A review of the recent literature published up to late 1985. 9781847555038, 1847555039

Table of contents :
Cover
Contents
Chapter I: Nuclear Magnetic Resonance Spectroscopy
1. Introduction
2. Stereochemistry
Complexes of 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 Os
Complexes of Co, Rh, and Ir
Complexes of Ni, Pd, and Pt
Complexes of Cu, Ag, and Au
Complexes of Zn, Cd, and Hg
3. Dynamic Systems
Fluxional Molecules
Equilibria
Course of Reactions
4. Paramagnetic Complexes
The Transition Metals
Compounds of the Lanthanides and Actinides
5. Solid-state N.M.R. Spectroscopy
Motion in Solids
Structure of Solids
Molecules Sorbed Onto Solids
6. Group IIIB Compounds
7. Group IVB Elements
8. Compounds of Group VB Elements
9. Compounds of Group VIB, Chlorine, Iodine, and Xenon
10. Appendix
References
Chapter 2: Nuclear Quadrupole Resonance Spectroscopy
1. Introduction
2. Main-group Elements
Deuterium
Group I (Lithium-7, Sodium-23, and Caesium-133)
Group III (Boron-10 and -11 and Aluminium-27)
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
Cobalt - 59
Copper-63 and -65
‘Niobium-9 3
Praseodymium-141
Tantalum-181
References
Chapter 3: Rotational Spectroscopy
1. Introduction
2. van der Waals and Hydrogen-bonded Complexes
3. Diatomic Species
4. Triatomic Molecules and Ions
5. Tetra-atomic Molecules and Ions
6. Penta-atomic Molecules
7. Molecules With Six and More Atoms
References
Chapter 4: Characteristic Vibrations of Compounds of Main-group Elements
1. Group I
2. Group II
3. Group III
Boron
Aluminium
Gallium
Indium and Thallium
4. Group IV
Carbon
Silicon
Germanium
Tin and Lead
5. Group V
Nitrogen
Phosphorus
Arsenic
Antimony
Bismuth
6. Group VI
Oxygen
Sulphur and Selenium Rings and Chains
Other Sulphur and Selenium Compounds
Tellurium
7. Group VII
8. Group VIII
References
Chapter 5: Vibrational Spectra of Transition-element Compounds
1. Detailed Studies
Resonance Raman Spectra
2. Scandium, Yttrium, and the Lanthanoids
3. Titanium, Zirconium, and Hafnium
4. Vanadium, Niobium, and Tantalum
5. Chromium, Molybdenum, and Tungsten
6. Manganese, Technetium, and Rhenium
7. Iron, Ruthenium, and Osmium
8. Cobalt, Rhodium, and Iridium
9. Nickel, Palladium, and Platinum
10. Copper, Silver, and Gold
11. Zinc, Cadmium, and Mercury
12. The Actinoids
References
Chapter 6: Vibrational Spectra of Some Co-ordinated Ligands
1. Carbon, Silicon, and Tin Donors
2. Carbonyl and Thiocarbonyl Complexes
3. Boron-containing Donors
4. Nitrogen Donors
Molecular Nitrogen, Azido, and Related Complexes
Amines and Related Ligands
Ligands Containing >X=N< Groups
Cyanides, Isocyanides, and Related Ligands
Nitrosyls
5. Phosphorus and Antimony Donors
6. Oxygen Donors
Molecular Oxygen, Peroxo, Aquo, and Related Complexes
Carboxylato and Related Complexes
Keto, Alkoxy, Ether, and Related Complexes
Ligands Containing O-N or O-P Bonds
Ligands Containing O-S, O-Se, or O-Te Bonds
Ligands Containing O-C1 Bonds
7. Sulphur Donors
8. Potentially Ambident Ligands
Cyanates, Thio- and Seleno-cyanates, and Their Iso Analogues
Ligands Containing N and O Atoms
Ligands Containing N and S Atoms
Ligands containing S and O Atoms
References
Chapter 7: Moessbauer Spectroscopy
1. Introduction
Books and Reviews
2. Theoretical
3. Instrumentation and Methodology
4. Iron-57
General Topics
Compounds of Iron
Oxide and Chalcogenide Compounds Containing Iron
Applications of Iron-57 Moessbauer Spectroscopy
5. Tin
General Topics
Inorganic Tin(II) Compounds
Inorganic Tin(IV) Compounds
Organotin(IV) Compounds
6. Other Elements
Main-group Elements
Transition-metal Elements
Lanthanide and Actinide Elements
7. Backscatter Conversion-electron Moessbauer Spectroscopy
Iron
Other Elements
References
Chapter 8: Gas-phase Molecular Structures Determined by Electron Diffraction
1. Introduction
2. Compounds of Elements in Main Groups I, II, and III
3. Compounds of Elements in Main Group IV
4. Compounds of Elements in Main Group V
5. Compounds of Elements in Main Group VI
6. Compounds of Transition Elements
References

Citation preview

Spectroscopic Properties of Inorganic and Organometallic Compounds

Volume 19

A Specialist Periodical Report

Spectroscopic Properties of Inorganic and Organometallic Compounds Volume 19

A Review of the Recent Literature Published up to Late 1985 Senior Reporters G. Davidson, Department of Chemistry, University of Notting ham E. A. V. Ebsworth, F.R.S.E., Department of Chemistry, University of €din burgh 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 8. 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 0-85186-1 73-3 ISSN 0584-8555

Copyright @ 1986 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-raphic, electronic, including photocopying, recording, taping or information storage and retrieval systems-without written permission from the Royal Society of Chemistry Printed in Great Britain by Whitstable Litho Ltd., Whitstable, Kent

Foreword The coverage of this volume is essentially the same as last year's; production by camera-ready copy has presented no insurmountable difficulties, though the result is of course less uniform and somewhat less pleasing to the eye than are books produced by traditional methods. I am as ever grateful to the authors for their excellent work, and I deeply regret that purchasers will have to pay so much to benefit from it. E. A. V. Ebsworth

Contents Chapter

1 Nuclear Magnetic Resonance Spectroscopy By B . E , Mann 1 Introduction

1

2 Stereochemistry

2 2

Complexes of 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 3 Dynamic Systems

Fluxional Molecules Bery 1L ium Magnesium Scandium Thorium and Uranium Titanium, Zirconium, and Hafnium Niobium Tanta 1um Chromium, Molybdenum, and Tungsten Manganese Rhenium Iron, Ruthenium, and Osmium Cobalt, Rhodium, and Iridium Nickel, Palladium, and Platinum Gold Zinc, Cadmium, and Mercury Boron Aluminium and Gallium Carbon Silicon Tin Phosphorus Arsenic Sulphur Se1enium Tellurium Equilibria Solvation Studies of Ions Group IA Magnesium The Lanthanides U ranium

3 5 6 12 13 18 23 27 28 30 31 31 31 31 31 31 32 32 32 35 35 36 39 40 42 42 42 43 43 43 44 45 46 46 46 47 47 47 47 48 48 48

viii

Spectroscopic Properties of Inorganic and Organometallic Compounds Vanadium Ruthenium Cobalt Rhodium Nickel P 1atinum Copper Zinc Aluminium and Gallium Oxygen Sulphur Fluorine Ionic Equilibria Group IA Group IIA The Lanthanides The Actinides Vanadium, Niobium, and Tantalum Chromium Molybdenum Tungsten Manganese Iron Ruthenium Cobalt Rhodium and Iridium Nickel P 1at inum Copper Gold Zinc, Cadmium, and Mercury Boron Aluminium and Gallium Indium Thallium Silicon Nitrogen Phosphorus Selenium Chlorine Iodine Equilibria Among Uncharged Species Titanium Chromium Mo 1ybdenum Iron Ruthenium Cobalt Rhodium Iridium Nickel Palladium and Platinum Copper Cadmium Boron A1 umin ium Ga 11ium Silicon Tin Phosphorus Antimony Sulphur

48 49 49 49 49 49 49 49 49 50 50 50 50 50 53 53 54 54 54 54 54 54 55 55 55 55 56 56 56 57 57 58 58 58 58 59 59 59 59 59 59 59 59 59

59 60 60 60 60 60 60 60 61 61 61 61 61 61 61 62 62 62

Contents

ix Course of Reactions Alkali Metals Uranium Titanium and Zirconium Niobium and Tantalum Molybdenum Tungsten Rhenium Iron Ruthenium and Osmium Cobalt Rhodium and Iridium Nickel Palladium and Platinum Gold Boron Silicon, Germanium, and Tin Phosphorus Chlorine 4 Paramagnetic Complexes

The Transition Metals Vanadium Chromium and Molybdenum Manganese and Technetium Iron, Ruthenium, and Osmium Cobalt Nickel Copper Compounds of the Lanthanides and Actinides Lanthanides Actinides 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 6 Group IIIB Compounds

Boron Hydrides and Carboranes Other Compounds of Boron Complexes of Other Group IIIB Elements

67 67 67 67 68 68 69 69 69 69 69 70 70 71 74 86 86 87 89 89 90 92

7 Group IVB Elements

92

8 Compounds of Group VB Elements

97

9

Compounds of Group VIB, Chlorine, Iodine, and Xenon

10 Appendix References Chapter

62 62 62 62 62 62 63 63 63 63 64 64 65 65 65 65 66 66 67

102 102

109

2 Nuclear Quadrupole Resonance Spectroscopy

By K . B . D i l l o n

1 Introduction

192

2 Main-group Elements

1 92

X

Spectroscopic Properties of Inorganic and Organometallic Compounds Deuterium Group I (Lithium-7, Sodium-23, and Caesium-133) Group I11 (Boron-10 and -11 and Aluminium-27) 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 Cobalt- 59 Copper-63 and -65 ‘Niobium-93 Praseodymium-141 Tantalum-181 References

Chapter

194 197 197

204 204 204 205 205 205 205

3 Rotational Spectroscopy By S. Cradock 1 Introduction

209

2 van der Waals and Hydrogen-bonded Complexes

209

3 Diatomic Species

211

4 Triatomic Molecules and Ions

216

5 Tetra-atomic Molecules and Ions

219

6 Penta-atomic Molecules

220

7 Molecules With Six and More Atoms

221

References

Chapter

192 193 194

222

4 Characteristic Vibrations of Compounds of Main-group Elements B y G. D a v i d s o n 1 Group I

228

2 Group I1

228

3 Group I11 Boron Aluminium Ga 11ium Indium and Thallium

229 229 230 232 233

4 Group IV

233 233 235 237 238

Carbon Silicon Germanium Tin and Lead 5 Group V Nitrogen Phosphorus Arsenic

239 239 241 242

Contents

xi Antimony Bismuth 6 Group VI

Oxygen Sulphur and Selenium Rings and Chains Other Sulphur and Selenium Compounds Tellurium

Chapter

Chapter

243 244 244 244 245 246 247

7 Group VII

247

8 Group VIII

249

References

24 9

5 Vibrational Spectra of Transition-element Compounds By G . D a v i d s o n 1 Detailed Studies Resonance Raman Spectra

260 261

2 Scandium, Yttrium, and the Lanthanoids

262

3 Titanium, Zirconium, and Hafnium

263

4 Vanadium, Niobium, and Tantalum

264

5 Chromium, Molybdenum, and Tungsten

265

6 Manganese, Technetium, and Rhenium

269

7 Iron, Ruthenium, and Osmium

271

8 Cobalt, Rhodium, and Iridium

273

9 Nickel, Palladium, and Platinum

274

10 Copper, Silver, and Gold

276

11 Zinc, Cadmium, and Mercury

278

1 2 The Actinoids

279

References

280

6 Vibrational Spectra of Some Co-ordinated Ligands

By G . D a v i d s o n

1 Carbon, Silicon, and Tin Donors

291

2 Carbonyl and Thiocarbonyl Complexes

299

3 Boron-containing Donors

306

4 Nitrogen Donors

306 306 308

Molecular Nitrogen, Azido, and Related Complexes Amines and Related Ligands Ligands Containing X = N ’ Groups Cyanides, Isocyanides, and Related Ligands Nitrosyls

310 313 315

xii

Spectroscopic Properties of Inorganic and Organometallic Compounds 5 Phosphorus and Antimony Donors

317

6 Oxygen Donors

318

Molecular Oxygen, Peroxo, Aquo, and Related Comp1exes Carboxylato and Related Complexes Keto, Alkoxy, Ether, and Related Complexes Ligands Containing 0-N or 0-P Bonds Ligands Containing 0 - S , 0-Se, or 0-Te Bonds Ligands Containing 0-C1 Bonds 7 Sulphur Donors

326

8 Potentially Ambident Ligands

328

Cyanates, Thio- and Seleno-cyanates, and Their Is0 Analogues Ligands Containing N and 0 Atoms Ligands Containing N and S Atoms Ligands containing S and 0 Atoms References

Chapter

318 320 323 323 325 326

328 329 332 334

335

7 Moessbauer Spectroscopy B y S . J . C l a r k , J . D . D o n a l d s o n , a n d S . M . Grimes

1 Introduction Books and Reviews

350 3 50

2 Theoretical

352

3 Instrumentation and Methodology

3 56

4 Iron-57

360 360 360

General Topics Nuclear Parameters and Metallic Iron Iron-57 Impurity Studies, Polymers, and Ion Exchange Frozen Solutions and Matrix Isolation Emission Studies Compounds of Iron High-spin Iron(I1) Compounds High-spin Iron(II1) Compounds Intercalation Compounds Containing Iron Mixed-valence Compounds and Unusual Electronic States Spin-crossover Systems and Unusual Spin States Low-spin and Covalent Compounds Biological Systems and Related Compounds Oxide and Chalcogenide Compounds Containing Iron General and Hydroxides Wustite, Haematite, and Related Oxides Magnetite and Spinel-type Oxides Other Oxides Inorganic Oxide Glasses Containing Iron Minerals Chalcogenides Applications of Iron-57 Moessbauer Spectroscopy Catalysts Coal, Soils, and Sediments Cements and Ceramics Other Applications

