened, Parkerized, and corroded steels, and the phase transformation of steels are analysed by c.e.m.s. and X-ray Mossbauer spectrometry (x.m.s.). A theory of Mossbauer spectra of conversion electrons under total reflection has been An equation was derived that describes the depth profiles of the integral resonance absorption of secondary emission. The multiple interference effects are considered important in films of thickness ~ 2 0 0 A.Preliminary calculations indicate that c.e.m.s. can be a powerful method for surface studies. Analysis of Mossbauer spectra of scattered characteristics of radiation of solid samples with spatially homogeneous distribution of Fe-containing phases gave717equations for calculating the integral intensities in resonance spectra. The equations are said to be suitable for quantitative interpretation of split as well as unsplit Mossbauer spectra. Babikova et aL718 have also developed a method for determining concentration profiles of Mossbauer atoms and phase compositions in depth analyses of solids using c.e.m.s. 71p

'16 '16 717

'18

J. A. Sawicki and B. D. Sawicka in ref. 5, p. 199. U. Ujihara in ref. 1, p. 166. M. A. Andreeva, S. F. Borisova, and R. N. Kuz'min, Zh. Tekh. Fiz., 1983, 53, 1395. Yu. F. Babikova and N. S. Kolpakov, Prikl. Yad. Spekrrosk., 1982, 11, 225. Yu. F. Babikova, 0. M. Vakar, P. L. Gruzin, and Yu. V. Petrikin, Prikl. Yad. Spektrosk.. 1982, 11, 228.

Mijssbauer Spectroscopy

369

An integral c.e.m. spectrometer, giving up to 61 % resonance effect with a thick, unenriched stainless-steel plate, has been described71eand used in a study of corrosion of plain carbon steel in alkaline water. A number of papers have appeared reporting the design of low-temperature equipment for c.e.m.s. studies. A new convenient spectrometer for measurements of conversionelectron Mossbauer spectra at low temperatures has been designed720and is shown in Figure 7. The resonant absorber and the channel electron multiplier are mounted in a small vacuum chamber and can be cooled down to 78 K or 4 K, together with the source, simply by insertion into liquid nitrogen or helium containers. The set-up greatly simplifies the construction and service of the equipment, facilitates rapid exchange and cooling of samples, and permits durable measurements at low evaporation rates. Owing to close sourcsto-absorber-todetector distance and high efficiency of the channeltron for detecting secondary electrons, more effective measurements than with the use of other spectrometers are possible. Low-temperature c.e.m.s. spectra of 67Fe,llBSn, 161Eu, and lS*W were presented as examples. velocity transducer p l e c t r ical contacts

k

s

a m pte

F m e 7 C.e.m.s. experimental set-up for experiments with the source, absorber, and channel electron multiplier cooled to 4 K (Reproduced with permission from Proc. Indian Nat. Acad. Sci., 1982, 800)

Ujihira et ~ 1 . ~report ~ ' the design of a low-temperature spectrometer with a ceramic electron-multiplier detector. A back-scatter electron counter used for c e.m. spectra of samples at low temperatures has been described in a paper by Atkinson and C r a n ~ h a wA. ~channeltron ~~ has been used to detect the secondary electrons produced by the collision of the conversion electrons with the surface. The operation of a He-filled counter was investigated72sat temperatures down to 77 K. Gas mixtures used at room temperature are unsuitable for use at low temperature because of the freezing of quenching gases. Of a number of gas mixtures tested, the one found to be most suitable down to 77.3 K was a N. K. Jaggi, K. R. P. M. Rao, Y. D. Dande, P. K . Chambers, and H. S. Gadiyar in ref. 1 , p. 313. 7*0 J. A. Sawicki and T. Tyliszczak in ref. 1, p. 800. '11 Y. Ujihira, K. Nomura, A. Handa, and M. Fujinami, Kenkyu Hokokrr-Asahi Garasrc Kogyo Goutsu Shoreikai, 1982, 40, 155. 7** R. Atkinson and T. E. Cranshaw, Nucl. Znstrum. Methods, 1983,204, 577. 7aa Y.Isozumi, M. Kurakado, and R. Katano, Nucl. Znstrum. Methods, 1983, 204, 571. 'lo

370


He5 %CO mixture, and 57Fe resonance-electron Mossbauer spectra were successfully obtained with this counter. The design of a film-plastic-scintillatorsum-coincidencesystem developed for c.e.m.s. has been By employing a prism-shaped light guide between a film plastic scintillator and two photomultipliers, signals picked up from both the photomultipliers were added in a sum-coincidence circuit and used for the measurements of c.e.m. spectra of ll0Sn. The authors have used the system to study tinplate corroded by 2M HN03 and for low-temperature applications. Most of the instrument designs reported over the past year are for low-temperature applications. One paper, however, a vacuum apparatus suitable for c.e.m.s. measurementsup to 1200 K. The apparatus allows c.e.m.s. measurements and in situ heat treatment of samples under ultra-high vacuum conditions to be made. The detecting system is based on the channel electron multiplier used in a close-to-sample geometry. A special technique of suppressing the background due to thermally activated electrons and ions is described. Finally, the operation and performance of a detector filled with Me2C0 vapours for the recording of conversion and Auger electrons from Mossbauer effect for surface analysis have been described and illustrated by signals from Armco iron enriched by 67Fe.

Iron.-As in previous years, because of favourable properties of the 67Fe Mossbauer y-radiation and its associated conversion electrons, most applications of the c.e.m.s. technique over the past year are concerned with the iron-57 effect. The applications are categorized under the following headings: films, steels, implantation studies, and chemical reactions. Films. The passage of conversion electrons through Al, Fe, Sn, and Au films has been studied by the Mossbauer effect with detection of Auger and conversion electrons.727In a review728of experiments on the magnetic properties of ferromagnetic surfaces and thin films the author reports results of some c.e.m. measurements. Ultra-thin (2 s t < 100 A) epitaxial 57Fefilms have been grown in ultra-high vacuum (UHV) on epitaxial Ag films.729The c.e.m. spectra are discussed interms of film thickness ( t ) . Clear features of the or-Fe spectrum can be seen down to 8 A, which corresponds to four atomic layers. However, a component with lowered hyperfine field is present for t < 8 A, which is indicated by line broadening. This is considered to be due to Fe atoms on the surface layers of the film, Below t = 5 A a superparamagnetic peak occurs and becomes predominant at a thickness of 2 A. This means that in this region the Fe film consists of isolated particles that show superparamagnetic relaxation at room K. Endo, A. Kato, M. Mizui, and H. Sano in ref. 1, p. 912. J. Kowalski, J. Stanek, T. Tyliszczak, and J. A. Sawicki, Nucl. Znstrrrm. Methods, 1983. 216, 299. 7asYu. V. Petrikin, V. N. Alekseev, V. A. Bychkov, 0. M. Vakar, A. A. Kasimovskii, V. A . Kondratenko, and A. I. Shamov, Zavod. Lab., 1983,49,46. 727 Yu. F. Banikova, 0. M. Vakar, P. L. Gruzin, and Yu. V. Petrikin. h . Vvs.rh. Urhehn. Zavod. Fiz., 1983, 26, 10. 728 G . Bayreuther, J . Magn. Magn. Mater., 1983, 38, 273. 728 G. Bayreuther and G. Lugert, J . Magn. Magn. Muter., 1983, 35, 50. 734

7a5


37 1

temperature. In another paper, Becker et al.730report a c.e.m.s. study of f.c.c. y-Fe(100) films, prepared by epitaxial growth in UHV on Cu(100) films, at 295 K using a H e C H , flow-gas counter. The Mossbauer spectra show that the y-Fe(100) films are paramagnetic at 295 K. Depending on the Fe film thickness, part of the Fe atoms are found to exist in the a-Fe phase. The depth sensitivity of energydifferential c.e.m.s. has been by using a 50 A 67Fefilm evaporated onto 1320 A natural Fe and coated by 0,50, and 100 A natural Fe. The average hyperfine field of 34 8, 57Feon 340 8, "Fe was found to be slightly smaller than (-326 kOe) the bulk field. Surface effects were drastically enhanced if Auger electron Mossbauer spectroscopy at 600 eV was performed. The energy spectra of 7.3 keV electrons passing through Fe films were with a highresolution electron spectrometer by use of a thin 57C0source. The energy resolution of the spectrometer was set for 1.3 % at 7.3 keV, and the thicknesses of the Fe films for electron scatterers were 63, 121, 175, 279, and 385 8,. From the spectra the energy distributionswere deduced and found to be in good agreement with those of a Monte Carlo calculation. C.e.m.s. with the 14.4 keV y-resonance of 67Fewas used733to study uncovered 5-50 8, thick Fe oxide films grown on single-crystal Fe(ll0) and Fe(100) substrates under UHV conditions; for both magnetite (Fe,O,) and haematite (a-Fe203)a decrease of the magnetic-hyperfine field and of the Mossbauer isomer shift was observed at room temperature with thickness < 20 A. Three papers by Saneyoshi et af.7349735#736 have been concerned with the study of rare-earth iron garnet films. In each paper, spin orientations of rare-earth iron garnet films were determined as a function of the depth for the top of the surface by means of an electron spectrometer combined with Mossbauer spectroscopy. From the transmission Mossbauer spectrum the average spin orientation of the films was found to tilt by 13 f 3" from the normal to the surface. The average tilt angle less than 1500 A in depth was determined to be 19 & 3" with a proportional counter. The spin orientations near the surface were obtained from the Mossbauer spectra taken with the three energy settings (7.3, 7.1, and 6.6 keV) of the electron spectrometer. The tilt angles were found to be 21 & 3" for &100A, 28 f 3" for 100-300~, and 14 k 9" for 300-1000 A in depth. Garnet bubble films implanted with 60 keV Ha+ ions have been investigated737 by c.e.m.s. With increased dosages the average hyperfine fields are reduced and their distributions broadened; there was no evidence of

730 731

W. Becker, H.-D. Pfannes, and W. Keune, J. Magn. Mugn. Muter., 1983, 35, 53. S. Staniek, T. Shigematsu, W. Keune, and H.-D. Pfannes, J. Magn. Mngn. Muter,, 1983. 35, 347.

78a

J. Itoh, T. Toriyama, K. Saneyoshi, and K. Hisatake, Nucl. Instrum. Methoh, 1983. 205. 279.

738

784

M.Domke, B. Kyvelos, and G. Kaindl, Surf. Sci., 1983, 126, 727. K. Saneyoshi, Y . Yoshida, J. Itoh, T. Toriyama, K. Hisatake, and S. Chikazumi in ref. I , p. 222.

K. Saneyoshi, T. Toriuama, J. Itoh, K. Hisatake, and S. Chikazumi, J. Mngn. Mngn. Muter., 1983, 31-34, 705. ia6 J. Itoh, Y. Yonekura, K. Saneyoshi, T. Toriyama, and K . Hisatake, J . Mugn. Mugn. Muter., 1983, 35, 340. 737 A. H.Momsh, P. J. Picone, and N. Saegusa. J . Mngn. Mugn. Muter.. 1983. 31-34, 923. 785

372


paramagnetic absorption. Etching is found to leave an uneven surface, with the greatest damage occurring at a depth of about 1800 A. Steels. In an article on the application of Mossbauer spectroscopy in the steel industry Ra0738stresses that the development of c.e.m.s. now permits detailed studies of corrosion, and he has presented examples of the use of the effect in studies of ores, coals for steel production, ashes, slags, steels, and corrosion products. Handa and Ujihira739v740 have used c.e.m.s. to analyse the layer structure of boronized steel surfaces. The surfaces of Cr-Mo-Ni and Cr-Mo steels were boronized by the solid-phase reaction with B,C powders at 900 "C for 5 h, and the surfaces of a Cr-Mo steel and pure iron were boronized by the gas-phase reaction in BCl, at 800 "C for 2 h and reheated at 800 "C under vacuum. The analyses of c.e.m. spectra of exposed surfaces by grinding to the desired depth revealed that the boronized surfaces prepared by the thermal diffusion of boron atoms in the iron lattice at 900 "C were composed of distinct multi-layers of four iron-boron compounds: FeB, + ( x > 0), FeB, Fe,B, and distorted a-Fe. Only the Fe,B was deposited on the steel surface boronized at 800 "C by the gas-phase reaction. No intermediate layer between any two compounds was recognized, in contrast with the nitrided steel surfaces. The effects of 40 keV He ion bombardment on amorphous alloys Metglas 2826 (Fe40Ni40P14B6) and by scanningMetglas 2605 (FesoBzo)and 304 stainless steel were electron microscopy and c.e.m.s. In Metglas 2826, surface blistering and crystallization were observed after a dose of 1 x lo1* He ions cm-2 at 400 "C. At 200 "C and 3 x 10l8ions ern-,, the blistering follows exfoliation of the surface. This change in surface magnetism is considered to be due to formation of FeB and (Fe,-,Ni,),P. In Metglas 2605, no blistering is observed, even at 3 x 10l8 ions cm-2, though a-Fe is present on the bombarded surface. to study the macro changes in alloy structure induced by C.e.m.s. was He+ irradiation of 304 stainless steel and Fe-Si-B amorphous alloy. In the core of 304 stainless-steel radiation-induced surface phase changes and sputteringinduced surface composition changes were observed. Radiation-induced a-Fe precipitation was observed in irradiated Fe-Si-B amorphous alloys. Using an integral c.e.m. spectrometer, giving up to 61 % resonance effect with a thick unenriched stainless-steel plate, corrosion of plain carbon steels at 310 "C and 10.5 pH has been in~estigated.~,~ Under low dissolved-oxygen content (less than 0.05 p.p.m.) a protective film of non-stoicheiometric, cation-deficient magnetite Fe3-,,04is first formed, which grows at the oxide-water interface, the composition approaching stoicheiometry as the film grows thicker. The film that grows at high oxygen levels (3-5 p.p.m.) consists of dominantly haematite

K. R. P. M. Rao in ref. 1, p. 159. A. Handa and Y . Ujihira, J. Muter. Sci., 1983, 18, 1887. 740 A. Handa and Y. Ujihira in ref. 1, p. 306. N . Hayashi, T. Takahashi, I. Sakamoto, and H. Sekiguchi, Denshi Gijutsu Sogo Kerikyusho Iho, 1983. 47, 479. 744 S. Nasu, Kyoto Daigaku Genshiro Jikkensho (Tech. Rep.), 1982, KURRI-TR-231, 7. 738

730

373


(about 85 %) and some Fe3-,,04.The top 4000 A or so is pure haematite, and the magnetite seems to be adjacent to the base metal. The results have shown that the presegce of even large amounts of haematite does not necessarily indicate the onset of 'catastrophic' corrosion because the haematite forms a protective thick film on an underlying thin spinel Fe,O, film which is coherent to the metal. Two papers have been published by Chen et and another by Meisel and G u t l i ~ concerned h ~ ~ ~ with the analysis of rust layers using c.e.m.s. techniques. Phase composition of the barrier-layer rusts of two alloy steels with different corrosion resistance in sea water was determined by c.e.m.s. for the first time.743 It seems that the barrier-layer rusts of the two kinds of steel after exposure to air have similar composition. They consist of about 80% P-FeOOH and 20% y-FeOOH. Problems arose from the above results such as the effect of alloy element on corrosion process and the formation of deposited-layer rust, and in an attempt to solve these difficulties the authors suggested that samples taken out from sea water are different from samples in the sea water and went on to prove this; their results of this are in their second paper.744Potentiostatic anodic polarization of low-alloy steels in 3.5% NaCl solution imitated the electrochemical process of local micropits corrosion in sea water. Thus, the true composition of the barrier-layer rust formed could be detected by the Mossbauer effect. Results showed that different low-alloy steels possess different phase composition of the barrier-layer rust. In addition to the final-state phases 8- and y-FeOOH, which were found in all the samples taken out from the sea water, they also contain amorphous intermediate-state iron rust of different composition. These intermediate-staterusts tend to oxidize very easily, dehydrate, and age in the atmosphere. The effect of the alloy elements on the composition of the barrier layer and on corrosion resistance has been discussed. According@ c.e.m.s. and corrosion electrochemistry, suggestions for developing and evaluating corrosion-resistant low-alloy steels in sea water have been made. A study has been made746of some phase transformations in rust layers. The composition and morphology of rust layers on steel surfaces have been determined by phase transformations of the initial oxidation products. These transformations, it is considered, can be best understood by use of a level scheme of Gibbs free formation energies, and the authors have demonstrated this by three examples using transmission and conversion electron Mossbauer spectroscopy: (i) the influence of the corrosivity in atmospheric corrosion on the phase composition of steel-corrosion products, (ii) the effect of so-called rust transformers on corroded steel surfaces, and (iii) the effect of organic corrosion inhibitors in aqueous solutions. Mild and stainless steels have been treated in an oxalate bath for surface finishing, and the chemical states of the iron species produced in the oxalate coating have been investigated746using c.e.m.s. The chemical states of the deposited iron(n) oxalate on both steels were not affected by rolling, although a ~

1

.

~

~

~

9

~

~

~

J. Chen, Z. Cai, Z. Wang, C. Wang, H. Zhang, W. Hu,F. Yu, andG. Zhanginref. 1. p. 261. J. Chen,.Z. Cai, Z. Wang, C. Wang, H. Zang, F. Yu, and W. Hu in ref. 1 . p. 264. W. Meisel and P. Gutlich in ref. 1, p. 284. 746 K. Nomura and Y . Ujihira, J . Muter. Sci., 1983, 18, 1751. 'Ia

744

374


large part of the oxalate coating on mild steel was easily stripped off by the process. It was found that (i) surface conditioning of stainless steel by oxalate was more effective than that of mild steel and (ii) the different states of FeC,O, were formed as a thermal-decomposition product by different thermal treatment. The thermal property of oxalate coating was similar to that of FeC20,.2H,0. It was concluded that the oxalate coating worked as a good lubricant rather than a corrosion-resistantmaterial, especially at the surface of stainless steel. Another phase analysis was carried out by Meisel et al.747in which steel plates were exposed in a controlled corrosive environment and then treated with concentrated phosphoric acid or commercial rust transformers containing phosphoric acid. The phase analysis was carried out using both transmission and conversionelectron Mossbauer spectroscopy. The product of concentrated-acid treatment was identified as FeH,(P0,),*2.5H20, which produced a singlet at 8 = 0.43 mm s-l. It was shown that no rust was converted into an oxide capable of forming a protective layer against rust. The corrosion reaction products of iron . ~ ~ authors ~ claim in SO, humid atmospheres have been studied by ~ . e . m . s The that in some cases they detect only Fez+species and that different products are obtained when atmospheric conditions are varied only slightly. The following compounds were said to be among the products : FeSO, 3H2S04,FeSO, - 4H20, FeSO,. H20, and Fe4(S04)(OH)10. Surface layers on steel samples formed by exposure in chromate solutions with fixed hardness and chloride content were studied by Mossbauer (c.e.m.s.) and e.s.c.a. ~pectroscopy.~~~ The layers were found to consist of oxidic compounds containing Cr3+ and, to a lesser extent, Fe3+ ions with no magnetic ordering found for the iron ions. The c.e.m.s. spectra of the samples were found to consist of the sextet of the metallic substrate and doublets with isomer shifts 6 = 0.31 and 0.38 mm s-1 for 300 K and 80 K, respectively, that are characteristic of Fe3+.The intensity of the doublets is about the same at 300 K and 800 K but does not appear in the spectra measured at 20 K. The quadrupole splittings (A = 1.03 and 1.05 mm s-' at 300 K and 80 K, respectively) are slightly larger than those expected for ferric oxides. The formation of very small Fe203clusters distributed in a relatively thick layer of Cr,O, was considered a reasonable explanation of the experimental data. Implantation Studies. A number of systems implanted with 57Feions have been with 57Feions at investigated using c.e.m.s. LiF crystals have been implanted750 dose levels from 5 x 1015atoms cm-, to 6 x 10ls atoms cm-2. The iron enters the implanted zone in three well defined charge states: Fe", Fe2+,and FeO(meta1). At low dose levels the relative fractions of Fe3+and Fez+are close to 80% and 20%, which correspond to the respective ionic fractions in an Fe-doped LiF sample obtained by vacuum co-deposition. With an increase in dose level the Fe2+and Feo fractions increase to 40 % and 30 %, respectively. Annealing in a

-

W. Meisel, H.-J. Guttmann, and P. Gutlich, Corros. Sci., 1983, 23, 1373. J. R. Gancedo, M. Gracia, and M. L. Martinez in ref. 1, p. 271. 74Q P. Gutlich, H. J. Guttmann, W. Meisel, and E. Mohs in ref. 1, p. 451. J. Kowalski, G . Marest, A. Perez, B. D. Sawicka, J. A. Sawicki. J. Stanek, and T. Tyliszczak. Nucl. Instrum. Methods, 1983, 209-210, 1145. 747