362 363 364 364 364 366 368 368 369 370 372 376 376 377 378 380 381 383 384 385 385 386 387 387

xiii

Contents 5 Tin

General Topics Inorganic Tin(I1) Compounds Inorganic Tin(1V) Compounds Organotin(1V) Compounds 6 Other Elements Main-group Elements Antimony (Sb-121) Tellurium (Te-125) Iodine (1-127 and 1-129) Transition-metal Elements Nickel (Ni-61) Zinc (211-67) Ruthenium (Ru-99) Tantalum (Ta-181) Iridium (Ir-193) Gold (Au-197) Lanthanide and Actinide Elements Europium (Eu-151) Gadolinium (Gd-155) Dysprosium (Dy-161) Erbium (Er-166) Thulium (Tm-169) Ytterbium (Yb-170, Yb-174) Neptunium (Np-237)

388 388 393 397 402 408 408 408 409 410 412 412 412 413 413 414 414 417 417 421 421 422 422 422 423

7 Backscatter Conversion-electron Moessbauer

Spectroscopy Iron Films and Implantation Studies Steels and Corrosion Products Chemical Reactions Other Elements R e f erences

Chapter

424 428 428 430 431 432

434

8 Gas-phase Molecular Structures Determined by Electron Diffraction By D . W . H . R a n k i n a n d H . E . R o b e r t s o n 1 Introduction

452

2 Compounds of Elements in Main Groups I, 11, and I11

453

3 Compounds of Elements in Main Group IV

456

4 Compounds of Elements in Main Group V

462

5 Compounds of Elements in Main Group VI

466

6 Compounds of Transition Elements

468

References

4 72

Conversion Factors 1 kcal

1 kJ mol-’ 2.3901 1.0364 8.3593 2.5061

x 10-1 kcal mol-’ x eV atom-’ -1 x 10 cm x lo6 MHz

4.1840 4.3364 x 3.4976 x lo2 1.0486 x lo7

1 cm-l 1.1963 2.8592 1.2399 2.9979

x

x x x lo4

kJ mol-’

eV atom-’ cm-l MHz

1 MHz

kJ mol-’ kcal mol-’ eV atom-’ MHz

9.6485 2.3060 8.0655 2.4180

mol-’

x 10 x 10 x lo3 x lo8

3.9903 9.5370 4.1357 3.3356

x kJ mol-’ x kcal mol-’ x lo-’ eV atom-’ x cm-l

kJ mo1-l kcal mol-I cm-’ MHz

Mossbauer spectra: E [57Fe) = 14.413 keV

4.639 1.109 4.808 3.878 1.162

x x x x x 10

kJ mol-’ kcal mol-I eV atom-’ cm-l MHz

For other Mossbauer nuclides, multiply the above conversion factors by Ev(keV)/14 -413

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 , where a complete Periodical Reports 'Nuclear Magnetic Resonance'' 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 H ' n.m.r. spectroscopy is used are only included when the H' n.m.r. spectra make a non-routine contribution, but complete coverage of relevant papers is still attempted where nuclei other than proton are involved. In view of the greater restrictions on space, and the ever growing numbers of publications, many more papers in marginal areas have been omitted. This is especially the case in the sections on solid-state n.m.r. spectroscopy, silicon and phosphorus. A number of reviews have appeared including 'N.m.r. and inorganic chemistry',* 'N.m.r. of metal nuclides. Part 11: the transition metals', 'Scalar spin-spin interactions of nuclei in diamagnetic coordination compounds' , 4 'Steady state techniques for low sensitivity and slowly relaxing nuclei',5 'Effect of substituents in RnM organometallic compounds and changes in direct constants of the -(M, 13C) spin-spin interaction' ,6 'Nuclear magnetic resonance 'J spectroscopy of organic analytical reagents and their metal complexes 'Nuclear magnetic resonance spectroscopy of chlorophylls and corrins' 'Structural properties of calmodulin, an intracellular calcium ion-modulator protein, as revealed by different n.m.r. and 'Elucidation of the structure and metal sequesttechniques ering properties of metallothionein by nuclear magnetic resonance 1 .lo A number of papers have been published which are too broadly based to fit into a later section and are included here. The general magnitudes of n.m.r. isotope shifts have been discussed." Recycled flow n.m.r. spectroscopy has been used to investigate 13C,

,'

,*

,'

2

Spectroscopic Properties of Inorganic and Organometallic Compounds

15N, 29Si, 31P, and '13Cd n.m.r. spectra of model compounds.12 Scalar relaxation of heteronuclear multiple quantum coherences and relative signs of nuclear spin-spin coupling constants have been examined and applied to g(35Cl,1H) and g(35C1,29Si), which have opposite signs in SiHC13.13 The 13C magnetic shielding in cyclopentadienyl complexes has been calculated by eliminating effects due to charge.14 The results for the first overlapping chemical shift calculations reproduce the trends in sphere 2,-SW 13C n.m.r. measurements for the CO, CS, CN, and C5H5 ligands in Ni(C0I4, Cr(C0)5CS, and Fe(C5H5) (C0)2CN.1S 13C n.m.r. spectra of RN=CHCH=NR in various coordination modes have been discussed with particular reference to the Ru3 (CO)12/RN=CHCH=NR system.l6 Metalally1 bonding has been studied by using 15(13C,13C). 1J(13C,13C) varies between 59 Hz for Li or K(C3H5) down to 4 0 Hz for some transition-metal complexes.17 N.m.r. data have also been reported for complexes of ethylenediphosphinetetraacetic acid ( 31P), 1,3-bis ( 2-hydroxyphenyl l-l,3-propanedione ( 13C1 ,l9 and 7-methylguanosine ( 13C). 2o 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 IIA.-lH, 7Li, and 13C n.m.r. spectroscopy has been used to show that Li[Ph2CCLiCPhl has this structure.21 A similar investigation has been carried out using -J(13C,13C) and g(13C,6Li) on isotopically enriched materials.22 Solutions of alkylaryllithium salts chelated by Me2NCH2CH2NMe2 or Me2N(CH2CH2NMe)3Me have been studied by 'Li n.m.r. spectroscopy. Good correlations between the chemical shift and the pK of the parent hydrocarbon were found.23 The 13C n.m.r. spectrum of 6Li-benzovalene shows 1J(13C,6Li) .24 'H, 7Li, and 13C n.m.r. spectra of MSiMenPh3-,, M = Li, K, have been discussed in terms of s-polarization of the phenyl rings.25 At low temperatures z(29Si,6Li) and J(29Si,7Li) in Ph3,nMenSiLi are observed.26 A wide range of unsaturated hydrocarbons-have been reduced by alkali metals in liquid ~ in ammonia, and detected in situ by 13C n.m.r. s p e c t r o ~ c o p y . ~K[K(15-~rown-5)~]+K- in Me20 has been observed by 39K n.m.r. spec-

Nuclear Magnetic Resonance Spectroscopy

3

troscopy.28 The 7Li and 31P n.m.r. spectra of LiPR2 show 15(31P, 7Li).29 The relaxation times El of free Na' and Na' bound to macromolecules have been determined simultaneously by the two-dimensional n.m.r. method by using 23Na n.m.r. s p e c t r o s ~ o p y . ~The ~ 39K n.m.r. spectrum of K/Cs alloy dissolved in 12-crown-4 or 15-crown-5 shows the presence of K-.31 N.m.r. data have also been reported for EtCMeCHCH2Li (13C),32 l-(Me2N)-3-lithiopropane (13C),33 ButMC=C=C=CMBut (M = Li, SiMe3; 13C),34 {Li(trned)l2C6H4(CHSiMe3)2 (l3C),35 L ~ { O C ( = C H Z ) C ~ H ~ C H Z N M ~ Z -(l3C) ~ ) ~ ,36 (C5Me5)Li(p-EBut)2(EBut)Li(tmed) ( E = 0, S; 13C),37 [But2C=NLi(hmpall, (7Li),38 and Li{(R10)2P(0)CH=COR2} (31P).39 A 13: n.m.r. study of the biosynthesis of bacteriochlorophyll using l80 has shown that l80 is incorporated into all possible sites.40 Similarly the incorporation of 1-[l-13Clglutamate and I 2-13C1-glycine into bacteriochlorophyll has been studied by 13C n .m.r. spectroscopy. 41 The structure of a bacteriochlorophyllide dimer in solution has been determined by H' n.m.r. s p e c t r o ~ c o p y . ~ ~ 43Ca and '13Cd n.m.r. spectroscopy has been used to investigate structural differences in the two calcium-binding sites of the porcine intestinal calcium-binding protein. 43 Shift reagents have been employed for 43Ca n.m.r. studies of calcium-binding proteins .44 Quadrupole coupling constants have been determined for 43Ca and 25Mg in M(acacIZ, M = Ca, Mg. 13C El measurements were also performed.45 N.m.r. data have also been reported for Mg(C5H5) (CH2But) (13C),46 Mg(C5H3R1R2I2 (13C),47 [Mg(anthracene)In ( 13C 1 ,48 l12-dimethylanthracenemagnesium ( 13C 1 ,49 Mg-inosine-5I monophosphate (13C),50 Be(R1COCHCOR2I2 (13C, 19F),51 and M U O ~ ( O A C ) ~ ( M = Mg, Ba, Co, Zn; 19F).52 Complexes of Groups IIIA and IVA, the Lanthanides, and Actinides. The 89Y n.m.r. spectra of some organoyttrium complexes such as (MeC5H4I3Y(thf) have been reported, and vary over a range of 4 0 0 p.p.m. For (MeC5H4I3Y(thf), 5(89Y,1H) = 27 H z . ~The ~ 170 chemical shifts are related to the lowest electronic transition energies of U02 complexes.54 'H, 170, and 79Br n.m.r. spectra have been recorded for aqueous-organic solutions of the perbromates of uranyl and neptunyl and the coordination of water and anion investigated.55, 56 The 19F relaxation in gaseous U F ~ ,W F ~ , and M O F ~ is consistent with relaxation dominated by spin-rotation interaction.57 The possibility of the use of 19F n.m.r. spectra in 235U enrichment determination in UF6 (gas) has been investigated. The

4

Spectroscopic Properties of Inorganic and Organometallic Compounds

linewidth modification induced by various 235U enrichments is related to the 19F-235U indirect scalar interaction, modulated by rapid 235U quadrupole relaxation.58r 59 N.m.r. data have also been reported for (C5Me5)LaC13Na(OEt2) (13C),60 Ln(g-CgHqCH2NMe2)3 (13C),61 (C5Me5)2NdCH(SiMe3)2 (13C),62 (C5Me5I2Sm(thfl 2 (13C),63 (C5Me5)Sm(p-I) (thf1212 (13C),64 (c,H5)L~C6H,PPh2cH2(13c) ,65, 66 (CgH512Lu(p-CH3I2Li(tmed) (13C),67 Yb{N(SiMe3)2)2(A1Me3)2 (13C),68 [(C5H5I3U(MW5019)215- (M = Nb, Ta; 170, 93Nb),69 [Th(BH3MeI4l2 ("B, 13C),70 (C5Me5)2Th(p-PPh2)2Ni(CO)2 (31P),71 [U02{C5H3N(CR=NCH2CH2N=CRI2C5H3N)12+ (13C),72 and UO2(R1COCHC0R2l2 (13C, 19F1 .73 The H ' n.m.r. spectrum of (~5:~5-C10H8)(CgHg)2M2(p-H)2,M = Ti, Nb, has been reported. The titanium analogue has a thermally accessible paramagnetic state, and hence the shifts are temperature dependent.74 lH n.m.r. spectroscopy has been used to show exchspectrum of ange in [(C5Me5I2Hf(N2) 12(p-N2),and the 13C n.m.r. ( C5Me5 2HfH2 ( CO 1 was recorded. 75 In ( C5H5 ) 2Ti ( p-CH2 1 2M(C5H5 1 2, M = Ti, Zr, Hf, both H ' and 13C n.m.r. spectra show high-frequency shifts for the methylene groups, which were discussed in relation to metal-carbene or metal-metal bonding in those complexes.76 47Ti and 49Ti n .m.r. chemical shifts, recently reported for ( C5H51 2TiX2 have been r e a ~ s i g n e d . ~ ~ In R2Si(C5H4)2MC12, M = Ti, Zr, the 13C n.m.r. signal of the bridgehead carbon is substantially to lowfrequency from the other ring carbon atoms.78 N.m.r. data have also been reported for (C5Me5)2ZrH(CH=CHBut) (13C),79 (C5H5I2M(SiMe3)(BH4) (M = Zr, Hf; 13C),80 (C5H5)2ZrR1R2 (R1, R2 = H, C1; 13C),81 M(l-norb~rnyl)~(M = Ti, Zr, Hf; 13C),82 (C5Me5){C5Me3(CH2)2)Ti (13C),83 [(C5H5)2M(CH2PPh2)2Rh(CO)Cl12 (M = Ti, Zr; 31P),84 4i(OC6H3ButCMe2dH2)(OArI2 (13C),85 Zr(CH2PhI4 (13C),86 ( B U ~ ~ C O ) ~ Z ~ M ~ ( O C M ~ ~ - O )(13C),87 Zr(CH2Ph)(n2-PhCH2C=NC6H3Me21 (13C),88 (C5H5)nTi(l-norbornyl)4-n (13C),89 T'iCH2CH2C(CH2)CH2CHR(C5Me51 ( 13C1 , (C5Me51 2T'iCMe=CMeCH2tH2 ( 13C1 , ( t5H4CPh21 2Ti 9 3 (C5H5 1 2ZrPh{CH( SMe 1 ( SiMe3I } (13C),92 (C5H51 2T'iCH=CHCH=bH (13C), (13C),94 (C5H5)2ZkAr(CH=PPh2) (13C, 31P),95 (C5H4Me)2ZkPh=CPh1 CPh=CPh (13C),96 (C5H5)2Zr(n1,n5-C5H5)(p-CO)Ru(CO)(PMe3) (13C),97 1 CH=CH2 (13C)," (C5H5)2HfEt(CH=PPh3)(13C, 31P),98

22

(C5H5)2~iNBut=BBut(!H2 ("B, 13C), l o o (C5H5I2Ti(PMe3)(CO) (13C),Io1 (C5H51 2ZrCH(CH2But)( SnR3)C1 ( 13C!, lo2 Ti2(C5Me51 ( CH2C5Me41 ( p - 0 ) (13C),Io3 (C5Me5)2ZrC1(CH2PPh21 (31P),lo4 (C5H5)2HWCHPhOZrPh(C5H5)2 (13C1 ,lo6 ( C5H512(13C, 31P), l o 5( C5H5 1 2ZkC1(Ph?=bPh 1 Clir ( C5H51 Z'rC6H4C{=W(CO)5}b (13C),lo7 (C5H5)2Zr(n-CH=NR)C1 (13C),Io8

Nuclear Magnetic Resonance Spectroscopy

5

(C5H51 2Zr (n2-C0SiMe3)(OS02CF31 ( 13C),log (C5Me5)HfC12(n2-COPBut21 (13C, 31P),110 (C5H5)2M(n4-diene) (M = Zr, Hf; 13C),111 (C5Me5)(C7H7)M (M = Ti, Zr, Hf; 13C),l12 TiW{p-C(tol)=CH2)(p-CO) ((20)(C5H5I3 (13C),113 (C5H5)TiC12(NHR) (13C),114 (C5H5I2Ti(PMe3l2 (13C, 31P),115 (C1jHg)TiM5018]~- (M = Mo, W; 170),116 [ (C5H4R)TiP2W17O61I7- ( 31P, 183W3),'17 ( C5H5 1 2Ti ( SCH2CH2PPh2Me 12 I 2+ ( 31P ,' 18 3C 1 ,l2 ( CgHg ) 2 Zr ( N=CHR 1 C1 ( 13C 1 ,l1 ( C5H5 ZrXNButBHNC5H6Meq ( "B, (C5H5)2Zr(p-PPh2)Mo(CO)4 ( 31P) ,121 (C5Hg1 2Zr(p-PR2 )2W(CO)4 (31P),122 (CgH512Hf(p-PEt2)2MO(C0)4 (31P),123 (C5Me5)Zr(p-OCH2PPh2I3Ni/L (31P),124 (C5H5)(C5H4PPh2)Zr(OBut)C1 (13C, 31P) ,125 (C5H5)2ZrC112 (13C),126 T ~ I P ~ B ( N B U ~ ) ~ B P(~ "B,} C ~ 13C) ~ ,127 MCl3tN(SiMe2CH2PMe2I2) (M = Zr, Hf; 31P),128 [ZrW5Ol9H2I2(183W33,12' and Zr(OAr)2(ArNCR)2 (13C).130

'

Complexes of V, Nb, and Ta.-51V chemical shifts vary over a range of 1400 p.p.m. with a temperature coefficient of up to +1.2 p.p.m. deg" for (C5H5)V(SnC13)(COl31-. 1g(117,119Sn,51V) and 1g(51V,13C) were determined.131 For [V(CO)5LI- the shielding of the 51V nucleus decreases in the order alkene > alkyne N2 > SO2 > CS2 > (0). Compared to sl-coordination, n2-coordination gives rise to a deshielding contribution of 100-280 p . ~ , m . l ~ ~In (C5H4Me)Nb(n2RC2R)C12 the 13C n.m.r. chemical shifts of the acetylenic carbon atoms suggest that the alkyne donates four electrons to the niobium atoms.133 The 13C isotope effect in the 51V n,m.r. spectra of [v(co)6]- has been determined. The 13C n.m.r. spectrum was also r e ~ 0 r d e d . l ~ In ~ [V(C0)5PR31- the 51V shift trends correlate with the integral ligand strength as quantified by Graham's 6- and a-parameters. The 31P n.m.r. spectra were also recorded. 135 51V and 55Mn chemical shifts of analogous compounds have been compared for [V(CO)5Ll-, V(N0) (COl4L, and Mn(NO)3L.136 N.m.r. data have also been reported for Ta(BH4) (C0I2(PMe3l3 (13C, 31P),137 [M(2-CH2C6H4)2(C5H5)21+ (M = Nb, Ta; 13C),138 (C5H5)2M(CO)C(CF3)=CH2 ( M =

-

Nb, Ta; ) F ' ,13' ;a{ ( B U ~ C H ~ ) ~ C ~ C H (13C) ~ C M,140 ~ ~ (But3SiOI2~ H ~ ~ C ~ ~ Ta(CHPh) (CH2Ph) (13C),141 ( B U ~ C ~ H ~ ) ~ M ( C O ) F ~ ~ ( C(p-CO) O ) ~ ~ ((~M -=H ) Nb, Ta; 13C),142 (C5Me5)Ta(n4-diene)C12 (13C),143 (C5H5)V(C0)4,n(CNR), (51V),144 (C5H5)2Nb(SC=CR2)(SCH=CR2) (13C),145 (C5Me5)$aC13 { OCH ( SiMe3 1C ( b 1 OEt 1 ( 13C 1 ,14' VX ( CNR 1 ( NO 1 ( 51V) ,147 and [v(co)5LI- (51V).148 A decrease of 51V shielding in the order [VO2Cl21- > [VOCl41- > IVX3tN3S2)122- ( X = N3 > C1) has been re~0rted.l~' For V(OR1)3-

6

Spectroscopic Properties of Inorganic and Organornetallic Compounds

(=NR2) the "V n.m.r. spectrum shows 1J(51V,14N) .150 [VO4HI2- has been investigated by 'lV n.m.r. spectroscopy in a mixed lyotropic mesophase.lS1 For a series of oxovanadium(Vi) compounds, linear relations exist between 6( 51V) and substituent parameters such as the electronegativity, Pearson's hardness parameter, and Taft's electronic and steric constants. lS2 High-f ield 'lV and 170 n.m.r. spectra have been determined for peroxyvanadates in aqueous soluttion; five new species, including four which are dimeric, were identified.153 [HPV1404218- shows a pH-dependent oxygen exchange, which correlates with 170, 31P, and 'lV chemical shifts.lS4 Mixed vanadium-tungsten polyoxo complexes in aqueous solutions have been identified by 170 and 51V n.m.r. spectra.l'' 31P and "V n.m.r. spectroscopy has been used to study vanadotungstophosphate heteropoly acids in s01ution.l~~ The influence of 51V, 93Nb, 181Ta, line widths has been deter95M0, "Mo, and la3W coupling on "0 mined. Only "V and 93Nb coupling affects 170 1ine~idths.l~~ N.m.r. data have also been reported for VC12(NBut)(NHBut)(NH2But) ("V) ,15* [Cl2VS2N3lZ, [C14MS2N31- ('b, 9 5 ~ o,)15' M(NBut)C13(NH2But) ( M = Nb, Ta; 13C),160 TaF5L (19F),161 TaBr3(PMe2PhI2 0 1(3+2)- (170, (19F, 51V),163 [pvnw12-~4 0 (31P),162 [VOF3(N03)131P, 'lV) ,164 [MwsO18sl3- (M = Nb, Ta; 170)5165 1 (OC)3M(*-Nb2W4019)13- (M = Mn, Re; 170),166 Ta2(0C6H4Me-P)10 (13C),167 and [Nb6S17I4- (93Nb).168 Complexes of Cr, Mo, and W.-The "Mo El and T2 have been measured for a number of compounds. Quadrupolar relaxation is the only significant mechanism involved, allowing El values to be interpreted in terms of the electric field gradient, molecular size and shape, solution viscosity, temperature, and solvent-solute interactions. 97M0 relaxation times were also re~0rted.l~' N.m.r. data have also been reported for CrH4(dmpeI2 (13C, 31P),170 (C5Me5)Cr(C0)3H (13C),171 [DFeCr(C0)91- (2H),172 [MoH(CNI7l4- (13C),173 MoH(SR1( dppe ) ( P ' 1, ( C 'H5 1MoH { C ( CN 1 =CHCN1 , ( C5H5 1 Mb { C5H4C( CF3 1=tH 1 {C(CF3)=CH2} (13C, 19F),17' (Mo(CgH5)(C0)2}2(p-H)(p-ER2) ( E = P, AS; 31P),176 I (C5H5)M(C0)2(p-H) (p-PPh2)Pt(PPh3)(CO) '1 (M = Mo, W; 31P),177 WHg(PMe3)3 (31P),178 WH4(T14-CgH8) (PMe3I2 (31P),I7' w(l14CgHg)(PMe3I3H2 (l3C, 31P),180 (C6H8)WH2(PMe3)3 (l3C, 31P),18' wc12H2(PMe3I4 (31P),182 WH(n2-CH2PMe2) (PMe3I4 (13C, 31P),183 (CsH4CH2)W(C5Me5)H (13C),184 (C5H5)WHI(NO)(PR3) (31P),185 (CgHg)W20s(C0)4( p-Ctol) (p-H)H (13C),18' ( 13C) W2H( OPri) 4( p-C4Me4 1 ( p-CPh 1

-

Nuclear Magnetic Resonance Spectroscopy

-

7

(OC)4drCH2PPh2CR1R2iPh2 (31P),188-190 (C5H5)(OC~)~C~{HC=CHC(O)M~) (13C),lgl (OC)5MC(OEt)=N=CR1R2 (M = Cr, W; 13C),lg2 (OC)5CrCCNR21+ (13C),lg3 (OCI5M=CROMe (M = Cr, W; 13C),lg4 (OC)5M=C(OR)C(OMe)=CHOMe (M = Cr, W; 13C),lg5 (OC)5Cr=CNHC(=PPh3)C(0)NMe (13C, 31P),lg6 (OC1 4Ck=C(OMe )C10H5 ( OMe (bMe ( 13C1 , lg7 (OC 5Cr=C=C=CPh(NMe2 (13C),lg8 (OCI5M=CPhSR (M = Cr, W; 13C), l g 9Co2MRe(p3-Ctol) (COll5 (M = Cr, Mo, W; 13C),200 (C5Me5)C1GeM(C0)5 (M = Cr, W; 13C),201 (C3H3BMeNBut)M1(M2Me3)(C0l3 (MI = Cr, Mo, W; M2 = Ge, Sn, Pb; "B, 13C, 119Sn, 207Pb),202 M2(CH2I4(NMe2l4 (M = Mo, W; 13C),203 (C5H5)Mo(02CCF3) (CH2CH2CF3) (13C, 19F),204 (C5H5)M(C0I3CH2C3H4Me (M = Mo, W; 13C),205 (C5H5)Mo(C0)3{CHROC(0)Me1 (13C, 31P),206 (C5H5)Mo{C4[Mo(C=CHPh)(dppe)(n7-C7H7)'1 (CF3)4}(SC6F5)(CNBut)2 (19F),207 ( 3C 1 , Mo2Br ( =CHSiMe ( PMe ( P ' , ( OC 5MC ( NR1R2 1 N=CPhR3 (M = Cr, Mo, W; 13C),210 (C5H5)MoI{d(NMe)(CH2)2kH21(C0)2 (13C),211 31P ,212 ( C5H5 )Mo(CO1 2(mesityl1 ( O2 )Mo=C(mesityl1 ( PBun3 ( 13C, ( SnPh =C ( CH2 1 3NMe ( 3C 1 ,21 ( C5H5 Mo { P ( OMe 1 2CCHRBut ( 3C, 31P) ,214 [ (C5H5)2Mo2(C0)4(CH2CCCH2OH) '1 (13C),215 (CgH513MoC02(p3-CMe)(p-CO)(COl2 (13C),216 [W(C0l5R1- (13C),217 [W03(CH2SiMe3)I(13C),218 (C5H5)W(0)(CHSiMe3)(CH2SiMe3) (13C),219 (C5H5)W(NO)(CH2W2C13(NMe2)2(CH2NMe)(CHCH2)(PMe2PhI2 (13C, SiMe3I2 (13C),220 31P),221 W(C5H5) (CH=CH2)I (13C),222 W{C(OEt)CHPhCHPhC(bEt)(PMe3)I -

(COI4 (13C, 31P) ,223 (C5H5)W(CO)(C2H2)(COR) (13C),224 W{C(CHO)( C5H5 ) W ( CO 1 3C { CPh=C ( CN 1 2 1 =C=C=O 1 ( CO 1 2 ( PPh3 2 ( NO 1 ( 3C, 31P , (CNI2 (13C),226 [ (OC)3(dppe)W(C2R)I- (13C),227 (Me3SiCH2I4W2(p-CSiMe3){p-MeCH(CH2)CCSiMe31 ( 13C),228 [ (C5H5 (CO)2W(p-CHR)M(CO)4Ll(M = Cr, MO, W; 13C),229 Fe2(CO)gW(CgHg) (CO)(p-PPh2)(p3-CR) (13C, 31P),230 RuW(p-Cl) (p-CMe)C1(COl2(PPh3)(C5H5) (13C, 31P),231 W2 (CO)8 (p-PPh2 ( p-PPh2C=C=CHCH=CMe2) ( 13C, 31P),232 (C5H5)(CO)2MnW(C0I4(p-C=CHCO2Me) ( l3C),233 Fe2W(p3-CMe)(p-co) (co)8 (C5H5 (13C),234 [W(CO),C(O) (CH2l3PPh21- (13C),235 W{=CH(p-tol) )I(C0)2(C5H51 ( 13C),236 (OC)5W=C(p-tol)O(CH21 2CH=CH2 (13C),237 (OC)4WC(OEt)CHPhCHPhCbEt ( 13C1 ,238 ( OC 1 5W=&CPh ( O E t 1 XC ( Y )NCy ( 13C ,240 [ ( SCN 1 ( OC 1 2( 13C , 39 Fe ( C5H4PPh21 C5H4C( OMe 1 =W( CO W=C=NEt2I2- (13C),241 W(CHBut) (OCH2But12X2 (13C),242f 243 (C5H5)W2 ( CO ( = C N B d ) ( 3C , C5H5 2W2Ir ( CO ( CHC02Me1 2 ( 3C 1 , C1(OCI2(pyl2WCR (13C),246 [W(CO)C12(CR)(py)(alkene) 'I (13C),247 W(CR)(ORI3 (13C),248 [(dppe)(OCl3WCCH2Ph1+ (13C, 31P),249 (PriO)( RN= 1W ( p -TI 2, n I-C SiMe 1 ( p -CSiMe W ( OPr W2 { ( p-to1 NCN( 3C , (p-tOl)}(OBUt)6 (13C),251 and [Et2NCW(C0)2(p-PPh2)2M(C0)41- (M = Mo, W; 13C, 31P).252