748

Mljssbauer Spectroscopy

375

vacuum was found to result in a growth of metallic-iron precipitates, whereas annealing in the presence of oxygen leads to precipitation of superparamagnetic particles of some Fe3+compound. Perez et al.761have also used c.e.m.s. to study magnesium oxide crystals implanted with 57Fe+ions at doses ranging from 10l6 to 1017 ions cm-2 (ion energy 70, 100, and 150 keV). It was found that implantation introduces iron in MgO in three charge states: Fez+, Fe3+, and metallic precipitates (FeO), with the dominant role of Fe3+ at low doses, Fe2+at medium doses, and metallic-iron clusters at the highest doses. The phase created in a medium range of doses can be compared with the magnesio-wiistite solid solution. The isochronal thermal annealings in air at temperatures between 300 and 700 "C gradually cause the oxidation and the nucleation of highly dispersed spinel-like clusters and then, at about 800-900 "C, the growth of magnesioferrite particles. In contrast, the heat treatment in vacuum converts all iron into well diluted Fez+ in MgO phase. The nature of point defects and their role in annealing processes are discussed on the basis of the optical-absorption data. A good correspondence between the results of Mossbauer and channelling data is indicated. The effect of the insulator-conductor transition occurring under iron-ion implantation in MgO and observed by electricalconductivity measurements is explained in terms of the atomistic properties of implanted crystals under study. Both integral and depth-selective c.e.m.s. have been to study 67Feimplanted Cu foils. The techniques have been used to analyse the phases present at various depths in copper-iron alloys produced by 57Feimplantation at a dose of 4 x 10l6 ions cm-2. Depth-selective c.e.m. spectra were recorded in the energy range 6.5-7.3 keV to ensure only K-conversion electrons were recorded. An increase in the degree of clustering was observed for increasing depth below the Cu surface. C.e.m.s. was to identify a magnetic splitting caused by atomic disorder resulting from the implantation of A1 ions into FeA1(40%). A paramagnetic component which decreased with increasing fluence was also observed. A hyperfine field of 189 kOe was obtained with a dose of 10" A1 ions cm-2. The authors also used a combination of electron-scattering spectra and transmission Mossbauer observations to A1 implantation in the Fe-40 atom % A1 alloy. C.e.m.s. showed a single line at 1014ions cm-2, while magnetic components appeared at 3 x 1014ions cm-2. This behaviour was considered to be due to partial atomic disordering. The hyperfine interactions had the same order of magnitude as those measured in transmission Mossbauer spectroscopy on either the crushed or filed alloy. In another Eymery et al. used this combination of techniques to characterize the amorphous layer obtained by ion o ~ ~ ~ implantation in Ti-50 atom % Ni alloy. Carbucicchio and T ~ s t analysed 'ti1

A. Perez, G. Marest, B. D. Sawicka, J. A. Sawicki, and T. Tyliszczak. Phys. Rev. B, 1983. 28, 1227.

G. Longworth, R. Atkinson, S. Staniek, H.-D. Pfannes, T. Shiematsu, and W. Keune in ref. 1, p. 375. 753 A. Fnidiki, J. P. Eymery, and J. Delafond, J . Mugn. Mugn. Muter., 1983, 40, 130. '64 J. P. Eymery, A. Fnidiki, and J. P. Riviere, Nucl. Instrum. Methods, 1983, 209-210, 919. '55 P. Moine, J. P. Eymery, R. J. Gab, and J. Delafond, Nurl. Instrum. Methods, 1983. 7 ~ 4

209-210, 768

267.

M. Carbucicchio and S. Tosto in ref. 1, p. 413.

376

Spectroscopic Properties of Inorganic and Organometaiiic Compounds

the surface of 38NCD4 steel samples ion-implanted with nitrogen at different currents using both surface Mossbauer spectroscopy and scanning-electron microscopy. The dose selected was 1017 ions cm-2, which was considered the best dose as far as wear and strain are concerned. Depth-selective c.e.m. spectra were recorded at energies in the 5.5-7.3, 6-7.3, 6.5-7.3, and 6.8-7.3 keV ranges. The results have shown that Fe,N-like nitrides are formed near to the surface while more iron-rich nitrides are formed in deeper regions, and the nature, arrangement, and morphology of the phases formed in the implanted layers have been determined. I6N implants into unalloyed iron and two steels 100C6 and 42CD4 at room temperature have been by nuclear analysis, using the 15N(p,o(y)12C reaction, and by Mossbauer spectroscopy. The relative amounts of nitrides present have been followed during heat treatments at 250 "C. It can be seen from a combination of the techniques that the evolution of the N content into the implanted zone is controlled by the transformation kinetics of the nitrides and not by the elementary N diffusion process. Chemical Reactions. Conversion-electron and transmission Mossbauer spectroscopies were to study problems associated with natural siderite. The in situ transformation of siderite to haematite by calcination could be effectively traced by transmission experiments. Using y-resonance spectroscopy, the nature and size of the particles formed after the natural transformation to the oxide were determined. Domke and K y ~ e l o report s ~ ~ ~the use of the c.e.m.s. technique to measure the initial stages of oxidation on a 100 A thick (110)57Fesinglecrystal face at 275 "C in the pressure range 2 x 10-4-8 x torr. Only and 8 x magnetite was formed at 2 x torr, and a magnetite/haematite conversion occurred at 2 x torr. The various oxide phases were investigated according to the growth behaviour and kinetics. Complicated changes in the kinetic behaviour were found with the magnetite/haematite conversion. Depthselective c.e.m.s. was used to measure qualitatively the depth distribution of the oxide phase and the Fe ion sites. Combined conversion-electronand transmission Mossbauer spectroscopy has been used760to study the structure of passivated layers of promoted and unpromoted iron-containing catalysts. In both catalysts the oxide-coated films consisted of small paramagnetic (at 300 K) clusters of Fe,O,. In situ c.e.m. spectra for 57Feelectroplated on Au film on Melinex in a borate-buffered pH 8.4 solution in the cathode's protection region and passive region have been The formation and growth of iron compounds in zinc phosphate and calcium-zinc phosphate coatings were by means G. Marest, C. Skoutarides, T. Barnavon, J. Tousset, S. Fayelle, and M. Robelet. N I d . Instrum. Methods, 1983, 209-210, 259. 768 A. Fnidiki and J. P. Eymery, Ann. Chim. (Paris), 1983, 8, 237. 769 M. Domke and B. Kyvelos, Corros. Sci., 1983, 23, 921. 700 Yu. V. Maksimov, R. A. Arents, Yu. V. Baldokhin, P. I. Suzdalev, D. M. Minaev, and R. V. Chernokova, React. Kinet. Catal. Lett., 1982, 21, 81. D. A. Scherson, S. B. Yao, E. B. Yeager, J. Eldridge, M. E. Kordesch, and R. W. Hoffman. J . Electroanal. Chem. Interfacial Electrochem., 1983, 150, 535. 763 K. Nomura, Y. Ujihira, and R. Kojima in ref. I , p. 310. 767


377

of c.e.m.s., t.m.s., X-ray diffractometry, and scanning-electron microscopy. In zinc phosphate coating, phosphophyllite was observed beneath hopeite and an amorphous iron(@ compound. The addition of strong oxidizing reagents such as NO3-, NO2-, CI3-, and H202or Ni2+in a zinc phosphate bath prevented the formation of phosphophyllite and favoured the deposition of hopeite. In calcium-zinc phosphating, the iron(@ compound (6 = 1.26 rnm s-l, A = 2.06 mm s-l) was formed beneath scholzite. In the zinc and calcium-zinc phosphatings the magnetic axes of interface layer tended to orientate at random with the increase of coating weight causing the flat surface of the steel to become rough with the development of the phosphate coating. In another study iron oxidation in phosphate glasses has been investigated by c.e.m.s. and t . m . ~ .The ~ ~ ionic ~ ratio Fee+/Fe3+measured by c.e.m.s. depends strongly on the conditions of the glass formation and on the subsequent thermal annealing and oxidation procedure. The technique has been shown to be suitable for studies of electronic phenomena in subsurface layers in glasses. Iron-57 has been deposited on (111)Si surfaces at room temperature, and the c.e.m.s. spectra have been m e a s ~ r e d The . ~ ~ 67Felayers have been coated with natural iron (2.2% 57Fe)or Ag to prevent them from oxidizing on exposure to air. The results show that when 7.2 A of Fe is deposited the in situ reaction converts all of the iron to a form that has a doublet spectrum corresponding to a line position of FeSi. Increased deposition of Fe on Si produces a spectrum that would be expected for a-Fe containing large amounts of Si. The presence of the Si in the Fe phase shows that the FeSi is forming by diffusion of the Si through the silicide layer and into the iron. When a thick layer of Fe (62 A) is deposited, almost all is in the form of a-Fe, and the lines from FeSi are relatively weak. Heating at temperatures from 200 to 650 "C enhances the formation of the silicide, and the Mossbauer spectrum becomes that of bulk FeSi. After annealing, no FeSi, or Fe-Si alloys are observed. Some samples show evidence of an interfacial barrier that prevents silicide formation and stabilizes the Fe layer against anneals of 2 hours at 650 "C. Transmission and back-scatter Mossbauer spectra of zeolite Fe and Fe-Co synfuel catalysts have been The Mossbauer spectra were obtained to characterize the fresh, the reduced, the carbided, and the used ZSM-5 with Fe or Fe-Co at the microscopic level. The back-scatter work was undertaken to see if the iron was on the top 30 nm layer of the Fe-Co catalysts formed with the ZSM-5system. However, the c.e.m. spectra of Fe-Co catalysts revealed the absence of Fe in the 30 nm layer, which was confirmed by ion-scattering spectroscopy. Further spectra show that the differences in selectivity between ZSM-5 (Fe) and ZSM-5 (Fe,Co) catalysts arise from the presence of bimetallic transitionmetal clusters in the latter, with consequent changes in the average number of 3d-electrons per transition-metal atom. The c e.m. spectra of thin layers of Sendust (Fe-Al-Si alloy) on a Si substrate were measured at room temperature.766 A transient layer was found in which the H. Binczycka and J. A. Sawicki, J . Phys. D, 1983, 16, 197. R. L. Cohen, L. C. Feldman, K. W. West, and P. J. Silverman in ref. I , p. 477. 766 L. N. Mulay, C. Lo, K. R. P. M. Rao, R. Obermeyer, and V. U. S. Rao in ref. 1, p. 457. 766 H. M. Van Noort, Solid State Commun., 1983,48,495. 768

378


composition deviated from the ideal Sendust composition, but in which the structure was still ordered. Crystalline processes and emerging phases in amorphous metal have been investigated,767and after crystallization of amorphous (FeNi)86B14 and (FeNi)83B17 a Ni-rich ferromagnetic and a Ni-poor paramagnetic y-(FeNi) phase were found to coexist. To study the surface behaviour of amorphous Fe33P5C12the authors measured bulk and surface properties simultaneously using the y-ray transmission and electron-emission geometries at room temperature. Drastic changes were observed in the relative line intensities of Fe8,P5Cl, after ageing for about I year in air at room temperature. To simulate this process, amorphous samples of Fe8,P,C1, prepared as ribbons about 40 pm thick and 2 mm wide by single-roller quenching were annealed at 630 K in air for various durations, and the transmission Mossbauer and c.e.m. spectra were obtained simultaneously. The peak-intensity ratio I2 : Il in the bulk spectra decreases rapidly when the annealing time is increased. Simultaneously with this change of domain structure new lines appear in the c.e.m. spectra showing the formation of iron oxides on the surface. Atomic rearrangements and crystallization within a 100 pm of the surface in annealed amorphous FellB13.5Si3.5C2ribbons have been investigated by c . e . m . ~ .Atomic ~ ~ ~ rearrangements at the dull surface, at the shiny surface, and in the bulk of the ribbon are all different. The onset of crystallization at the two surfaces occurs at lower temperatures than for the bulk. Crystallization occurs in three stages. In the first stage precipitations of Fe-( 2.0-3.0 atom% Si) and Fe-( 2.3-3.5 atom % Si) occur at the shiny and dull surfaces, respectively, and in the second step crystallization of Fe3C occurs. The process is completed by crystallization of Fe2Band a decrease of 1 % in the Si concentration of the Fe-Si alloys.