8

Spectroscopic Properties of Inorganic and Organometallic Compounds

=-

13C and 31P n.m.r. spectra have been used to show that W(CoI3I P ( o M ~ ) ~ I ( ~ ~ - is c ~aH mixture ~) of and E-isomers.''' The effect of slippage of the cyclopentadienyl ring on n.m.r. parameters has been investigated for (indenyl)M~(CO)~(l-Me-allyl)and ( indenyl)IrH(PPh31 I+. 254 For a number of molybdenum compounds such as [ ( C ~ H ~ ) M O ( C O ) ~ ( N R ~ = C RI+, ~C~ the H ~ 95M0 N) signal shows the ~ of the aryl 13C chemical presence of d i a ~ t e r e o m e r s . ~A~study shifts and 15(13C,1H) for (3-8-n-[2.21paracyclophane~chromium and some related complexes has shown that they correlate with chromiumcarbon distances. 256 The geometric configuration of ( n6-9-RC13Hg ) Cr(C0I3 has been determined using H' ASIS.257 It has been shown that the enantiomeric purity of (arene)Cr(C0)3 complexes bearing an A comparison aldehyde group can be determined using Eu( hfc) .258 shows of the H ' n.m.r. spectra of veratrole and (~eratroleICr(C0)~ that protons ortho to Me0 are less shielded upon complexation and this was discussed in terms of relative regioselectivity. 259 H ' and 13C n .m. r spectroscopy, including two-dimensional techniques, has been used to distinguish between the two isomers of Cr(n6-estradiol)(CO)3.260 The 31P chemical shift of the n6-bonded ligand in Mo ( n6-PhPR21 ( PPhR21 (dppe1 correlates with the sum of the cone angles of the three m-bonded ligands in each complex.261 N.m.r. data have also been reported for [M(C2H4)2(C02)(PMe3)212 (M = Mo, W; 13C, 31P),262 (C5Me5)Mo(C0)2(C3HPh2C02) (13C),263 (C5H5)WMe(C2H4)( 0 ) (13C),264 (C5H5)Mo(CO)(NO)(olefin) (13C),265 Mo(C0l4( 13C, 31P 1 , 266 Mo(Me3CS 1 (ButNC) (R1C2R21 (PMe20CHPhCH=CH21 (13C),267 Mo(S-2,4,6-C6H2Pri3)4(alkyne) (13C),268 W2Cl4(NMe2I2(C2Me2)(pyl2 (13C),269 MX2(S2CNR2)2(CgH12) (M = MO, w; l3C),270 W(C2H4)2(CO) (PMe3I3 (13C, 31P),271 W(HC2Ph)(maleic anhydride)[ (C5H5)W(PMe3)2(R1C20R2) '1 (13C, 31P),273 (CNEt212 (13C),272 MO2 ( co 4( 3c , MOW { p-C2 ( to1 2 1 ( CO 4 ( C5H5 { 1? 5-CgH6( COMe 1 ( 3C1 , ( C5H5 1 2Mo ( n 2-0=CH2 1 ( p-n', n 2-CCH 1 ( C5Me 1 ( 3C1 , ( 13C1 , 277 (OC1 4Mn ( p-PPh2 )Mo( C5H51 (CO)[ (OC1 5W1 { p 2 ;n2-Se=CH (to11 1 ( C4H7 1 ( 13C 1 ,278 ( C5H5 1 Mo ( CO 1 ( n 3-CH2PPhNMe1 ( 13C1 ,279 M( CO 1 3 ( PR31 {n3-MeC(S)SMe) (M = Cr, Mo, W; 13C, 31P),280 (C5H5)M(C0)2(C3R3CO) (M = Cr, Mo, W; 13C),281 M O ( C ~ B U ~ ~ ) { O C ( C F ~ (13C, ) ~ ~ ~ L"F, ~ 31P ) ,28 W ( CO ( C3H3R1C0 ( S2CNR22 ) 2 ( 3C ,28 Zn [ W ( co 2 ( rl -MeCHCsH4Me) (C5H5)l 2 (13C),284 { W ( O B U ~ ) ~ ~ ~ ( ~ - C ~ H ~ (13C) N C N ,285 C ~ H Cr(n4~) C4Ph4)(C2Ph2) (COl2 (13C),286 (C5H5)Mo(N0)(n4-diene) (13C),287 ( 1 3 ,288 ~ ~ 2 1H~ C~1 O ( M = M ( S ~ C N 1R ~ ( co { ( C Mo ( norbornadiene ( C0 Mo, W; 13C),289 [W(n4-C4Ph4H) (SzCNEt2'21' (13C),290 ICrtn5-C5H5C=C(CH=CH2)2)(C0)3](13C),291 (C5H5)(OC)2M]2(p-PPhH)2 (M = Cr,

.

Nuclear Magnetic Resonance Spectroscopy

9

Mo, W; 31P),292 (C5H5)M(C0)2P(CF3)2 (M = Cr, Mo, W; 19F, 31P),293 (C5H5)2Cr2(C0)4Sell (" = 1, 2; 13C),294 (C5Me5)Cr(N0)2Br (13C),295 (C5Me5)2M204 (M = Cr, Mo; 13C),296 (C5H5)Mb(CO)2{PPh(OCH2CH2)2Nl ( 3 l ~,297 ) (f~lvene)Mo~(CO)~L~ ( 1 3 ~ , 3 1 ~,298 ) (C5H5)M(C0)3~=~(SiMe3I2 (M = MO, W; 13C, 31P),299 {(C5Me5)Mo}2(p,~6-P6)(13C, 31P),300 [ (C5H5)(OC)2(Ph3P)Mo(OCMe2)' 1 ( 31P),301 (C5H5)Mo(dppe)C1 ( 31P),302 ( 31P), 303 (C5H51 zM02 (CO)4(C5H5)2M02 (co)4 ( p-PC6H2BUt3 (ButCP)RhC1( PF2NMe2)CO ( "F, 31P 1 ,304 (C5H5)Mo(CO)2C02(CO)&( C02R 1 (13C),305 (C5H5)2M02FeTe2(C0)7 (13C, 125Te),306 1 (C5H4Me)MoFeTe2IrCl(PPh31 (CO)'1 ( 31P, 125Te1 , 307 (C5H5)W(CO) ( PPh2BH31 ("B, 31P, 183W),308 (C4S4){W(C5H5)(CO)3)2 (13C),309 (C5H5)W(C0)2(PMe3)( 31P),310 (ButO)O2W(n5,n5-Et4C5CH2CH2C5Me4)Rh(CO) SbButMeC1l+ (13C),311 Fe2W(p3-OCCH2R)(p-PPh2)2(CO)5(C5H5) (13C, 31P),312 [ (benzocycloheptatrienyl)Cr(~~)~~( l 3 ~,313 ) c ~ ( ~ ~ - c ~ H (CO) ~cHo) (13C),314 Cr(n6-arene) (COI3 (13C),315 Cr(r~~-naphthalene)~ (13C),316 ( l3C ,317 ( 3c ,318 MO ( CqHqC=CCr ( CO ) 3 ( C14H12R Cr ( co 3 ( c18H22 Ph2)(COI3 (13C),319 and [Mo(n-C7H7) (dppel21+ (31P).320 Spin-lattice relaxation times of 95M0, 97M0, 170, and 13C for MO(CO)~have been reported. The rotational correlation time of the molecule was obtained from the c.s.a. relaxation of 13C. Quadrupolar coupling constants were calculated for 170, 95M0, and 97~o.321 The 95M0 n.m.r. parameters have been measured for was determined for 9 5 and ~ 136 ~ for some complMO(C0)6-n(py)n. exes.322- The 95M0 chemical shift range of some seven coordinate 13C, 14N, molybdenum( I1 1 isocyanide complexes is about 1100 p.p.m. and 31P n.m.r. spectra were also recorded where relevant.323 19F and 31P chemical shift data support the 6-donor/r-acceptor model of the Cr-P bond in Cr(C0I5L and e-Cr(COI4L2, L = RPSCH2CH2S.324 95M0 chemical shifts have been reported for a range of complexes, [MO(CO)~XI-. The chemical shift values extend over 1000 p.p.m. and reflect the importance of ligand field strength, polarizability, and electronegativity factors in determining the 95M0 chemical shifts. The decreasing shielding effect is in the order H- > [CNI> I- > [NCOI- > [NCSI- > INCSel- > Br- > [N31- > [NO2]- > C1- > [02CH1' > [02Nl- > [OMel- > F-.325 The 13C, 170, 29Si, and 31P n.m.r. spectra of (OC)4Mo(Ph2P0)2SiMeR have been studied. The chemical shift ranges of the carbonyl 13C and 170, the phenyl C(1) 13C and 31P resonance are relatively large, and, with the exception of the cis CO 170 chemical shifts, the correlations between the chemical shifts of the various resonances are excellent. 326 For

r1

10

Spectroscopic Properties of Inorganic and Organometallic Compounds

Mn4C0)4(substituted bipy) the influence of the solvent on the t--emical shifts of the bipyridine ring increases significantly as a 'esult of coordination to the Complexes of the type M o ( C O ) ~ ( P ~ ~ P O ) Sexhibit ~ M ~ R two 13C resonances for the e - C O and phenyl carbon atoms. The differences between the chemical shifts of the two resonances can be correlated with the Taft steric parameters of the R groups.328 The 31P n.m.r. spectrum of N.m. r Mo ( CO 1 ti ( OCMe2CH2) 2NI 3 shows ' g ( 9 5 ~ o3, 1 1 ~= 210 Hz 329 data have also been reported for [Cr(C0)5NCCPh(BH3)(0Me)l(13C),330 (OCI5MNH=CPh2 (M = Cr, W; 13C),331 (OC)5Cr(PHPhPXPh)Cr(C015 (31P),332 (C6H2BUt3P=CHPh)Cr(C0)5 (13C, 31P),333 M(CO)5(R3PTe) (M = Cr, Mo, W; 13C, 31P, 125Te),334 t(OC)5M12RP=PR ( M = Cr, Mo, W; 31P),335 tR1PC(0)CR2=CR21M(CO)5 (M = Cr, Mo, W; 13C, 31P),336 (C6H2BUt3p=pC6H2But)M(co)5 ( M = Cr, MO, W; 31P),337 R2NPHM(C0I5 (M = Cr, W; 13C, 31P),338 M(C0)5(CNNPPh3) (M = Cr, Mo, W; 13C, 31P),339 M(C0)5(PC4H2Me2)2Fe (M = Cr, Mo, W; 31P),340 (C5H5)Fe(CO)2PH(NPri2)M(C0)5 (M = Cr, Mo, W; 31P),341 (OC)5MtPh2POS(O)RI (M = Cr, Mo, W; 31P),342 [OPh2PM(CO)51- (M = Cr, Mo, W; 31P),343 Ph2PN3M(C0I5 (M = Cr, W; 31P),344 M2(CO)10(SbRPR3) (M = Cr, Mo, W; 31P),345 {C4H3(COMe)PhIMo(CO)5 (13C, 31P),346 [W(C0),l2( OC 1 5WNH=CHR t C2Ph2 ( C02Et 1P I W ( CO ) 5 ( 3C, ( 13C) , ( 13C1 , 31P),349 (OC)5WPPh20sH(C0)2(PPh2H)(PPh2Me) ( 31P),350 tC4Me2H2(CH2C1)PIW(C0)5 (13C, 31P),351 (Et2N)2P(CH=CH2)W(CO)5 (31P),352 tC2PhH(CH2CH2C1)IW(COI5 (13C, 31P),353 teH2CH2CH=CMeCMe=CHP(OMe)IW(COI5 (13C, 31P),354 (OC)5h(p-PPh2)de(CO)4 (13C, 31P), 3 5 5 (OCI4Cr(R1N=CR2CR3NR1) (13C),356, 357 Cr(C0)4(Ph2P)3N (31P),358 (OCI4Cr(R12P)2C=PR23 (31P),359 {(OC)4M12ER2 ( E = S, Se; M = Cr, Mo, W; 13C),360 (OC)4MtEMe2P(CF3)212M(CO)4 ( E = P, A s ; M = Cr, Mo, W; 19F, 31P),361 M O ( C O ) ~ B ~ ~ ( P ~ ~ P C H ~ S ~ M (31P) ~ ~ C ,362 H = C H ~PriNtPPh(NH) Pri)}2Mo(CO)4 (31P),363 (OC)4W(py)L (31P),364 (OC)4W(R2P)2Te (13C, 31P, 125Te),365 Cr3(C0110(ButP=PBut)(PBut) (31P),366 (PhCO)(OCI3W ( p-PPh2 1 2Re(CO1 Et 31P 1 ,367 ( 1,5,9-triazacyclododecane 1 ( 13C, ( 13C1, 369 Cr (CO1 (dppm) HB( pz I3Mo(CO1 3X Mo (CO1 ( 9 5 ~ 1, o 368 (31P),370 M(C0)3{RSi(OCH2EMe2)31 (M = Cr, Mo, W; 31P),371 Mo(COI3( ~ P P ~ ) { M ~ N ( P F ~(31P) ) ~ I ,372 (MeNPMe)4Mo(C0)3 (31P),373 M(COI3{Phk6H4PPh(CH2)3X(CH2)2kH2} (M = Mo, W; X = PPh, NMe; I3C, 31P 1 ,374 (NC1 2Pd ( dppm 1 2Mo(CO1 ( 31P 1 ,375 MoRu ( CO 16(dppm)2 ( 13C, 31P),376 (OC)3W(p-dppm)2MX (M =. Cu, Ag; 31P),377 [Cr(C0)2(CS)tHB(Me2pz)3Mo(C0)212S ( 9 5 ~ o,379 ) tP(OMe)?I12 (13C, 31P),378 [W2(0Pr1I6(p-CO)l 2 (13C),380 and W(0)C13(CNR) (13C).381 15N !C1 and l5N-{'HI n.0.e. measurements have been reported for

.