-

N

-

Other Elements.-In principle c.e.m.s. can be used for any of the Mossbauer isotopes. However, in addition to those papers reporting applications of the 67FeMossbauer effect, a small number of papers was published in the past year describing studies involving the use of ll9Sn, 151Eu,lS2W,and lg7Auisotopes. Amorphous Sil-,Sn, : H alloys were prepared by d.c. and radiofrequency of composite Si targets in Ar-H, gas ll9Snc.e.m.s. and X-ray diffraction revealed that the tin was incorporated into the films in at least four distinct sites, the relative populations of which depended on the conditions of preparation. The Mossbauer resonance from the substitutional tin in the a-Si : H matrix was well characterized by a quadrupole splitting of 0.46 f 0.05 mm s-l independent of x and the preparation conditions. Magnetic-hypefine fields at ll9Snnuclei implanted into Ni and post-implanted with He have been using c.e.m.s. In all spectra there is a component with shift between 0 and 1.3 mm s-l attributed to the precipitation and oxidation of Sn near the surface. The substitutional component has 6 = 1.4, A = 1.55, U. Gonser, M. Ackermann, H . J. Bauer, H. Guafari, H.-P. Klein. and H.-J. Wagner i n ref. 1, p. 338. N. Saegusa and A. H. Monish, Phys. Rev. B, 1983, 26, 6547. 760 D. L. Williamson and S. K. Dab, J . A p p f . Phys., 1983, 54, 2588. i67

379


and I‘ = 1.24 mm s-l. A high-field component with 6 = 2.1, A = 2.34, and I? = 1.58 mm s-l is observed in the annealing temperature range 935-937 K. It is concluded that Sn implanted in Ni even to concentrations of 1.4% traps He-decorated vacancies resulting in larger than substitutional hyperfine fields. Tin eniiched in ll9Sn was electrodep~sited~~~ on both surfaces of thin sheets of silver, copper, and iron. The thickness of the tin layers was between 20 and lo00 nm on each side of the substrates. The deposited tin was studied by transmission and c.e.m.s. at room temperature. The samples were measured after electrodeposition and in some cases also after heat treatments at different temperatures. In the Sn/Ag spectra the components identified were P-Sn, SnO,, and Ag,Sn, in the Sn/Cu spectra they were P-Sn, c-CU,Sn, and 3-Cu,Sn,, and in the Sn/Fe series they were P-Sn, SnO,, Fe,Sn,, and FeSn,. C.e.m.s. has also been used to study the corrosion of tinplate.724

-20

10

0

-10

Velocity/mm s-’

98.81

, -2

, -1

,

,

,

0

1

2

1

Velocity/mm s-’

Figure 8 C.e.m.s. spectra for (a) metallic tin measured at 300 K and 78 K with 200 pCi BaSnO, source, (b) Eu,O, and oxidized europium metal at 78 K, and (c) tungsten at78 K (Reproduced with permission from Proc. Zndian Nut. Acad. Sci., 1982, 800)

380


In order to demonstrate the new technique developed for low-temperature c.e.m.s. studies, Sawicki and T y l i s z ~ z a krecorded ~ ~ ~ spectra of metallic iron foil, metallic tin foil, natural Eu203and metallic europium foil, and natural tungsten foil. The c.e.m.s. spectra of metallic tin measured at 300 K and 78 K with a 200 pCi BaSnO, source are given in Figure 8 along with the 78 K spectra of Eu,O, and oxidized europium and the 78 K spectrum of natural tungsten foil (26% lS2W).There is evidence of a mixture of Eu2+and Eu3+oxides formed on the surface of freshly prepared metallic Eu surface, at a depth of at least 200 nm. The spectrum of tungsten is a result of a preliminary experiment with the 100 : 1 keV transition of 182W. For the first time a paper has appeared in the literature concerned with the use of the lg7Auisotope for c.e.m. The Mosssbauer spectra of the 77.3 keV transition in lg7Auwere measured for the first time in the conversion-electron scattering mode, with the use of a channel electron multiplier at low temperatures. The high magnitude of the resonant effect obtained makes the investigation of various phenomena in very thin Au films feasible.

770 i71

A. Vertes, S. Nagy, and M. Lakatos-Vaksanyi in ref. 1, p. 479. J. A. Sawicki, T. Tyliszczak, J. Stanek. B. D. Sawicka. and J. Kowalski, Niicf. Instrum. Methods. 1983. 215. 567.

Gas- phase Molecular Structures Determined by Electron Diffraction BY D. W. H. RANKIN AND H. E. ROBERTSON

1 Introduction

The raw material for this report is much the same as that for last year’s review,’ being accounts of the structures of 74 inorganic molecules (five more than last year) published in 1983. We aim to include any compound having a bond between two atoms other than carbon and hydrogen, and we also cover compounds having several atoms other than carbon and hydrogen, even if they are not connected. Within this set of compounds the large majority, not surprisingly, are derivatives of elements of Groups IV, V, and V1, but it is noticeable that this year, as last year, there are no Group I1 compounds at all, and this time there are no transition-metal organometallic derivatives. Although not always dealing specifically with inorganic molecules, papers concerned with the analysis of electron-diffraction data are important. Of particular interest are an account of the use of amplitudes of vibration determined by electron diffraction in fitting force fields to spectroscopic data* and a report of a careful and systematic study of TiF,, ZrF,, and HfF4.S For these molecules the vibrational frequencies derived from the force fields were fitted to electron-diffraction data collected at two temperatures, to data collected at one temperature but with some approximations made, or to diffraction data with one or more of the vibrational frequencies fixed. The technique was extended to (NbF&, but it is impossible with such a complex molecule to tell whether this was successful. This method of analysing data has been applied in several of the studies discussed in t1L review. Other papers deal with the analysis of anharmonic vibrational effects, applied particularly to C024and to curvilinearity effects in planar AB3 molecules.6 These effects are small when the frequency of the out-of-plane vibration is above 400 cm-l, but otherwise they can be very large. For LaBr,, with a frequency of 35 cm-l, the r,(Br...Br) distance is 4.634 A; this is corrected to 4.613 8, (r,) in a conventional analysis but to

D. W. H. Rankin and H. E. Robertson in ‘Spectroscopic Properties of Inorganic and Organometallic Compounds’, ed. E. A. V. Ebsworth (Specialist Periodical Reports), The Royal Society of Chemistry, London, 1983, Vol. 16, p. 350. V. A. Sipachev, N. I. Tuseev, and R. F. Galimzyanov, J . Mol. Strut., 1983, 96, 353. G. V. Girichev and N. I. Giricheva, Zh. Strukt. Khim., 1983,24(1), 14. A. G. Gershikov and V. P. Spiridonov, J . Mol. S t r u t . , 1983, 101, 315. A. G. Gershikov, V. P. Spiridonov, and E. Z. Zasorin, J. Mol. Strur., 1983, 99, 1.

381

382


4.686 A when the curvilinearity effects are included. Finally, an alternative to Fourier-transform methods for deriving radial-distribution curves from electrondiffraction data has been proposed., On the experimental front there have been few advances. A stroboscopical method of investigating short-lived species has been described,' and intensity data are presented for the products formed on irradiation of CF31 with an i.r. laser. However, the data have not been analysed, and it is impossible to judge the success of the experiments from the information given. Two more stable molecules, C02*and have been studied over a range of temperatures up to 940 and 980 K, respectively. In both cases the temperature effects are in good agreement with those obtained in a variational-wavefunction analysis. Comparative studies of gas- and solid-phase structures are surprisingly rare. Some examples of the structural changes found when the phase is changed have been discussed,lobut to a large extent the differences are at present unpredictable. There has been one interesting attempt to start to put this right. An ab initio study of CO(CN)(NH,) has been made,ll firstly for an isolated molecule and then for a representation of a molecule in the crystal, with a set of atomic point charges being used to represent the crystal-field effects, these being placed in positions determined in the crystal-structure analysis. The observed structural differences were accounted for quite well, and the calculated structure for the solid was actually better than that calculated for the gas. The division of compounds into groups in a chapter such as this is inevitably somewhat arbitrary, so they are all listed here in order that those of particular interest can be located quickly: Section 1, Introduction: CO,, SO,, TiF4, ZrF,, HfF4, (NbF5),, CO(CN)(NH,); Section 2, Group T : Cs,CrO,, RbAIF4, CsAIF,, KAICl,, RbAICI,, CsAlCl,, (KOH),; Section 3, Group 111: Ga,O, In,O, T1,0, AlF,, Me,N.BI,; Section 4, Group IV : SiCl,, SiBr,, SnBr,, SnI,, PbF,, PbBr,, PbI,, Ge(C,H,Me),, Sn(C,H,Me),, Ge[N(SiMe,),],, Pb[N(SiMe3),I2, perfluorospiropentane, cyclobutylsilane, CH,(SiMe,),, O(SiCIMe,),, O(SiH,Me),, O(SiHMe,),, MeCOSGeH, ; Section 5, Group V : Nz05,Me,CHNO,, Me,CNO,, Me,C(NO,),, c,H,(NO,),, C,H,Cl(NO,), N,Me,, ClN= CCl,, MeN= CHCCI,, PCI,, PCI,Me, PCl,Pr', PClBu',, PH,Ph, PF,NCO, AsMe,, SbMe,, OCH,CH,O~SCI, ZsBr, kH2CH,SksBr; Section 6, Group VI : SF,SF, SO,(CCl,),, SO,CI(C,F,), SO,Me(CH,Br), SO,Me(CBr= CH,), S(PF,),, Se(PF,),, PF,(SMe), SF,NCO, SeF,NCO, TeF,NCO, SeCl,, TeMe, ;

--

V. S. Luytsarev, V. P. Spiridonov, and B. S. Butayev, J. Mol. Struct., 1983, 101, 173. V. P. Spiridonov, A. V. Zgurskii, A. S. Akhmanov. M. G. Vabishevich, and V. N. Bagratashvili, Appl. Phys. B, 1983,32, 161. R. J. Mawhorter, M. Fink, and B. T. Archer, J . Chem. Phys., 1983, 79. 170. O R. J. Mawhorter and M. Fink, J. Chem. Phys., 1983, 79, 3292. lo D. W. H. Rankin, J. Moi. Struct., 1983,97, 129. l1 S. S a e b ~ B. , Klewe, and S. Samdal, Chem. Phys. Lett., 1983,97, 499.