.

'

Nuclear Magnetic Resonance Spectroscopy

11

15N in N2 complexes of Mo, W, Re, and Os, together with 13C and 31P n.m.r. data. It was found that the relaxation is predominantly due to c.s.a. and the rotational correlation times were determined. The N, in the rhenium complex is also relaxed by 185,187Re. The 14N linewidths were also determined. The 31P relaxation is fully dipolar.382 95M0 and I4N n.m.r. studies of seven coordinate molybdenum(V1) monoxo, nitride, and phenylimido complexes have been reported. The chemical shifts of the complexes increase in the order L = NPh < NO < N < 0 < NS, while the linewidths of these compounds increase in the order L = 0 < N Hg(C5Me5)2.1438 ring is Hg(C5H5)2 > Hg(C5H5)C1 The enantiomerisation of ML2, M = Ni, Zn, Cd, Hg, Pb, HL = ( 9 1 , has been studied by dynamic n.m.r. spectroscopy. The activation barrier of the process depends on M, E, and Rl, R2, and R3 in the order: Hg, Pb < Ni < Cd < Zn; 0 < Se 5 S ; CH2Ph < Pri < cyclohex~ 1 . l ~ ~ The ' temperature dependence of the 13C n.m.r. spectrum of [Cd(02CNMe2){CH2(CH2NMeCH2CH2NMeCH2I2CH2} I' is due to methyl orientati011.l~~' In [Hg(s1-dppm)212+ the 31P n.m.r. spectrum is temperature dependent due to exchange between the coordinated and free ends of the dppm ligand.1441

-

R3

W

I

Boron. Hindered rotation of the Me3Si group in (Me3Si)2CHC(BR)2H has been examined by 'H, "B, and 13C n.m.r. spectroscopy and AS' determined.1442 The L3H groupings in 6,6,6,6-(Me2PhPI3H-nido-6-Re-

Nuclear Magnetic Resonance Spectroscopy

43

BgH13 and related compounds show a dual pseudorotational fluxiona30 kJ mol-l, respectively, accordlity with AS* of 45 to 60 and and 31P n.m.r. spectra.1443 The 31P n.m.r. specting to 'H, "B, shows two phosphorus rum of [closo-2,2-(PPh3)2-2,1,7-RhC2B9Hl11' signals at low temperature and one at high temperature. The activation energy was determined and the "B n.m.r. spectrum recorded.1444 The H' n.m.r. spectrum of (C Me5)Rh(B10H11C1) (PMe2Ph) shows Rh-H-B and B-H-B exchange with AS' = 3 3 kJ mo1-l. TheB'' n.m.r. spectrum was also reported.1445 "B n.m.r. spectroscopy has been used to determine the isomerisB ~ toM determine ~ ~ its fluxionality. The 1 3 ~ ation of H ~ c ~ and n.m.r. spectrum was also recorded.1446 AG* for B-NMe2 rotation in PhB(NMe2) (NHBut) has been determined using variable-temperature 13C n.m.r. spectroscopy.1447 Exchange in R ( H O ) B C ~ H ~ C H ~ N Mhas ~ Z been studied and determined. The "B n.m.r. spectrum was also recorded. 1448 13C n .m. r spectroscopy has been used to determine the barrier to rotation about the B-N bond in a m i n o b ~ r a n e s . ' ~ ~ ~

E.

Act

-

.

Aluminium and Gallium. Variable-temperature H' n.m.r. spectroscopy has been used to show that Me2Si ( ButN) ( A1Ph2 1 is fluxional 1450 Variable-temperature 'H, 13C, and 31P n.m.r. spectroscopy has been used to demonstrate that (101, M = Al, Ga, is fluxional with the inequivalent phosphorus atoms exchanging roles. 1451, 1452

.

Carbon. The rotational correlation times for [NO3I' and [C031 2anions in dilute aqueous solution have been determined by 14N and 170 n.m.r. spectroscopy. 23Na n.m.r. spectroscopy provides evidence for Na' and IC0312- association.1453 Silicon. Variable-temperature 13C, 29Si, and 35Cl T1 measurements of C13SiH, C12SiMeH, and C1Me2SiH have been used to investigate molecular dynamics .1454 The fluxionality of (111 has been investi-

Me&

gated

by

H'

and

SiMc,

(11) 13C n.m.r.

Me&i

spectroscopy.1455

SiMq

'H,

13C, and 29Si

44

Spectroscopic Properties of Inorganic and Organometallic Compounds

.

n .m.r spectra of XCH2SiMe20CR1=CHCOR2 have indicated the presence of mixtures of & and trans isomers. The & isomer undergoes intramolecular s i1y1otropic rearrangement The terminal-chain diffusional spectrum of fractionated, molten dimethyl siloxane has been characterised from relaxation of transverse magnetic components of H' or 13C nuclei.1457 A hindered twist-to-twist interconversion in (Ph01(S1P(MeNNMe12SiPhZ has been detected at low temperatures by H ' n.m.r. spectroscopy.1458 The rates of ligand permutation in (121, M = Si, have been measured by 19F n.m.r. spectroscopy for the CF3 groups. 1459 A similar study of (121, M = SiO=CHC6H4NMe2, using 'H, 19F, and 29Si n.m.r. spectroscopy, has shown that inversion of the silicon proceeds by a non-dissociative intramolecular pseudorotation with AG' = 10.2 kcal mol" According to a 1 9 F n.m.r. study of (131, the energy barrier to intramole-

.

(12) (13) cular fluorine equilibration is 7.5 kcal m~l-'.'~~'

Tin. The behaviour of

2,2-dibutyl-1,3,2-dioxastannolane has been examined by 'H, 13C, and ll'Sn n.m.r. spectroscopy. There is a fast intramolecular shift with inversion at tin with AS' = 4 2 kJ m01-1.1462 l1'Sn two-dimensional NOESY has been used to demonstr-

ate unambiguously that CH2tPhSn(SCH2CH212NMe)2 isomerises at the tin centre in an uncorrelated way.1463 31P and "'Sn n.m.r. spectroscopy has been used to investigate Bun3P0 adducts of Ph2SnX2. A two-dimensionThere is pseudorotation in Ph2SnC1Br(OPBun31 al n.m.r. study of the modes of rearrangement in PhSnCl(PhCOCHC0MeI2 has been reported. The results were explained in terms of the Bailar twist .1465 The temperature - dependent H' n.m.r. spectra of SnC12(8-quinolinato)2 have been analysed in terms of intramolecular exchange.1466 The 31P and l19Sn n.m.r. spectra of (14) have been

Nuclear Magnetic Resonance Spectroscopy

45

reported. A Berry pseudorotation is observed with Ag' = 12.7 kcal rn01-l.l~~~ The 'H, 13C, 31P, and '19Sn n.m.r. spectra of Sn2(PR2)2(p-PR2)2 and Sn2(SR)2(p-SR)2 have been reported. In the case SR exchange was observed. 1468 The mechanisms of of Sn2 (SR) ( p-SR) Me2S intermolecular exchange and trans-cis isomerism of SnC14(SMe2I2 have been studied by variable-pressure H' n.m.r. and varispectroscopy. able-temperature '19Sn magnetisation transfer n.m.r This work provides a rare example where both magnetisation transfer and line shape analysis have been performed at the same temperature. 1469

.

Te2 LqMez

MezP

I ,PMe2 Sn

Me2

Me2N

Ph>P-a Y L R 1 R20 Ph

NMe,

I 0 R2

PMe2

(15)

(14)

(16)

Phosphorus. 7Li, 13C, and 31P chemical shifts and 'T1 have been used to investigate C6H4(PR2I2 and the di-lithiated species. A phosphorus inversion barrier of 100 to 110 kJ mol" was determined.1470 H ' n.m.r. spectroscopy has been used to determine the activation energy for flipping in RP(CH=CHI2PR. H' n.0.e. measurements were used to assign the structure and the 13C and 31P n.m.r. spectra measured.1471 Similarly, the activation energy for ring inversion in (15) has been determined as 28.9 to 29.6 kcal 'H, I3C, and 31P n.m.r. spectroscopy has been used to m01-l.l~~~ determine P-But rotation barriers in But2PR and compared with molecular mechanics calculations. 1473 Pseudorotation in (16) has been studied using H' and 31P n.m.r. spectroscopy.1474 Permutational isomerism in (171 has been studied It proceeds an irregular by H' and 31P n.m.r. spectroscopy. mechanism with dissociation of the P-N bond.1475 H ' and 13C n.m.r. spectra of (Me2NI2CHC(=N2)PR1R2(0) show restricted rotation about the C-N and C-C bond.1476 The barrier to rotation of the P-N bond in RP(X)NEt2 has been studied by 'H, 13C, 19F, 31P, and 77Se n.m.r. spectroscopy. It is determined by steric l3C, and 31P n.m.r. spectroscopy h a s been used to study 'H, intramolecular

1igand

rearrangement in ACAr1=CAr 2oPN ( CH2CH2CH2k-

Spectroscopic Properties of Inorganic and Organometallic Compounds

46

MeI2. 1478

A

similar study using

'H,

13C, "F,

and 31P n.m.r.

spectroscopy has been performed on &Ar1=CAr20PN CH2CH2CH&Me)2. The first example of an intramolecular sequential [1,31-migration of a phosphoranyl group in an ambidentate N=CN=CN pentad has been demonstrated for (18) with an activation energy of

(17) (18) 16.9 kcal mol". 1480 AS* has been determined for CH2(C6H40) 2P(ORI3 using 'H, 13C, 19F, and 31P n.m.r. spectroscopy.1481 Different isotopic shifts are produced by equatorial and axial P-l80 single bonds in 5-coordinate, trigonal-bipyramidal oxyphosphoranes. This difference can be used to follow permutational isomerisation by variable-temperature 31P n.m.r. spectroscopy.1482 The rotationhave been studied using al motions of [P04J3-, [S04J2; and IClO,]' 170 spin-lattice relaxation times. The electric field gradients at the oxygen site were calculated by using the & initio M.O. method, and hence the correlation time calculated. The activation energies were also derived.1483 Arsenic. The I3C T1 has been measured as a function of temperature for three 2-phenyl-1,3,2-dioxarsolanes. The data were interpreted in terms of isotropic overall molecular tumbling, rotation about the As-Ph bond,and internal methyl rotation.1484 Sulphur. 170 n.m.r. spectroscopy has been used to study the rotational motion of the sulphate anion in aqueous solutions.1485 Selenium. The inversion barrier and the A value of the PhSe group in PhSe(cyclohexy1) have been determined by dynamic 77Se n.m.r

.

Nuclear Magnetic Resonance Spectroscopy

47

spectroscopy. The 6 ( 77Se 1 show large diamagnetic shifts in substituted analogues due to -gauche CH2 interactions.1486 The activation energy for Pri2N rotation in Pri2NC(Se)Ph has been determined.1487 The barrier to rotation about the Se-Se bond in PhSe-SeCH2Ph has been determined as 6.3 kcal mol" as indicated by changes in the H' n.m.r. spectrum.1488 Tellurium. 19F, "As, and 125Te n.m.r. spectra have been observed for Te(OTeF5I4, As(OTeF5l5, and related species. In As(OTeF515 the 75As signal is sharp enough to observe 2g(125Te,75As) = 430 Hz. The activation energy for intramolecular exchange in Te(OTeF5I4 was determined as 31 kJ mo1-1.1489 Equilibria.-Solvation Studies of Ions. The sources of disagreement of ion coordination numbers in aqueous solutions, determined by different methods, have been examined.1490 The basic physical principles for determining the structure and dynamics of liquids from n.m.r. relaxation have been presented and applied to solvation structures around "F-, 23Na+, and 127~-.1491 H' chemical shifts of aqueous electrolyte solutions have been measured as functions of salt concentration, ionic size,and ionic charge/radius ratio. The observed shifts were interpreted in terms of the breakdown of the hydrogen-bonded structure of water and the ability of the ions to polarize water molecules. 1492 Macroscopic counterion diffusion in solutions of cylindrical polyelectrolytes has been studied using 7Li n.m.r. self-diffusion experiments.1493 H' n.m.r. spectroscopy has been used to investigate methanol exchange on Mg(II), Co(II), and Zn(I1) complexed by 1 5 - c r o ~ n - 5 . ~ H'~ ~ El ~ measurements of ethylene glycol in the presence of Gd(II1, Mn(II), Co(II1, Ni(II), and Cu( I1 1 have been reported and correlation times derived.1495 Group Ia. The pressure, temperature, and concentration dependence of 2H T1 in supercooled LiC1-D20 has been measured. Hydrostatic pressure suppresses anomalies and turns water into a normal viscous 1 i q ~ i d . l ~ ' ~ The water orientation in the hydration sphere of Li' has been determined by 7Li relaxation measurements. 1497 The rates of H' magnetic relaxation have been determined at a variety of Licl concentrations in aqueous solution containing 1.2 x 10-3 M MnC12. The temperature dependence of El was determined. 14'* Solvation effects of Li+, Na+, and Mg2+ in dmf/H20 have been investigated by H' n.m.r. spectroscopy.1499 The spin-lattice relaxation time of 7Li of concentrated LiN03-NH3 solutions has been

48

Spectroscopic Properties of Inorganic and Organometallic Compounds

measured and correlated with viscosity data.1500 The 7Li n.m.r. relaxation of molten (Li-Cs)N03 has been measured as a function of composition and temperature. The relaxation rates increase with increasing concentration of CsN03. This behaviour was explained in terms of the anion polarization effect due to the introduction of cations with different ionic radii .1501 The hydration of Na' and [OH]- in aqueous solutions of NaOH has been determined by 23Na n.m.r. spectroscopy.1502 Self-diffusion of water molecules in aqueous solutions of NaCl has been investigated.1503 The 23Na relaxation rates in aqueous NaC104, NaI, NaBr are proportional to (concentrationI 1/2 at low concentration.l5O4 The spin-lattice relaxation times of 2H, 23Na, *'Rb, and 133Cs in basic solution have been measured. The hydration numbers of Cs' and [CO3I2- were estimated, and the hydration numbers of Br-, L i ' , and N a ' , measured earlier, were confirmed.1505 The coordination and mobility of water have been studied in NaSCN, Ca(SCN12, and Ba(SCN12 solutions by 2H and 23Na T1 measurements.1506 The solvation of 23Na+ in binary mixtures of solvents has been studied. The solvation abilities follow the order water > acetone 2 acetonitrile > EtOH and dmf > MeOH.1507 The molecular reorientation and Na' solvation in (Me2NI3PO have been studied using 2H, 14N, and 23Na relaxation measurements.1508 Solutions of the metals Na, K, Rb, and Cs in some amides have been investigated by 13C, 23Naf 3 9 K f 85Rb, and 133Cs n.m.r. spectroscopy. Although the 23Na n.m.r. spectrum showed the presence of Na-, solutions of the heavier alkali metals showed no evidence of genuine alkali ions.1509 Maqnesium. Solvent exchange kinetics of [Mg(l5-crown-51 (dmf)212' have been studied in DMF-CD3N02 by n .m.r spectroscopy.l5lo The Lanthanides. The solvation of La3+ in aqueous dmf has been studied as a function of dmf mole fraction and type of anion by 13'La n.m.r. spectroscopy.1511 H ' chemical shifts of aqueous solutions of rare-earth ions have been studied and only small paramagnetic shifts were found.1512 The hydration of Lu3' has been investigated by H ' and 35Cl n.m.r. spectroscopy in water-acetone mixtures .I513 Uranium. Low-temperature 15N and 31P n.m.r. spectroscopy has been used to investigate the species formed in the organic layer following the extraction of uranium from nitric acid solution with di-2ethylhexyl phosphoric acid.1514 Vanadium. Water exchange with [V(OH2I6l3+ has been studied as a function of temperature and pressure by 170 n.m.r. spectroscopy.