' A. A. Ishchenko, V. V. Golubkov,

383

Gus-phuse Molecular Structures Determined by Electron Difraction

Section 7, Group VII: ClF3, BrF,; Section 8, Transition Metals: MnF,, UFq, WC14, WC15, MoCI,, (MoF,),, (NbF,),, CrO,F,, Cu(acetylacetonate),.

2 Compounds of Main-group I Elements Once again, there are the results of high-temperature studies of alkali-metal salts to report. At 1500 K CszCr04has a structure with D2dsymmetry, with each caesium atom bound to two oxygens, and a tetrahedral CrO, group.12 The Cr-0 and Cs-0 distances CIp) are 1.675(6) and 2.850(40) A, and Cr- .Cs and Cs. - .Cs non-bonded %stances are 3.360(16) and 6.203(126) A, respectively. This last distance is more than 0.5 8, less than twice the Cr. - .Cs distance, and this difference is believed to be a vibrational effect, as amplitudes of vibration for all distances involving caesium are very large. Structures have also been reported for AlF,- salts of rubidium and caesiuml’j and AlC14- salts of potassium,14 rubidium, and caesium.16 In each case the aluminium has approximately regular tetrahedral co-ordination, and results of refinements in which regularity is imposed are presented. The best results were obtained for structures with C,,symmetry, with the alkali-metal atoms bound to two halogens. For KAlC14,results are also given for refinement of a structure with three bridging halogens and C,, symmetry, but, although the fit is only marginallyworse for this arrangement, some of the parameters Seem unreasonable, with the K . . -A1 distance being less than K-CI. Some distances in the C,, structures are given in Table 1. It is also interesting to note that the amplitudes of vibration for the metal. * .metal atom pairs are fairly small (0.12-0.22 A), and always smaller than those for the alkali-metal-halogen bonded pairs. The picture that emerges, as with other salts, is of a close association of an ion pair, but with fairly free movement of the cation over the surface of the anion. 6

Table 1 Structural parametersfor some alkali-metal tetrahaloaluminates, MAIXl rg(Al-X)/A r,(M-X)/A r,(M. * *Al)/A

RbAlF,

CsAlF,

KAlCl,

RbAICI,

CsAICl,

1.696(5) 2.64(3) 3.32(7)

I .695(6) 2.84(9) 3.51(8)

2.153(6) 2.98(5) 3.71(7)

2.151(6) 3.16(3) 3.80(5)

2.149(9) 3.31(7) 3.8Y1 0 )

A short report of a study of potassium hydroxide vapour has also appeared.16 A dimeric structure is described, with each potassium atom bound equally to two oxygen atoms, and with overall D Z h symmetry. G. V. Girichev, N. I. Giricheva, E. A. Kuligin, and K. S. Krasnov. Zh. Sfrukr. Khim.. 1983, 24(1), 63. Is Yu. Sh. Kalaichev, K. P. Petrov, and V. V. Ugarov, Zh. Srrukt. Khim., 1983, 2 4 ( 5 ) , 176. l4 Yu. Sh. Kalaichev, K. P. Petrov, and V. V. Ugarov, Zh. Sfrukr. Khim., 1983, 24(5), 173. lb Yu. Sh. Kalaichev, K. P. Petrov, and V. V. Ugarov, Zh. Sfrukr. Khim., 1983, 2 4 ( 5 ) , 179. G. V. Girichev and S. B. Vasil’eva, Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol.. 1983, 26, 1137. l2

384


3 Compounds of Main-group 111 Elements New electron-diffraction data for the suboxides of gallium, indium, and thallium, at 1160, 1180, and 860 K, respectively, have been analysed in terms of the equilibrium interatomic distances (in the harmonic approximation) and the four force constants, which define the complete force field for each The geometrical parameters obtained are an order of magnitude more precise than those previously available, and they show that all three molecules are substantially bent whereas it had been thought that the observed angles of around 145" might arise from a shrinkage effect, with the equilibrium configuration being linear. The M-0 distances (r!) are 1.821(3), 2.016(3), and 2.092(3) A, and the MOM angles (Lt) are 142.9(3)", 145.0(4)', and 145.5(5)"for Ga,O, In,O, and T1,0, respectively. The refined force fields reproduce the observed vibrational frequencies quite well, but there is considerable uncertainty about the experimental values. Aluminium trifluoride vapour has been studied at 1320 K.18 The bond length (r,) is 1.6278(5) A, and the FAlF angle, without shrinkage correction, is 118.9". The F. - Fshrinkage is estimated to be 0.020 A, and there is no doubt at all that the average structure does have D3,,symmetry. The structure of the adduct of trimethylamine with boron tri-iodide at 480 K has been determinedl9and compared with the solid-phase structure. The main difference is in the B-N distance, which is longer by 0.08 A [r, is 1.663(13)A] in the gas; similar changes have been observed for other boron-nitrogen complexes. Other important parameters (re)are: r(B-I) 2.245(4),r(C-N) 1.497(5) A, LIB1 108.6(4)",and LCNC 106.0(8)".The barrier to rotation about the B-N bond is estimated to be ca. 15 kJ molt1, which is about the same as in the analagous BF3 complex but three times less than in the BBr, compound and five times less than in the chloride. The anomalously small value for the fluoride is thought to reflect the small van der Waals' radius for fluorine.

4 Compounds of Main-group IV Elements Somewhat surprisingly, the majority of the compounds described in this section have a Group IV atom formally in oxidation state 11. Quadrupole mass spectrometry has been used to find optimum conditions for the study of SiCl, and SiBr,, which were prepared by passing Si,CI, and SiBr, over elemental silicon at 1470 K.,O In the analysis of the SiCl, structure the fit was improved by including a small amount (less than 3%) of Si,C14, but otherwise the samples were apparently pure. The Si-Cl and Si-Br distances obtained (r,) were 2.083(4) and 2.243(5) A, respectively, and the angles at silicon were 102.8(6)" and 102.7(3)". The angle in SiCl, agrees with that derived from vibrational frequencies for the molecule trapped in an inert matrix. A. V. Demidov, A. G. Gershikov, E. Z. Zasorin, V. P. Spiridonov, and A. A. Ivanov, Zh. Srrukr. Khim., 1983, 24(1), 9. G. V. Girichev, A. N. Utkin, and N. I. Giricheva, Zzv. Vyssh. Uchebn. Zuved.. Khim. Khim. Tekhnol., 1983, 26, 634. K. Iijima and S. Shibata, Bull. Chem. SOC.Jpn., 1983, 56, 1891. 2o I. Hargittai, G. Schultz, J. Tremmel, N. D. Kagramanov, A. K . Maltsev, and 0. M. Nefedov, J. Am. Chem. SOC.,1983,105,2895.

Gas-phase Molecular Structures Determined by Electron Diffraction

385

Dihalides of tin and lead have been studied at temperatures between 550 and 10oO K by methods similar to those described above for Group 111 suboxides.17 In each case the angle at the metal atom is very close to loo", and there is little differencebetween the ro and r! structures. The bond lengths and angles in the 'harmonic equilibrium' approximation are: SnBr, 2.508(3) A and 100.1(7)", SnI, 2.701(4) 8, and 104.1(7)",PbF, 2.030(3) 8, and 97.2(20)", PbBr, 2.591(3) A and 99.2(15)", PbI, 2.796(4) A and 100.1(8)". There is impressive agreement between vibrational frequencies calculated from the refined force fields and from those measured experimentally, but as the published spectroscopic data from various sources are often contradictory and as the selection for comparison was made by the authors of the present study the agreement may appear better than it really is. However, this method of analysing diffraction data is clearly a useful one, at least for small molecules with symmetrical structures. Both 1,l'-dimethylgermanocene and 1,l '-dimethylstannocene21 have 'bent sandwich' structures of C,symmetry, with distances from the central atoms to the planes of the rings of 2.221(8) (Ge) and 2.400(6) (Sn) A. These correspond to average Ge-C and Sn-C distances ( r a )of 2.531(7) and 2.689(6) A, respectively. In both compounds there are large amplitude vibrations involving movement of the C,H,Me rings relative to each other and to the metal atom, and this picture is supported by molecular-orbital calculations on Ge(C5H5),.Consequently, the angles between the ring planes are not well determined, being 34(7)" in Ge(C5H4Me),and 50(6)" in Sn(C,H,Me),. Another group of derivatives of Group IV elements in oxidation state I1 are the amides M[N(SiMe,),],. The gas-phase structure of the tin compound has already been described, and now the germanium and lead compounds have also been studied;22 solid-phase results for the tin and lead compounds are also reported. In each case the central NMN unit is sharply bent and the nitrogen atoms have planar configurations, with the SiNSi groups approximately perpendicular to the NMN plane. The lightest central atom naturally has the shortest bonds [ra Ge-N 1.89(1), Sn-N 2.09(1), Pb-N 2.20(2) A], but to minimize steric interactions the short bond must be associated with wide angles, so LNGeN is 101(1.5)", LNSnN is 96", and LNPbN is 91(2)". However, in the crystal the latter angles are widened to 104.7(2)" and 103.6(7)", respectively. Other important parameters for the germanium and lead compounds (in that order) are: $3-N) 1.743(6) and 1.75( 1) A, r(Si-C) 1.883(6) and 1.880(6) A, LMNSi 121.1(7)"and 119.6(8)",and ,LNSiC 115.9(8)"and 112(1)". There seems to be a tradition that halocarbons are included in these reviews as inorganic compounds. Perfluorospiropentane23is an ideal subject for an electrondiffraction study, as it has a high degree of symmetry (&), and the structure is defined by just five parameters. Thus, although the two types of C-C distance

22

J. Almlof, L. Fernholt, K. Faegri, A. Haaland, B. E. R. Schilling, R. Seip, and K. Taugbal. Acra Chem. Scund., Ser. A , 1983, 37, 131. T. Fjeldberg, H. Hope, M. F. Lappert, P. P. Power, and A. J. Thorne, J . Chem. Soc.,

23

W. R. Dolbier, S. F. Sellers, B. E. Smart, and H. Oberhammer, J. Mol. Struct., 1983. 101.

21

Chem. Commun., 1983, 639. 193.

386


are very similar, they can easily be distinguished, with r(C-1-C-2) 1.487(6) A and r(C-1-C-3) 1.492(4) 8, (C-3 is the central spiro atom). In unfluorinated spiropentane C-l-C-2 is longer than C-1-C-3 by 0.05 A, and the different behaviour is attributed to the effects of electron withdrawal by the fluorine atoms. The C-F distance is 1.325(2) A, and the angles FCF, C-3-C-l-F, and C-2-C-1-F are 110.8(2)", 118.8(5)", and 120.0(5)", respectively. The bonds in four-membered carbon rings are much longer than those in three-membered rings, and in cyclobutyl silaneZ4the average C-C distance (r,) is 1.565(4) A and the Si-C distance is 1.873(3) A. An ab initio study was also done, and using results from this the C-C bonds adjacent to the silyl group were constrained to be 0.016 8, longer than the opposite ones. The refined CCC angle at the carbon with the silyl substituent was 88.5(8)". The ab initio study showed that non-bonded interactions were reduced by ring puckering but that the potential well was slightly asymmetric, so that the conformer with the silyl group in an equatorial position was preferred to the axial conformer. The experimental results supported this with 59(5) % equatorial, corresponding to an energy difference of just 0.8(4) kJ mol-l. The angles between the Si-C-I bond and the C-2-C-1-C-4 plane were 132.0(31)" (equatorial conformer) and 123.6(37)" (axial), and the ring-puckering angles (between C-2-C-1-C-4 and C-2-C-3-C-4 planes) were 31.8(30)" and - 23.3(41)" for the two conformers. In a study of bi~(trimethylsily1)methane~~ C3"symmetry was assumed for the SiMe, and Me groups, with no tilting parameters, and overall the symmetry was C,.Steric strain arising from the bulky trimethylsilyl groups was relieved by opening of the central SiCSi angle to 123.2(9)" and terminal SiCH angles to 115(1)O, lengthening of the central Si-C bonds to 1.889(4) A, compared with 1.874(2) A for the other Si-C bonds, and torsional displacement of the methyl groups from the staggered conformation by 25". The C(central)SiC(terminal) angles were 112.4(6)", which also shows the effect of the crowding. The structures and conformations of three silyl ethers, O(SiC1Me,),,26 O(SiH,Me),, and O(SiHMe2)2,27 have been reported. Important parameters are given in Table 2. In these and other ethers the range of Si-0 distances and SiOSi angles is remarkably small. The effect of methyl groups is to increase the angle very slightly, but the electronegative chlorine substituent has more influence, reducing the Si-0 distance a little and widening the oxygen angle. The conformations adopted are interesting, and in each case it is the arrangement of the silyl groups with respect to each other, rather than to the oxygen, that seems to be important. I n O(SiH,Me), there are at least two conformers. In the major one [64(8)%] the methyl groups are mutually anti when viewed along the Si- - .Si axis, with SiOSiC dihedral angles of 58(8)" and 124(4)". In O(SiHMe,), the SiOSiH dihedral angles are IOl(8)' and -41(4)", so that in the Si- - .Si view there is again a staggered arrangement but with just one anti pair of

25 26

M. Dakkouri and H. Oberhammer, J . Mol. Struct., 1983, 102, 315. T. Fjeldberg, R. Seip, M. F. Lappert, and A. J. Thorne, J. Mol. Struct., 1983, 99, 295. Q. Shen, J. MoI. Struct., 1983, 102, 325. D. W. H. Rankin and H. E. Robertson, J . Chem. SOC.,Dalton Trans., 1983, 265.

Gas-phase Molecular Structures Determined by Electron Diflraction

387

methyl groups and the two Si-H bonds gauche with respect to each other. However, in O(SiCIMe,), the SiOSiCl dihedral angles are 39(19)" and 102(6)' (60"and 120" gives a staggered Si * .Si arrangement with the chlorines nnti to each other), although a model with two conformers with angles 72" and 72" (2 parts) and 72"and 166" ( 1 part) gave an almost equally good fit to the data. *

Table 2

Structural parameters" for some silyl ethers

O(SiH,Me), O(SiHMe,), r(Si-O)/A 1.642(3) 1.635(2) r(Si--C)/A 1.864(3) 1.864(3) r(Si-Cl)/A LSiOSil" 143.0(6) 148.4(9) LOSiC/" 109.7(5) 110.1(6) LCSiC/" 107.4(17) LClSiO/" LClSiC/" 0 r p and L, for O(SiClMe,),, otherwise ra

O(SiCIMe,), 1.624(2) 1.852(2) 2.067(2) 154.0( 1 5) 110.0(8) 107.6 110.2(8: I O9.6(7)

In the germyl ester of thioacetic acid28the germyl group is bound to sulphur, whereas in the analogous silyl ester there is an Si-0 bond. There is a cisO=C-S-Ge arrangement, to within 5", with the result that the non-bonded Gee - -0distance is only 2.972(14) A, compared with the sum of van der Waals' radii for germanium and oxygen of ca. 3.6 A. Similar short contacts are found in many silyl and germyl esters. Important bond lengths and angles in the ra structure are: r(C-C) 1.493(lo), r ( C = O ) 1.224(8), r(C-S) 1.765(7), r(Ge-S) 2.233(4) A, LCCO 1 16.4(13)", i.SCO 124.1( lo)", and L GeSC 96.7(4)". The C-S distance is shorter than those in alkyl sulphides, just as C - 0 distances in esters are shorter than those in ethers, and the Ge-S bond is longer than in digermyl sulphide, which parallels the fact that Si-0 bonds are longer in silyl esters than in silyl ethers. 5 Compounds of Main-group V Elements

Dinitrogen pentoxide is probably the least well known of the oxides of nitrogen, and it is good to see a reliable report of its It has two terminal NO, groups (assumed to have local CZvsymmetry), joined by a central oxygen atom. The bond lengths ( r g )are 1.188(2) and 1.498(4) A for the double and single N-0 bonds, respectively, and the O=N=O and N-0-N angles are 133.2(6)" and 111.8( 16)".The overall symmetry is C,, with the NO2 groups twisted about 30" away from the all-planar positions, but there are large-amplitude torsional motions. These were modelled by a potential representing competition between forces stabilizing the planar form and repulsive forces between oxygen atoms destabilizing it. a8

E. A. V. Ebsworth, C. M. Huntley, and D. W. H. Rankin, J. Chem. SOC.,Dalton Trans..

ao

B. W. McClelland. L. Hedberg, K. Hedberg, and K. Hagen, J . Am. Chem. SOC.,1983, 105.

1983, 835. 3789.

388


Three more nitromethanes have been studied, and some important geometrical parameters are listed inTable3. I n Me2CHN02:30 the NOzgroup is twisted 17.9(21)" from the position in which one N=O bond eclipses the unique C-H bond, while in Me,CNO, the equivalent angle is 16.5(33)",with respect to one of the three were defined to be equivalent C-C bonds. The twist angles in Me2C(N02)231 zero when N=O bonds eclipsed C-N bonds, and they refined to 74.5(32)' and 13.1(21)".This molecule therefore has no symmetry. The nitro groups in are structurally similar to those m-dinitrobenzene and 1 -chlor0-3-nitrobenzene:~~ in the nitromethanes, with r,(N=O) 1.2232) and 1.243(3)A, and L O N 0 125.3(7)" and 122.6(10)".The NO2 groups are twisted slightly out of the ring planes, by 23(3)" and 13(6)".The aromatic rings are somewhat distorted from regular hexagons, with ring angles at the substituted carbon atoms increased to 121.5-123", and the angle at the intermediate atom reduced to ca. 118". The C-N distance in C,H,(NO,), is 1.461(6)& and in C,H,CI(NO,) the C-N and C-CI distances are 1.442(10)and 1.746(6) A, respectively. Table 3 Structural parameters (rp)for some nitromethanes r(N=0)/8,

;:--:;/;

L ONO/" LNCN/" L NCC/" LCCC/"

}mean

Me,CHNO, 1.226(2) 1.51 8(10)

Me,CNO, 1.240(2)

125.4(3)

122.2(6)

124.5(6) I 11.6(12)

109.2(9) 1 13.5( 17)

108.1(11) 1 10.9(11)

108.1 I 13.1 (23)

1.533(15)

Me,C(NO,), I .227(2) I .5 17( 15)

The effect of increasing methyl substitution on the structure of hydrazine seems to be mainly to decrease the N-N bond length.33 The distance ( r , ) is 1.401(4)A, less than in hydrazine or dimethylhydrazine. The C-N bond length is 1.463(1)& and the CNC and NNC angles are 110.8(16)" and 113.5(6)", respectively. It was found that there was a 70 : 30 mixture of gauche and trans conformers, with the dihedral angle in the gauche form being 78S0, compared with close to 90" in hydrazine and dimethylhydrazine. The N-CI and C-Cl distances in perchloromethylene imine, CIN= CC12,34 are perfectly normal, unlike the N-F and C-F bonds in FN=CF2. The distances (rao)are 1.683(10) and 1.718(6) A, and the CNCI, NCCl(cis), and NCCl(tvans) angles are 1 17.1 (4)", 127.5(4)", and 1 18.7(5)", respectively. The N=C distance is 1.266(5) A, insignificantly different from the distances in HN=CH2 and FN= CF,, which is somewhat surprising given the electronegativity differences involved. However, in MeN= CHCCI ,the corresponding I. F. Shishkov, N. I. Sadova, L. V. Vilkov, and Yu. A. Pankrushev, Zh. Strukt. Khint. 1983, 24(2), 25. 31 I. F. Shishkov, N. I. Sadova, L. V. Vilkov, and Yu. A. Pankrushev, Zh. Strukt. Khim.. 30

33 34

1983, 24(3), 173. 0. G. Batyukhnova, N. I. Sadova, L. V. Vilkov, and Yu. A. Pankrushev, J . Mol. S t r u t . . 1983, 97, 153. V. A. Naumov, 0. A. Litvinov, H. J. Geise, and J. Dillen, J . Mol. S t r u t . , 1983, 99, 303. D. Christen and K. Kalcher, J . Mol. Struct., 1983, 97, 143.