.

Nuclear Magnetic Resonance Spectroscopy

49

The kinetics and activation parameters were determined and the mechanisms of exchange were discussed. 1515 51V n.m.r. spectroscopy has been used to investigate the interaction of vanadate with ethanol in water.1516 DMSO exchange in [VO(DMS0I5l2+ has been investigated by H' n.m.r. spectroscopy and the kinetic parameters determined. 1517 Ruthenium. The electron-exchange rate of the [Ru(OH2 I2+l3+ couple in acidic solutions has been measured directly by 170 and "Ru n.m.r. spectroscopy at 252 to 366 K. The 170 n.m.r. signals for the coordinated H20 of [ R U ( O H ~ ) ~ ] and ~ + I R ~ ( o H ~ ) occur ~ I ~ +at -200 and 35 p.p.m. from H20, while the "Ru n.m.r. signal for [RU(OH2)6I2+ is at 16 050 P.P.m. from [RU(CN)6]4-.1518 Cobalt. A recently reported n.m.r. method for measuring 2H equilibrium isotope effects has been applied to the hydration of The Co(I1). An isotope effect of G . 1.3% was measured.1519 catalytic effect of nitrate ion on water exchange on e - [ C o ( e n I 2 (OH2I2l3+ has been determined by 170 n.m.r. spectroscopy.1520 Activation energies have been determined from a H' n.m.r. study of (Et2NI2NCHO exchange on [C0{2,2',2"-(Me~N)~triethylaminel{(Et~N)~NCHO) 12+ and its Cu(I1) a n a 1 0 g u e . l ~ ~H~ ' n.m.r. spectroscopy has been used to show that the loss of solvent ligands at the two sites in I C O { N ( C H ~ C H ~ N H ~ ) ~ ) ( O S Moccurs ~ ~ ) ~ Iat ~ + the same rates.1522 Rhodium. The activation energy for the interconversion of has and [Rh(acetone1 (OH21 {P (OPh1 12' 1 [ Rh( acetone 1 {P(OPh 1 ) ' 1 been determined by H' and 31P n.m.r. spectroscopy.1523 Nickel. The H' El of water in aqueous Ni2+ has been measured as a fu'nction of temperature, frequency, and pH.1524 Platinum. Water exchange on [Pt(OH2I4l2+ has been studied by "0 n.m.r. spectroscopy and activation parameters determined.1525 Copper. H' relaxation measurements of water in the presence of Cu2+ and ethylene glycol have been made as a function of temperature. Information on molecular motion was obtained.1526 Zinc. The hydration number of Zn2+ has been determined as 3 . 8 from H' n.m.r. measurements. The compounds formed in (Bun0)3PO-CC14 extraction of ZnC12 have been determined using H' and 13C n.m.r. spectroscopy. 1527 Aluminium and Gallium. The H' El of free . and coordinated water signals in aqueous AlClO4 solytions has been measured between 10 and -65 OC. It was concluded that the coordinated water molecules undergo anisotropic rotational motion as an axially symmetric ellipsoidal body, and this motion is slowed at low aluminium

50

Spectroscopic Properties of Inorganic and Organometallic Compounds

concentrations The transverse relaxation rate of H20 in IA1(OH2)613+ has been measured as a function of temperature and pressure using 170 line broadening in the presence of Mn2+. At high temperatures, the relaxation rate is governed by chemical exchange with bulk water, while at low temperatures quadrupole relaxation is prevailing. The water exchange parameters were obtained.1529 The 27Al n.m.r. chemical shift of IA1(OH2I6l3+ is medium dependent due to possible outer - sphere effects.1530 27Al n.m.r. spectroscopy has been used to investigate the preferential solvation of A13+ in a DMF-DMSO mixed-solvent system. The effect of inert diluent on preferential solvation was also examined.1531 The outer-sphere interactions of solvated Ga3+ and A13+ with F- and C1- have been studied in ethylene glycol by 19F n.m.r. spectroscopy.1532 Oxygen. The 2H and 170 quadrupolar splittings of H20 in a lyotropic mesophase have ratios widely different from all previous observations. 1533 Sulphur. The 170 !C1 values for aqueous NaHS03 have been measured as a function of pH, temperature,and concentration. The rate law for oxygen exchange between [HSO31- and water was determined.1534 Fluorine. The hydration of F- has been studied by 19F n.m.r. spectroscopy. The dipole-dipole contributions of H ' and 170 to the 19F' were calculated to test various models.1535 The I9F chemical shifts for solutions of various fluoride salts have been measured. 1536 Ionic Equilibria. 31P T1 and T2 have been used to investigate complex formation between H 2 N ( C H 2 ) 2 N H ( C H 2 ) 2 N H ( C H 2 ) 2 N H 2 , phosphate, and metal ions .1537 The influence of micellization on complexing properties of amphiphilic ligands towards Mn2+, Ni2+, and [VO12+ has been studied using 31P n.m.r. spectroscopy.1538 13C n.m.r. spectroscopy has been used to investigate conformational changes of crown ethers on metal ~ o m p 1 e x a t i o n . l ~The ~ ~ complexes formed by Co(II1, Mn(II), and Cu(I1) with glycine, alanine, and proline have been studied by I4N and 170 n.m.r. spectroscopy.1540 Group Ia. BunLi exists in THF as a tetramer in equilibrium with a dimer. The rates of exchange were measured by 'Li n.m.r. spectroscopy at variable temperature.1541 The influence of aggregation on the reactivity of BunLi towards benzaldehyde and cyclopentadiene has been studied at -85 OC by rapid injection n.m.r. spectroscopy.1542 The temperature and Concentration dependences of 13C n.m.r.

Nuclear Magnetic Resonance Spectroscopy

51

spectra of 6Li and 13C labelled organo-lithium compounds have been fitted and the thermodynamic parameters determined for 6Li13CHBr2, 6Li13CH2SPh, and 6Li13CH2Prn Complex formation between diarylmethylenemalonaldehydes with Mg2+ and Li' has been studied by H' n.m.r. spectroscopy.1544 7Li and 35Cl n.m.r. spectroscopy has been used to investigate association of L i ' , [enolatel-, and [C1041-.1545 13C n.m.r. spectroscopy has been used to investigate equilibria in the PhM/Mg(OCH2CH20Et)2, M = Na, Li, K, system.1546 H ' n.m.r. spectroscopy has been used to determine the stoichiometry M = Li, Na, K, Rb, Cs, Ca, Sr, of the crown ether complexes ML,, and Ba, L = 12-crown-4, 15-crown-5, and 1 8 - c r o ~ n - 6 . 7Li, ~ ~ ~ ~13C, 170, 23Na, and 39K relaxation studies have been used to study the complexation of metal ions by crown ethers.1548 The stability constants of LiSCN, NaSCN, KSCN, and NH4SCN with poly(ethy1ene glycol) have been determined by 7Li, 13C, and 23Na n.m.r. spectroscopy.1549 The nuclear magnetic relaxation rates of 7Li, 23Na, 35Cl, 'lBr, and 133Cs have been measured for alkali -metal halide-poly (ethylene glycol 1 -water mixtures 'Li n .m.r. spectroscopy has been used to investigate Li' interaction with phosphatidylcholine-phosphatidylglycerol membranes. 1551 The interactions between ATP, monovalent cations, and divalent cations on rabbit muscle pyruvate kinase have been examined by 'H, 7Li, and 31P n.m.r. spectroscopy.1552 An n.m.r. technique has been developed for the determination of formation constants of metal-ion complexes that uses competition of two metal cations for a given ligand and applied to 23Na and 133Cs.1553 'H, 13C, and 23Na n.m.r. spectroscopy has been used to investigate the structure of NaBu" in thf.1554 23Na !F1 has been used to show that there is no interaction between Na+ and IMeS041-.1555 The kinetics of complexation of Na+ with 18-crown-6 have been studied using 23Na n.m.r. spectroscopy.1556 23Na n.m.r. spectra of "a(l8-crown-6) I'Nasolutions in MeNH2 have been studied as functions of temperature and mole ratio of crown ether to Na. Na+/Na- exchange rates were determined and activation parameters determined.1557 The influence of anions on the kinetics of complexation of Na' with 18-crown-6 has been investigated in thf by 23Na n.m.r. spectroscopy and activation parameters determined.1558 The effects of the salt concentration and counterion on the stability of alkali- ion-18-crown-6 complexes in aqueous and methanolic solution have been studied using 23Na n.m.r. spectroscopy.1559 The exchange kinetics for complexation-decomplexation of NaBPh4 with dibenzo-24-crown-8 in MeN02 have been studied by 23Na n.m.r. spec-

52

Spectroscopic Properties of Inorganic and Organometallic Compounds

troscopy.1560* 1561 23Na n.m.r. spectroscopy has been used to study sodium dibenzo-30-crown-10 aggregation in solution, and ' equilibrium constants have been determined.1562 23Na !F1 and H chemical shifts have been used to investigate the association of alkali-metal ions with polyene macrolides in methanol s 0 1 u t i o n . l ~ ~ ~ Lamellar liquid crystalline phases containing sodium n-octanoate, water, and an alcohol have been studied by 2H n.m.r. spectroscopy.1564 The importance of the alcohol chain length and the nature of the hydrocarbon for the properties of ionic microemulsion systems have been studied by H ' and 23Na n.m.r. spectroscopy.1565 23Na n.m.r. spectroscopy has been been used to investigate m i ~ e 1 1 e s . l ~ ~ ~ The effect of terminal unsaturation on the CMC values of sodium ll-dodecenoate and sodium 12-tridecenoate has been probed by 23Na n .m. r spectroscopy.1567 Sodium diethyl-2-hexyl phOSphate/H2O/CgHg inverted micelles have been investigated by 23Na n.m.r. spectroscopy.1568 The importance of the cosurfactant and the oil for the properties of microemulsions has been investigated by 23Na n.m.r. spectroscopy.1569 A 23Na n.m.r. study of NaBr in methylamine solutions that contain macrocyclic polyethers has been reported. The donor number of some aprotic cyanamides has been determined by using 23Na n.m.r. spectroscopy.1571 The interaction of cysteamine with DNA has been studied using 23Na n.m.r. spectroscopy.1572 The monensin-mediated transport of Na+ through phospholipid bilayers has been studied by 23Na n.m.r. spectroscopy.1573 The 23Na n.m.r. spectrum of intact bovine lens and vitreous humor has been reported.1574 The interaction of 23Na+ with gramicidin channel has been studied by n .m. r spectroscopy. 1575 Intra- and inter-cellular Na+ and K+ have been discriminated, in the 23Na and 39K n.m.r. spectrum, by using shift reagents.1576 The interaction of group Ia cations with carrageenans has been studied by 23Na, 39K, 87Rb, and 133Cs n.m.r. spectroscopy.1577 The state of intracellular Na+ in human and dog erythrocytes has been characterised by 23Na n.m.r. spectroscopy using dysprosium complexes as shift reagents. The extracellular volume was determined from 59C0 n .m.r. spectra of [ C O ( C N ) ~ I ~ -The . ~ effect ~ ~ ~ of Ca2+ on vascular smooth muscle has been studied by 23Na n.m.r. spectroscopy.1578a Intracellular sodium concentrations in erythrocytes1579 and mammalian cardiac m y o ~ y t e s lhave ~ ~ ~been ~ determined by 23Na n.m.r. spectroscopy. The complexation of cyclohexaned ioxydiacetamides' and p h e n y l e n e d i o ~ y d i a c e t a m i d e s ' ~ ~ ~by K+ has been confirmed by H ' and 1% n.m.r. spectroscopy. A lyotropic ternary system containing

.

.

Nuclear Magnetic Resonance Spectroscopy

53

potassium has been studied by 2H n.m.r. spectroscopy.1582 A 13C n.m.r. study of K+ and T1+ binding to gramicidin A transmembrane channel has been reported.1583 The kinetics of complexation of Cs+ with large crown ethers in acetone and methanol have been studied by 133Cs n.m.r. spectroscopy.1584 The interaction of Cs+ with gramicidin transmembrane channel has been investigated by 133Cs relaxation and two dimensional H ' n.m.r. spectroscopy.1586 Group IIa. 'Be and 13C n.m.r. spectroscopy has been used to investigate the Be2+/malonic acid system and Be{ (OZC)2CH2), [Be{(02C)2CH2) 1 2-, and [Be3(OH1 3{ (02C1 2CH2) I 3- identified.1587 TheF'' T1 of molten LiBeF3 has been measured. The relaxation is due to the dissociation of F- from IBeF41-.1588 Trans-1,2-diaminocyclohexane-N,N,N"'-tetraacetate has been shown to be a superior ligand to edta for sequestering Mg2+ in 31P n .m.r. experiments involving ATP .lS8' Charge-transfer interactions of chlorophyll g, pheophytin 5, and their metal derivatives with 2,4,7-trinitrof luorenone have been studied by H ' and 13C n.m.r spectroscopy.1590 13C n.m.r. spectroscopy has been used to study the complexation of Mg,2+ and A13+ by cimetidine and ranitidine.15'l A multicomponent self-diffusion n.m.r. study of aggregation of nucleotides, nucleosides, and nucleic acid bases with divalent metal ions has been re~0rted.l~'~The exchange rate between free Mg2+ and Mg2+ complexed to ATP has been determined from 31P n.m.r. spectra.1593, 1594 A similar study has been made for Mg2+ with adenos-

.

ine-5'-tetraphosphate using 31P n.m.r. spectroscopy.1595 Stability constants of Ca2+ or Pr3+ with aspartame have been determined by n.m.r. spectro~copy.~~'~ 43Ca, 25Mg, 39K, and 67Zn n.m.r. spectroscopy has been used to study trifluoroperazine-calmodulin solutions.1597 H' and 13C n.m.r. spectroscopy has been used to study Ca2+ complexation by lasa10cid-A.~~'~ 2H n.m.r. spectroscopy has been used to investigate the liquid crystallinity in barium surfactants. 1599 The Lanthanides. A H ' and 13C n.m.r. study of La3+ and Lu3+ with triaza triacetic acid has been reported.1600 H' and 13C n.m.r. spectroscopy has been used to investigate the structure of [R(C813C H17 1 3NI+ ion pairs with some rare-earth-containing anions n.m.r. spectroscopy has been used to investigate the binding of Gd3+ and Mn2+ to B-gluconamide. 1602 Mixed-ligand heteronuclear complexes of Gd3+ and Cu2+ with malic and mandelic acids have been studied hy H ' n.m.r. spectroscopy.1603 A H' n.m.r. study of lanth-

Spectroscopic Properties of Inorganic and Organometallic Compounds

54

anide complexes of aspartate and glutamate residues has been reported.1604 A 6Li, 7Li, "0, 23Na, and 31P n.m.r. study of lanthanide cation binding to sodium triphosphate has been reported.1605 The interaction of ATP with Sc, La, and Lu has been studied by 'H, "0, and 31P n.m.r. spectroscopy.1606 The water relaxation properties of proteins labelled with Gd3+ and Mn2+ have ,beenre~0rted.l~'~ The Actinides. The kinetics of the ligand-exchange reactions in Th(2-thenoyltrifluoroacetonate)4 and its DMSO complex have been determined using H' n.m.r. spectroscopy.16'* The interaction of pyridoxal with UO2(0AcI2 has been studied by H ' and 13C n.m.r. measurements.I609 Vanadium, Niobium, and Tantalum. The system VOS04-histidine-glycol-H20 has been studied by 13C n.m.r. spectroscopy.1610 H' and 13C relaxation rates have been measured for the system [V0l2+-glutathione in aqueous solution.1611 In the catalysis of H202 disproportionation by NH4V03, intermediate peroxo complexes of V5+ were detected by 51V n.m.r. spectroscopy.1612 A 31P and "V n.m.r. study of the formation of high-vanadium vanadotungstophosphate heteropoly compounds has been reported.1613 31P n.m.r. spectroscopy has been shown to be a useful analytical technique for determining V(V), Nb(V), and Ta(V) as the h e t e r o m o l y b d ~ p h o s p h a t e .The ~~~~ 170 and 51V n.m.r. spectra of K2S2O7.~V2O5 melts during the catalytic oxidation of SO2 have been reported.1615 'lV n.m.r. spectroscopy has been used to study the binding of vanadium(V1 oligoanions to sarcoplasmic reticulum 1616 and saccharomyces cerevisiae.1617 Chromium. Paramagnetic shifts and !C1 have been determined for alcohols in CC14 solutions of Cr(acacI3. Stability constants were calculated.1618 Molybdenum. H' n.m.r. spectroscopy has shown that (C5H5)Mo(C0)2I + are in equilibrium.1619 CH2CH=CH2 and [ (C5H5)Mo(C0)2(~-CH2=CHMe) Equilibria in the H+-[Mo0412--[HP0412have been studied by 31P n .m. r spectroscopy.1620 Tungsten. Complexation of k-malic acid with W(IV) has been studied by H ' n.m.r. spectroscopy.1621 The temperature dependence of the bridging-hydrogen H' chemical shift of C13W(p-H) (p-Me2S)2WC12(SMe2 1 has been attributed to an equilibrium between isomers. The 2H n.m.r. spectrum was a l s o recorded.1622 Manganese. The [Mn(CNR)6 1+/2+ electron self-exchange in acetonitrile has been studied by 55Mn n.m.r. spectroscopy.1623 13C and '31P n.m.r. relaxation has been used to study the stability and dynamics of complexes in the glycine/Mn(II)/ATP system.1624 13C n.m.r.

.

Nuclear Magnetic Resonance Spectroscopy

55

spectroscopy has been used to determine the mode of interaction of Mn2+ and Cu2+ with c i s - i n o s i t 0 1 . l ~ ~ ~ The conformation of the hydrocarbon chains of micellar amphiphilic molecules has been studied by n.m.r. relaxation of the surfactant nuclei, induced by Mn2+.1626 The volume of activation for electron transfer between [MnO41- and IMnO4I2- ions has been determined by 55Mn n.m.r. spectroscopy.1627 Iron. 'H, 13C, 31P, and lg9Hg n.m.r. spectroscopy has been used to demonstrate the interconversion of isomers of [Fe4(HgMe)(C0)131and Fe4(AuPEt3)(C0)12(COMe).1628 Electron self-exchange rate constants in a series of dicyanoiron p o r p h y r i n ~ land ~ ~ ~bis ( imidazole ) iron p o r p h y r i n ~ l ~ ~ 'have been measured by H' n.m.r. spectroscopy. H' and 13C n.m.r. spectroscopy has been used to investigate carbon monoxide dissociation kinetics from haemoglobin. 1631 The pH-dependent axial ligation changes of monomer and dimer forms of iron(II1) uroporphyrin I have been investigated by H' n.m.r. spectroscopy.1632 The formation of Fe(II1) mixed malic-mandelic acid complexes has been studied by H' n.m.r. spectroscopy as a function of pH.1633 H' n.m.r. spectroscopy has been used to study Fe3+-aspartic acid complexes.1634 H' and 19F n.m.r. spectroscopy has been used to investigate the equilibrium1635 [Fe4(SPh)1012+ 6[PhSl- ,d 4[Fe(SPh)412Ruthenium. The rate constants for electron exchange between [ Ru ( bipy ) ( acac ) ]+I2+ and [ Ru ( bipy 1 ( hf ac 1 ]+I2+ have been determined from H' and 19F n.m.r. line broadening measurements.1636 Cobalt. The equilibrium constant for ~ [ C O ( C N R ) ~ L I + v? CCo(CNR)3L21+ + [Co(CNRl51+ has been determined by H' n.m.r. spectroscopy.1637 H' n.m.r. spectroscopy has been used to measure the hydrogen exchange rate of trans-[Co(en)2x~]!+.1638 The absence of intramolecular proton transfer in the con jugate bases of trans- [ Co (en1 2XY ';1 has been established by H' n.m.r. spectroscopy.1639 H' T1 and chemical shifts have been used to characterise the outer-sphere complex formed between [ C O ( M ~ O H12+ ) ~ and pyridine in d4-methanol.1640 H' n.m.r. studies of the complex formation of Co(I1) with 12-crown-4 has been investigated by 2H n.m.r. spectroscopy.1641 H' n.m.r. spectroscopy has been used to study the composition and stability constants of chloro complexes of Cu, Ni, and Co in HC1, H20-MeCN, H20-acetone, and aqueous dioxan. 1642 Rhodium and Iridium. 31P n.m.r. spectroscopy has been used to demonstrate the equil i b r i ~ m l ~ ~ [Rh(dppel2I' + IRh(dppe)21+ 2Rh(dppeI2

56

Spectroscopic Properties of Inorganic and Organometallic Compounds

The PMe2Ph ligands in mer-[MC12(0H2) (PMe2Phl31+ rapidly exchange on the n.m.r. time-scale, giving coalescence in the H' and 31P n.m.r. spectra .I644 Nickel. The Evans' method has been used to investigate the planar-octahedral equilibrium in aqueous solutions of [Ni(Me4-cyclam)12+.1645 Steric effects on the rates of redox reactions involving nickel (11I / ( I11 1 macrocycles have been studied by 13C n.m.r. spectroscopy.1646 The kinetics and mechanism of chelation of Ni(I1) by a-(8-quinolylazo)-a-acetoacetonitrile have been investigated by H' and 13C n.m.r. spectroscopy.1647 The 13C n.m.r. specshow a pentadentate-hexadentate equilibritra of [Ni(edta)12um.1648 H' n.m.r. spectroscopy has been used to study the complexation of Zn(II1, Cd(II1, and Ni(I1) by 6-methyl-pyridine-2-phosphonic acid.1649 A H' and 170 n.m.r. study of acetic acid exchange processes of nickel chloride, nitrate, and acetate have been reported.1650 The binding of Cu2+ and Ni2+ to serum albumin has been studied by 35Cl n.m.r. spectroscopy.1651 Platinum. 31P n.m.r. spectroscopy has been used to examine the equilibrium between PtPh(OH)(Ph2PCH=CHPPh2) and [PtPh(OH2)(Ph2PCH=CHPPh2) H' n.m.r. spectroscopy has been used to demonstrate the simultaneous binding of Pt(I1) to three different sites of a guanine n u ~ 1 e o b a s e . l ~ H~' ~ n.m.r. spectroscopy has been used to determine the formation constant for [(NH3)2Pt(C5H5N202)2Zn(OH2)312+.1654 H' n.m.r. spectroscopy has been used to investigate the unwinding of an undecamer DNA fragment on binding to &-PtC12(NH3)2.1655 Copper. The equilibrium 2Me2CuLi # Me3Cu2Li + MeLi has been investigated by H' and 7Li n.m.r. spectroscopy.1656 13C n.m.r. spectroscopy has been used to investigate the complexation of Cu( I1 1 by H2NCH2CH20CH=CH2. 1657 H' n.m. r. spectroscopy has been used to investigate complexation between Cu(II)-histidine-kascorbic acid.1658 The structure and dynamics of the Cu(II)-h-proline complex have been investigated by H' and 13C relaxation measurement~.H ~ ~ ' ~ ~n.m.r. broadening has been used to investigate complex formation between Cu( 11) and (HOCH2CH2)3N.1660 13C relaxation has been used to investigate the binding of Cu(I1) to H02CC5H3CH2N2C8H130 The interaction of Cu (111 -histidine complexes with the vitamin C redox system has been investigated by H' n.m.r. spectroscopy.1662 H' and 31P !PI and T2 have been used to investigate Cu( I1 1 binding to hydroxyethylidenediphosphonic acid. 1663

Nuclear Magnetic Resonance Spectroscopy

57

N.m.r. spectroscopy has been used to investigate the binding of Cu(I1) to hyaluronic acid.1664 Gold. A 31P n.m.r. study of Ph2P(CH2)6PPh2 and [AuBr21- has shown the presence of 2 - , 3-, and 4-coordinate gold, and their interchange above -50 0C.1665 H' and 13C n.m.r. spectroscopy has been used to investigate the interaction of [CNI- with aurothiomalate. 1666 Zinc, Cadmium, and Mercury. 13C n.m.r. spectroscopy has been used to determine the stability of complexes formed between trien and Zn(I1) ,1667 and between Zn(I1) and 2,2'-ethylenediiminobis(ethylamine) and related ligands.1668 The stability constants of mixed ligand complexes of the type [Zn(phen)(amino acidate)'1 have been determined by H' n.m.r. spectroscopy.1669 H' n.m.r. spectroscopy has been used to investigate the binding of N,N'-dipyridoxyethylenediamine-N,g*-diacetic acid to Zn2+.1670 lH and 13C n.m.r. spectroscopy has been used to investigate the binding of Zn2+ to oxidised g 1 ~ t a t h i o n e . l ~The ~ ~ binding of Zn2+ to glycylhistidine and alanylhistidine has been investigated by H ' n.m.r. spectroscopy.1672 The complexation of zinc by g l y c y l h i ~ t i d y l l y s i n e ~and ~~~ L - h i ~ t i d y l g l y c y l g l y c i n e ~ has ~ ~ ~ been studied by H ' n.m.r spectroscopy. The complexing of zinc with aspartic acid has been studied by lH n.m.r. spectroscopy.1675 Ligand exchange kinetics of (Me2NI3PS on Zn(I1) and Cd(I1) have been determined by 31P and 35Cl n.m.r. spectroscopy.1676 'H, 13C, 31P and '13Cd n.m.r. spectroscopy has been used to study the binding of Cd2+ to ATP.1677 13C, 31P, and '13Cd n.m.r. spectroscopy has been used to study equilibria between Cd2+ and ethylenediamine-N,N,Nl ,N' -tetraphosphonate.1678 The binding of Cd2+ to osteocalcin has been studied by 'H, 31P, and '13Cd n.m.r. spectroscopy.1679 '13Cd n.m.r. spectroscopy has been used to investigate the binding of the lanthanide ions to parvalbumins 13C and '13Cd n.m.r. spectroscopy has been used to investigate the chelation of metal ions by parvalbumin.1681 Metal-ion binding at the activating site of rabbit muscle phosphoglucomutase has been studied by 7Li, 31P, and l13Cd n.m.r. spectroscopy.1682 '13Cd n.m.r. spectroscopy has been used to study exchange reactions between Cd( S2NR2 1 and mercury.1683 '13Cd n.m.r. spectroscopy has been used to investigate cadmium iodide complexes in supercooled aqueous solutions lg9Hg n.m.r. spectroscopy has been used to study the complexation of [MeHgI' with a series of pyridine~.'~~~'H, 13C, and 199Hg n.m.r. spectroscopy has been used to investigate [MeHg]+ derivatives of adenine with refer-

-

.