Gas-phase Molecular Structures Determined by Electron Difraction

389

distance is much greater, I .308( 13) A (ra).35This compound exists mainly or entirely in the E isomer, in which the CCI, group is trans to the methyl group, and with one C-Cl bond almost eclipsing the N=C bond. Other important parameters are: r(C-N) 1.467(13), r(C-C) I .534( 13), r(C-CI) t .778(5) A, LC=N-C 1 1 5.2(20)", LN=C-C 114.2(20)", LCl-C--CI 109.5(4)". The structure of PCI, at 360 K has been rein~estigated,~~ with allowance being made for partial (26%) dissociation into PC13 and Cl,. The results are very similar to those of the last study, with r,(P-CI) (mean) 2.060(2) A and the axial bonds 0.107(4) A longer than the equatorial ones. Non-bonded distances were refined without any model constraints, to give Cl,; * *Clax2.929(3), CI,,. *C1,,3.494(5), andC1,; - .Cla,4.248(6)A. Refined amplitudes of vibration are slightly different from those obtained earlier, but they agree well with values calculated from spectroscopic data. This is taken as evidence that PCIs, like PF6 but unlike VF,, has no low-lying polar states. Parameters for PCl,Me,37 PC12Pri,3*PCIBU',,~~ and PH2Ph3' are given in Table 4, and these illustrate very nicely several of the factors influencing bond lengths and angles. The P-C distance in PH,Me is 1.858 A, but this is reduced to 1.839 A in PH2Ph, reflecting the change in hybridization of the carbon atom from sp3 to sp2.In PC1,Me the corresponding distance is 1.831 A, the shortening this time being attributable to electron withdrawal by the electronegative chlorine atoms. This effect is partially reversed in the i-propyl compound, but in PClBu', the P-C bonds are lengthened to 1.894 A, a consequence of the steric strain caused by bulky t-butyl groups. The CPC angle in this compound is unusually wide, at 108.9'. Other parameters are much as would be expected. No significant distortion of the phenyl ring from a regular hexagonal shape was detected.

Table 4 Structural parameters (r,) .for some phosphines PCl BU'2 PC1,Me PCI,Pri 2.079(4) r(P-Cl)/ A 2.061(3) 2.058(2) r(P-C)/A r(C-C)/A LCIPCI/o LClPC/O L CPC/" L CCP/" L CCC/"

1.831(10) 100.7(5) 98.8(6)

1.847(1 3) 1.550(10) 100.5(4)

101.7(8) I13.1(11) 108.0(34)

1.894(5) 1.548(3)

PH2Ph

1.839(5) I .399(3) (mean)

101.7(7) 108.9(13) 108.4(8) 110.6(8)

A short discussion of the problems involved in combining electron-diffraction and liquid-crystal n.m.r. data in studies of difluorophosphinopseudo-halides has been published.3 B Large-amplitude vibrations are particularly troublesome, but using n.m.r. data relating only to the PF2N group of PF2NC0 reduces correlatione between parameters, and improves the precision of the results. The best parameters (r") for this molecule are : r(P-F) 1.573(I), r(P-N) 1.678(4), V, A, NrUov, 0. A. Litvinov, and A. M. Kibardin, Zh. Strukt. Khim., 1983,24(2). 159. B, W, McClolland, L. Hedberg, and K. Hedberg, J. Mof. Struct., 1983,W. 309. nt V. A. NImov and 0. N. Kataeva, Zh. Srrukt. Khim., 1983,24(2), 160. aa V. A. NaWOv and 0. N. Kataeva, Zh. Strukt. Khim., 1983,24(5), 96. w P. D.Blatr, J. Mol. Struct., 1983, 97, 147. 88


395

atoms [r,(Mo-F,) 2.012(10) A] and four terminal fluorine atoms [r(Mo-F) 1.814(6) A], two of which are in axial and two in equatorial positions [r(Mo-Fa) 1.804(35), r(Mo-F,) 1.821(30) 4. The angles at molybdenum are: F,MoF, 79.4(1l)", F,MoF, 100.5(21)", and F,MoF, 160.1(10)". Niobium pentduoride at 330 K is also t r i m e r i ~ with , ~ ~ Dsh symmetry, and its structure is very similar to that of the molybdenum analogue described above. 2.053(6), r(Nb-Fa) 1.830(20), Important parameters (r,) are : r(Nb-F,) r(Nb-F,) 1.837(20) A, LF,NbF, 80.6(18)", LF,NbF, 101.1(28)", and LF,NbF, 165.9(15)".The vibrational frequencies for this compound have also been ~alculated,~ using a force field that reproduced the observed vibrational amplitudes. This is not an ideal arrangement for such a complicated molecule, but it is better than nothing. There are 32 vibrational modes, six of which are inactive in both infrared and Raman, and only 11 frequencieshave been observed. Those 11 all lie quite close to calculated values - perhaps not surprisingly with 32 frequencies packed into less than 800 cm-l! Chromyl fluoride has also been reinvestigated,68as earlier results were not consistent with a published interpretation of the microwave spectrum, or with VSEPR predictions. Analysis was difficult, as the radial-distribution curve contained just two peaks, but the final conclusion is that the previous electrondiffraction and microwave results are both wrong and that VSEPR theory fails for chromyl halides! No dotbt we will hear more of this compound. The results (rp, La)are: r(Cr=O) 1.575(2), r(Cr-F) 1.720(2) A, LOCrO 107.8(8)", and L FCrF 11 1.9(9)", with C,, symmetry. Copper(@ bis(acety1acetonate) has a monomeric with the copper atom having square-planar co-ordination, but there is a dihedral angle of 18" between the planes of the ligand heavy atoms and the CuOl plane. The equivalent angle is 13.6"in the crystalline phase and 16" for gaseous Zn(acac),, and in this respect and all others this structure is consistent with related ones. Important bond lengths and angles (ra) are: r(Cu-0) 1.914(2), r(0-C) 1.273(2), r(C-C) (ring) 1.402(3), r(C-C) (methyl) 1.512(4) A, LOCuO (Cu-0 bonds from one ligand) 92.3(9)",and LCuOC 124.8(10)".

67

G. V. Girichev, V. N. Petrova, V. M. Petrov, and K. S. Krasnov, Zh. Coord. Khim., 1983, 9, 799.

R. J. French, L. Hedberg, K. Hedberg, G . L. Gard, and B. M. Johnson, Inorg. Chem., 1983, 22, 892. ss S. Shibata. T. Sasase, and M. Ohta. J. Mol. Struct., 1983, 96, 347.

Gas-phase Molecular Structures Determined by Electron Di'raction

391

to apply two constraints based on the ab initio results. Labelling the atoms as shown in structure (1) the differences r(S-F) - r(S-F,) and r(S-F) -

r(S-Fa) were fixed. The final r," parameters were then: r(S-S') 2.040(5), r(S-Fa) 1.624(6), r(S-Fa') 1.722(8), r(S-F,) 1.569(8), r(S'-F) 1.602(5) A, LFaSS' 92.2(6)", LFa'SS' 76.0(10)", LF,SS' 1O4.9( 14)", LFS'S 105.9(10)", LFaSFa' (dependent parameter) 167.0", LFaSF, 89.8(13)", LFa'SF, 84.4(31)". The F,SS'F dihedral angle was 95.1(43)". Thus the final structure corresponds to the VSEPR model with fluorine atoms in axial positions, but there are very large distortions from an idealized trigonal bipyramid. N.m.r. spectra indicate that the barrier to rotation about the S-S bond is high.

Table 6 Some structural parametersa for sulphones, S0,XY

x = Y = CCl, r(S=O)/A r(s--c)/A r(C-halogen)/A LOSO/"

L OSC/O L OSCl/"

1.419(3) 1.894(5) 1.757(4) 120.8( 10) 10633) 109.8(4)

LCSC/"

x = c1, Y = CsF5 1.415(3) 1.798(6) 1.326(3) 123.6( 10) 108.2(6) 105.3(2) 104.8(8)c

X Y

=

Me,

X

=

=

CH2Br

Y

=

Me,

1.437(3) 1.784(5)" 1.943(7) 116.8(12) 105.7(7)"

CBr=CH,, 1.438(4) 1.765(6)" 1.877(9) 121.6(26) 105.6(17)"

104.312)

1O4.4(25)

Distances are ro for the first two structures but not specified for the others. symmetry was assumed for the SOpClskeleton. CSCl angle

a

C,

Sulphones have been popular subjects for electron-diffraction studies for some time, and some parameters for four more are listed in Table 6. The bulky CCl, groups in S0,(CCl,)243make their presence felt most noticeably in the long C-S bonds, the longest yet found in a sulphone, but there are also an unusually wide CSC angle and a tilt of 5" of the CCl, groups away from each other. The ClCCl angles in these groups are 110.2(1)", and the groups are twisted 12" from the staggered positions, giving overall C, symmetry. Attempts to collect data for SO,(CBr,), were unsuccessful, owing to the instability of the sample. In S0,Cl(C,F,)44the effect of the fluorine atoms is to increase the S-C distance, from 1.764 in S0,ClPh to 1.798 A, and to decrease the S-Cl distance from 2.05 to 2.027(5) A. Otherwise, the structure is much as would be expected, with no significant distortion of the ring, which is twisted 61.8(22)" from the S0,Cl

a

48

M. Hargittai, E. Vajda, C. J. Nielsen, P. Kloeboe, R. Seip, and J. Brunvoll, Acta Chcrm. Scad., Ser. A, 1983,37, 341. E. Vajda and I. Hargittai, 2. Naturforsch., Teil A , 1983,38, 765.

392


mirror plane so that it almost eclipses one S=O bond. In BrCH2S02Me46 the SCBr angle is 113.3(8)"and the CSCBr dihedral angle 64.4(23)",so that a staggered conformation is found, with the bromine between the methyl group and one oxygen atom. In CH2=CBrS02Me45the C=C distance is 1.350(13) A, and C=C-S and C=C-Br angles are 120.9(28)"and 123.0(27)",respectively. The most interesting feature of this structure is the conformation, as the C=C bond almost eclipses one S=O bond, with the dihedral angle 3(3)", and the bromine atom therefore again lies between the methyl group and one oxygen atom. Both S(PF2)2and Se(PF,), have average structures with C,, ~ y m m e t r ywith ,~~ the phosphorus lone pairs syn with respect to the further S-P or Se-P bond, but there are large-amplitude torsional vibrations, with root-mean-square torsion angles of 22(2)" and 20(4)" for the sulphur and selenium compounds, respectively, corresponding to (harmonic) frequencies of 25(3) and 27(5) cm-l. Because the angles at the central atoms are small, there are quite strong interactions between each lone pair and its neighbouring phosphorus atom, and this is believed to account for the large, and strongly temperature-dependent, PP n.m.r. coupling constants. For PF,(SMe) three conformations fit the data almost equally well, with the PF2 group twisted 19(3)", 106(9)",or 171(5)" away from the position in which the methyl group lies syn to the phosphorus lone pair. The second of these conformations is favoured and is thought to be stabilized by weak non-bonded He - * F interactions. Important parameters for all three compounds are given in Table 7. Most striking are the variations in P-S bond length and in angles at sulphur or selenium.

Table 7 Structural parameters (r,) .for some Group VI jluorophosphine derivatives r(P-F)/A r(P-Y)/A r(s-C)/A L FPF/" LFPYI" LPYP/" LPYC/"

PF2(S Me) 1.589(3) 2.085( 3) 1.822(5) 95.6(6) 101.2(3)

S(PF,), 1.572(2) 2.1 32(4) 97.4(5) 100.2(4) 91.3( 1 1)

Se(PF2)2 1.573(3) 2.273(5) 100.6(1 I ) 98.7(4) 94.6(8)

102.0(12)

The three compounds SF,NCO, SeF,NCO, and TeF,NC04' are all clearly identified as isocyanates with the NCO groups in staggered positions with respect to the MF, groups: infrared evidence had previously been interpreted as indicating that the selenium compound was a cyanate. The geometrical parameters are listed in Table 8. No deviation from regular octahedral co-ordination at the central atom was observed, nor were any differences between axial and

45 O6

O7

V. A. Naumov and R. N. Ziatdinova, Zh. Strukt. Khim.,1983, 24(3), 48. D. E. J. Arnold, G. Gundersen, D. W. H. Rankin, and H. E. Robertson, J . Chern. Soc.. Dalton Trans., 1983, 1989. H. Oberhammer, K. Seppelt, and R. Mews, J. Mol. Strucf., 1983, 101, 325.

Gas-phase Molecular Structures Determined by Electron Diflraction

393

equatorial M-F bond lengths found, and this regularity was assumed in the published refinement. Quoted errors may therefore be a little optimistic. In each case N=C bonds are somewhat longer than in other isocyanates, and the M-N bonds are shorter than expected, based on covalent radii with corrections for electronegativity differences. It is most remarkable that the S-N and Se-N distances are 0.101 and 0.1 12 A longer than S-F and Se-F, respectively, but that the Te-N bond is only 0.033 8, longer than the Te-F bonds. Angles at nitrogen are all small, but in the selenium compound the angle is the smallest yet recorded for an isocyanate. This may be connected in some way with the anomalous vibrational spectra for this compound.

Table 8 Structural parameters (r,) .for XFJNCO (X = S, Se, or Te) SFSNCO 1.234(8) r(C=O)/A 1.179(7) r(X-F) (mean)/A 1.567(2) r(X-N)/B( 1.668(6) 124.9(12) LXNCI" L NCO/" 173.8(37) r(N=C)IA

SeF,NCO I .260(1I ) 1.187(9) 1.677(2) 1.789(6) 116.9(8) 172.9(32)

TeFgNCO 1.244(13) 1.186(11) I .826(6) 1.859C21) 126324) I75.7(26)

Vapour from a sample of SeC14passing through a nozzle at 450 K was found to consist of 80% SeCl, and 20% Cl,.48The Se-CI distance (r,) was 2.157(3) 8, and the ClSeCl angle was 99.6(5)". The latter value is some 5" less than the angles at selenium in Se,CI,, which has longer Se-CI bonds. Similar differences have been noted between SCIaand S,CI,. A study of TeMe,, assuming Ca, symmetry, yielded r,(Te-C) 2.142(5) 8, and LCTeC 94(2)".40 7 Compounds of Main-group VII Elements

The trifluorides of bromine and chlorine have been reinve~tigated,~~ and now data from all sources agree. (Some old diffraction data had h n interpreted in terms of C,, symmetry models.) Both compounds are T-shaped, as expected from electron-pair repulsion theory for 10-electron species with two lone pairs, with Fax-CI-F,, and Fa,-Br-F,, angles of 87(2)" and 85(2)", respectively. In CIF, the axial and equatorial C1-F bond lengths are 1.703(14) and 1.584(12) A, while the corresponding distances in BrF, are 1.809(17) and 1.728(15) A, the difference in the latter case being somewhat less than it is in the former.

8 Transition-metal Compounds It is most remarkable that this year there is only one report of the structure of a transition-metal complex, other than simple halides and oxyhalides. Clearly this is a neglected, if difficult, field, as gas-phase structures are needed for comparison with the plethora of crystalline-phase structures that are published. However, L. Fernholt, A. Haaland, R. Seip, R. Kniep, and L. Korte. 2. Naruyforsch., Teil B, 1983, 38, 1072. 40 A. A. Ishchenko, I. N. Myakshin, G. V. Romanov, V. P. Spiridonov. and V. F. Sukhoverkhov, Dokl. Akad. Nauk SSSR, 1982. 267, 1143. 48

394


the work with halides is interesting and of much higher quality than was normal a few years ago. Work on titanium subgroup tetrahalides, lanthanide trihalides, and some cyclic M2F2molecules has been reviewed.50 Mention must also be made here of the studies of the feasibility of determining vibrational frequencies from electron-diffraction data, applied particularly to TiF4, ZrF,, Hf F4, and (NbFS)3,which is discussed in the introduction to this ~ h a p t e r . ~ Manganese difluoride has been studied at 1400 KS1The Mn-F distance reported (rp) is 1.813(5) A, and the refined F. . . F distance is 3.615(50) A, so that the molecule is linear within experimental error. In fact the observed shrinkage [0.011(55)A]is less than that expected (0.09 A) for a linear molecule. Uranium tetrafluoride has been rein~estigated,~, and the results confirm that it is not tetrahedral, but unfortunately C,, and Dzd models fit the data (obtained at 1300 K) equally well. The scattering is dominated by the U-F atom pairs, and both models give mean U-F distances (r,) of 2.067(1) A. The non-bonded F . . F distances were refined independently, to 3.520(8) and 3.178(17) 8, in the C3, model and to 3.481(9) and 3.153(19) A in the D2d model. Apart from Td, C4, and Dphmodels were tried; rather curiously, C,, was not. However, tungsten tetrachloride has been shown to have C2, symmetry, with a trigonal-bipyramidal ~ t r u c t u r e Axial . ~ ~ and equatorial W-Cl distances are 2.295(6) and 2.202(6) A, respectively, and the angles between the two equatorial and between the two axial bonds are 90(4)" and 170(10)". By making a number of assumptions to simplify the force field, the authors have been able to use observed vibrational amplitudes to define a force field and then to calculate a complete set of vibrational frequencies. Tungsten penta~hloride~~ and molybdenum pentachl~ride~~ have also been reinvestigated, as the original D3h symmetry proposed for the molybdenum compound had been disputed and C,,symmetry claimed instead. Both molecules still have trigonal-bipyramidal structures at the experimental temperatures (670 and 770 K for WCI5,430 and 770 K for MoCl,), with axial bonds longer than equatorial ones [r,(W-CI,) 2.286(20), r(W-Cle) 2.246(20), r,(Mo-CI,) 2.291(5), r(Mo-CI,) 2.251(1) A]. The gas-phase Raman spectrum of MoCl, has been studied, and it is compatible with the D3hstructure. In the present work a force field was developed that reproduced both observed frequencies and vibrational amplitudes and thus enabled hitherto unobserved frequencies to be calculated. at which temperature Molybdenum pentafluoride has been studied at 330 K,58 it exists mainly as a cyclic trimer of D3,, symmetry. (The remainder was 28% of MoF40.) Each metal atom is six-co-ordinated, with two bridging fluorine

-

K. S. Krasnov, Zh. Strukt. Khim., 1983, 24(1), 3. G. V. Girichev, N. Yu. Subbotina, and N. I. Giricheva, Zh. Strukt. Khim., 1983, 24(2), 158. s2 G. V. Girichev, V. M. Petrov, N. I. Giricheva, E. Z . Zasorin, K . S. Krasnov, and Yu. M. Kiselev, Zh. Strukt. Khim., 1983, 24(1), 70. 53 Yu. S. Ezhov and S. A. Komarov, Zh. Strukt. Khim., 1983, 24(2), 156. 64 Yu. S. Ezhov and A. P. Sarvin, Zh. Strukt. Khim., 1983,24(1), 149. O5 Yu. S. Ezhov and A. P. Sarvin, Zh. Strukt. Khim., 1983,24(1), 57. G. V. Girichev, V. N. Petrova, V. M. Petrov, K. S. Krasnov, and V. K. Goncharuk, Zh. Strukt. Khim., 1983, 24(3), 54. Lo 61


395

atoms [r,(Mo-F,) 2.012(10) A] and four terminal fluorine atoms [r(Mo-F) 1.814(6) A], two of which are in axial and two in equatorial positions [r(Mo-Fa) 1.804(35), r(Mo-F,) 1.821(30) 4. The angles at molybdenum are: F,MoF, 79.4(1l)", F,MoF, 100.5(21)", and F,MoF, 160.1(10)". Niobium pentduoride at 330 K is also t r i m e r i ~ with , ~ ~ Dsh symmetry, and its structure is very similar to that of the molybdenum analogue described above. 2.053(6), r(Nb-Fa) 1.830(20), Important parameters (r,) are : r(Nb-F,) r(Nb-F,) 1.837(20) A, LF,NbF, 80.6(18)", LF,NbF, 101.1(28)", and LF,NbF, 165.9(15)".The vibrational frequencies for this compound have also been ~alculated,~ using a force field that reproduced the observed vibrational amplitudes. This is not an ideal arrangement for such a complicated molecule, but it is better than nothing. There are 32 vibrational modes, six of which are inactive in both infrared and Raman, and only 11 frequencieshave been observed. Those 11 all lie quite close to calculated values - perhaps not surprisingly with 32 frequencies packed into less than 800 cm-l! Chromyl fluoride has also been reinvestigated,68as earlier results were not consistent with a published interpretation of the microwave spectrum, or with VSEPR predictions. Analysis was difficult, as the radial-distribution curve contained just two peaks, but the final conclusion is that the previous electrondiffraction and microwave results are both wrong and that VSEPR theory fails for chromyl halides! No dotbt we will hear more of this compound. The results (rp, La)are: r(Cr=O) 1.575(2), r(Cr-F) 1.720(2) A, LOCrO 107.8(8)", and L FCrF 11 1.9(9)", with C,, symmetry. Copper(@ bis(acety1acetonate) has a monomeric with the copper atom having square-planar co-ordination, but there is a dihedral angle of 18" between the planes of the ligand heavy atoms and the CuOl plane. The equivalent angle is 13.6"in the crystalline phase and 16" for gaseous Zn(acac),, and in this respect and all others this structure is consistent with related ones. Important bond lengths and angles (ra) are: r(Cu-0) 1.914(2), r(0-C) 1.273(2), r(C-C) (ring) 1.402(3), r(C-C) (methyl) 1.512(4) A, LOCuO (Cu-0 bonds from one ligand) 92.3(9)",and LCuOC 124.8(10)".

67

G. V. Girichev, V. N. Petrova, V. M. Petrov, and K. S. Krasnov, Zh. Coord. Khim., 1983, 9, 799.

R. J. French, L. Hedberg, K. Hedberg, G . L. Gard, and B. M. Johnson, Inorg. Chem., 1983, 22, 892. ss S. Shibata. T. Sasase, and M. Ohta. J. Mol. Struct., 1983, 96, 347. s8

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