58

Spectroscopic Properties of Inorganic and Organometallic Compounds

ence to disproportionation and syn-anti isomerism.1686 Boron. A H ' n.m.r. study of the DMSO-H3B03-KOH-H20 system has "B n.m.r. spectroscopy has shown the presence of [B(OH)41-.1687 been used to study the equilibrium between borate and peroxide.lda8 "B and 13C n.m.r. spectroscopy has been used to investigate the nature of ester formation between borate and Q-mannitol, Q-glucit01, Q-fructose, and g - g l u c o ~ e . A ~ ~"B~ ~ and 27Al n.m.r study of the H+-Al3+-B(0Hl3 system has indicated that no or very weak aluminium-borate complexes form in sea water .1690 Aluminium and Gallium. The 27Al n.m.r. spectra of Na[H2A1COCH2CH2OMe)2] show that disproportionation has the solvent dependence C6H6 SOF2 > S02F2.312

SF4

T h e Raman s p e c t r u m o f S C l S A s F i g a v e t h e

f o l l o w i n g c a t i o n wavenurnbers:

Vs

6s

5 2 0 ~ m - ~ , V a s5 3 1 / 5 4 7 c m - l ,

2 8 5 ~ m - l v~a s 2 1 7 ~ m - l . ~ ~ ~ Raman s p e c t r a s h o w e d t h a t S e 0 2 s o l u t i o n s i n a q u e o u s H B r

H S e 0 2 B r , SeOBr;,

c o n t a i n e d H2Se03,

m e n t s were p r o p o s e d f o r b a s i s of for

Cs

symmetry.315

a ferroelectric

SeBr;

a n d SeBri-.314

t h e hydrogen s e l e n i t e ion,

on t h e

Raman s p e c t r a o f RbHSe04 g a v e e v i d e n c e

p h a s e t r a n s i t i o n . 316

Reasonably complete

v i b r a t i o n a l a s s i g n m e n t s w e r e p r o p o s e d f a r CF3SeD3H, CF3SeF4C1.317

Assign-

HSeO;,

T h e Raman s p e c t r a o f S e x 2 ,

CF3SeF5 a n d

where X = C 1 o r B r ,

i n

MeCN s o l u t i o n shqw t h a t t h e d i h a l i d e s a r e t h e d o m i n a n t s p e c i e s 3 18 b u t t h a t Se2C12, SeC14 a n d S e 2 B r 2 a r e a l s o p r e s e n t . vTe-C(alky1)

6.4 Tellurium.X = C1,

Br or

I,

R = Et,

i s a t 5 3 0 - 5 4 0 ~ m - ~i n (16), w h e r e 319 CH2COPh e t c .

CH Ph, CH2=CHCH2, 2

(16) vTe-0

(340-390cm-l)

was a s s i g n e d i n Ph3Te[RCOCH=C ( O ) R ] ,

where

R = C H 3 , CF3 o r Ph, w i t h u n i d e n t a t e B - d i k e t ~ n a t e s . ~ ~B i' T e O The

g i v e s i.r. bands c h a r a c t e r i s t i c o f t e t r a h e d r a l Tea4 vibrational spectra of crystalline the orthorhombic

show t h a t i n

(Ph4As)2TeClg

form the anion i s of

0

t r i c l i n i c f o r m t h e symmetry i s lower.329

symmetry

but that

i n the

1 . r . a n d Raman s p e c t r a

o f o r t h o r h o m b i c T e B r g a v e e v i d e n c e f o r low-wavenumber 2 323 phonons w i t h very l a r g e p o l a r i s a b i l i t i e s .

(E.20cm-l)

7 Group V I I T r a n s i t i o n i n t e n s i t i e s o f n a t u r a l i s o t o p i c HF a n d H C 1 v a p o u r s were measured a t D o p p l e r - l i m i t e d r e s o l u t i o n . 3 2 4 (HF)

(HF)(DF)

and (DF)

3826cm-':

(HF)(DF)

3831,

of

Raman s p e c t r a o f structures.326

gave t h e f o l l o w i n g

Matrix-i.r.

(HF)2 2 2 8 0 8 ~ m - ~ (, O F ) 2 2 6 0 3 c m - ~ . 1 ~ .~r .~ a n d

l i q u i d HF a n d o f H 2 F t

were used t o d i s c u s s t h e i r

V i b r a t i o n a l s p e c t r a o f KF.nHF

(2

= 3 o r 4 , b a n d s d u e t o F3H;

= 1, 2,

3 or 4 )

were seen. 327 s p e c i e s i s a l s o p r e s e n t i n l i q u i d HF s o l u t i o n s o f KF.

were r e p o r t e d .

For

spectra

assignments:

This

248

Spectroscopic Properties of Inorganic and Organometallic Compounds

Co-deposition

o f HF a n d N

c o m p l e x w i t h vHF

i n argon m a t r i c e s produces an N

3881.4cmZ1,

vNN

...HF

( c o n f i r m e d b y ''N15N

2332.lcm-1

a n d l 5 N 2 s u b s t i t ~ t i o n ) .H~y d ~ r~o g e n - b o n d e d c o m p l e x e s o f H2X ( X

=

S , S e ) a n d HF w e r e d e t e c t e d i n A r m a t r i c e s a t 1 2 K .

vsHF w e r e a t

3652,

HF...HSH

3655cm-1

H2S

for

...HF,

H Se...HF

respectively.

was

2 -1 ) , a n d t h e r e was e v i d e n c e f o r

a l s o s e e n (vHF

3799cm

H2S...(HF)2.329

H X a d d u c t s (X = F,

C1 o r B r ) w i t h oxygen-

-

(CH ) 0 , w h e r e n = 2, 3, 4 , o r 2n ( C H ) 4 0 , w e r e c h a r a c t e r i s e d i n l o w - t e m p e r a t u r e m a t r i c e s . T h e uHX 3 30 modes s u g g e s t t h a t b a t h HX.L a n d HX.2L s p e c i e s a r e f o r m e d . containing heterocycles,

Matrix-i.r.

e.g.

spectra o f HX

= Et,

ments:

or tBu)

iPr

(for R

a n d 3667cm-1,

show t h a t VHX i s a l w a y s s h i f t e d t o l o w e r

1 . r . s p e c t r a o f 1:1, 1 : 2

wavenumbers.331 (R

= F, C1, B r ) complexes with m e t h y l -

(X

s u b s t i t u t e d cyclopropanes

w i t h HF,

2 = 1

= tBu)

i.e.

and 1:3

RCN(HF)n,

3522cm-l,

fi

=

?

3630cm-l,

861cm-1

(VaSNCO),

a n d 529cm-1

2

= 3 3678

332

F-NCO h a s b e e n i d e n t i f i e d i n a n A r m a t r i x , 2172cm-1

adduct o f RCN

g a v e UHF a s s i g n -

(GFNC).

assignments. 333

(VNF),

695crn-1

w i t h i.r. bands a t :

(SNCO),

646cm-1

(6NCO)

1 5 N s u b s t i t u t i o n was u s e d t o c o n f i r m t h e

1.r. spectra o f m a t r i x - i s o l a t e d C1F w i t h various

o x y g e n b a s e s g a v e e v i d e n c e f o r t h e f o r m a t i o n c f 1:l c o m p l e x e s 334 C 1 t o t h e 0 o f t h e base.

1 . r . d a t a s h o w e d t h a t H2S formed i n low-temperature

...X 2

( X = C 1 o r B r) c o m p l e x e s w e r e

o r N2 m a t r i c e s . 3 3 5

A r

via

1.r. band

s t r e n g t h s were measured f o r t h e f u n d a m e n t a l and f i r s t o v e r t o n e o f H C 1 and D C 1 i n l i q u i d xenon s o l u t i o n . 3 3 6 modes was s t u d i e d i n r a r e - g a s where X = Cl.

or B r , Y = A r ,

P e r t u r b a t i o n o f VHX

hydrogen h a l i d e complexes

K r o r Xe.

(HX)Y,

The d i s s o c i a t i o n energy of

(HC1)Xe was c a l c u l a t e d t o b e 2 2 0 c m - l . ~ ~ ~ A vibrational

N2 X

a n a l y s i s o f most o f t h e ~ 2 c + - ~ 2 1 1 a n d

s y s t e m s o f XCN'

B r or

(X = C 1 ,

o f t h e s e c a t i o n s i n t h e i r ?211

i . r . a n d Raman d a t a f o r X O and Ba2+ c o u n t e r - i o n s . Good a g r e e m e n t

I)

g211-

g a v e v i b r a t i o n a l wavenumbers

states.338

Several papers r e p o r t 2t Br o r I) w i t h S r

a n i o n s (X = C 1 ,

339-321

was a c h i e v e d b e t w e e n o b s e r v e d a n d c a l c u l a t e d

d e p o l a r i s a t i o n r a t i o s of

Q-branches i n t h e continuous resonance

Raman s p e c t r u m o f 7 9 B r 2 . 3 4 2

1 . r . a n d Raman d a t a f o r MF.2BrF3 a n d

MF.3BrF3, u h e r e M = C s o r R b , a r e c o n s i s t e n t w i t h t h e f o r m u l a t i o n s MtBr2F;, Mt8r3F;0 r e s p e c t i v e l y . 34 3

249

Characteristic Vibrations of Compounds of Main-group Elements Iodosomethane, a t 17K. VI-180

CH310,

has been c h a r a c t e r i s e d i n an a r g o n m a t r i x

i s a t 688.lcrn-l,

vI-l6O

a t 723.7crn-l.

v S I O 2 a t 7 9 5 . 9 ~ r n - ~ ,v a s I 0 2 a t 829.8cm-1.344

CH3102 h a s

The s p l i t t i n g o f v I C l

i n I C 1 complexes w i t h c a r b o n y l bases i s e x p l a i n e d b y t h e presence 345 s t e r e o i s o m e r i c c o m p l e x e s ( o n e l i n e a r , one b e n t ) .

o f t w o 1:l 8

Group V I I I

T h e FTIR e m i s s i o n s p e c t r u m of v a l u e s were o b t a i n e d f o r 22NeH+ 2 6 7 2 . 4 9 6 0 ( 1 0 ) c r n - l t

NeH'

20NeOt

T h e Raman s p e c t r a o f Xel'OF; t h e p r e s e n c e of

h a s been observed. The f o l l o w i n g

(1,O) b a n d s : 2 0 N e H t

2677.8565(5)~m-~,

1984.5937(33)~rn-~.~~~ a n d Xe180F;

are consistent with

a stereochemically active lone pair. This gives a

d i s t o r t e d o c t a h e d r a l arrangement o f t h e f i v e f l u o r i n e s and one oxygen.

The f o l l o w i n g

assignments were proposed f o r t h e 1 6 G

m o l e c u l e : vXe=O 8 8 3 c r n - l , vsXeF ( o u t o f p h a s e ) 5 4 4 c m - l , v s X e F 4 5 2 4 -1 crn , v a s XeF4 473, 4 6 8 , 435crn-.', v X e F ' 4 2 0 c m - l . Raman d a t a w e r e (XeOF4)3F-.347 a l s o g i v e n and a s s i g n e d f o r

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1985,

&,

,2835.

Characteristic Vibrations of Compounds of Main-group Elements 116 117

118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133

134 135 136 137

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103,

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3,

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10,

.

18,

58,

70,

16,

127,

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2,

30,

102,

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,

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.,

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112,

111,

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15,

g,

g,

x,

l l L U .

257

Characteristic Vibrations of Compounds of Main-group Elements

S.J.Cywin, B .N.Cyvin, C .Wibbelrnann, R . B e c k e r , W.Brockner 709. a n d M.Parensen, Z . N a t u r f o r s c tI , T e i l A,1985, 249 1984, 21,611. J.J.Barieux a n d M.C.Dernarc : q , R e v . C h i m . M i n . 250 M.Takami a n d H . K u z e . R e z a K a o a k u K e n k y u , 1 9 8 4 , S , 1 6 7 (Cherni Abs., 1985, 157133). 1985, M.Takarni a n d K . K u c h i t s u , J. Chern. P h y s . , 2 5 1 S.Yarnamoto, 82, 3 8 7 9 . 2 5 2 K B . E n a l i s h a n d A.M.Heyns, J. C r ~ s t a l l o g r . S p e c t r o s c . R e s . , 1964, i 4 , 531. 25 3 N . A . C h Z a e w s k i i , 1984, 1015. R u s s . J. I n o r q . Chern., 25 4 J.Sharnir, S.Luski, A.Bino, S.Cohen a n d D.Gibson, 2 30 1 I n o r g . Chern., 1985, I n o r q . Chirn. 255 R.C.M e h r o t r a and V.K.Jain, R.K.Gupta, A.K.Rai, A c t a , 1 9 8 4 , 88, 201. C h i m . Phys., 1984, 397. 256 M.Joannidou and F . F i l l a u x A c t a, 25 7 E .H u s s o n , Y .f? e p e l i n a n d M.T . V a n d e nb o r r e , Spec t r o c h i r n 1017. F a r t A, 1984, e r , Z . a n o r q . a l l q . Chern., M.Sorner a n d W.Bro 25 8 W.Bues, 1 9 8 4 , 51F;, 42. c h a c k and R.D.Wilson, I n o r q . Ch e m K . C h r i s t e , W.W.Wilson, 25 9 C. 1985, 303. and R .Minkwitz, Z. anorq. a l l q . 26 0 F . C l a u s , M . G l a s e r , V.Wf3lf Chern., 1 9 8 4 , 517, 2 0 7 . a n o r q . a l l q . Chern., 1985,523, 45 and U . M t l l e r 26 1 A.T.Mohammed c t a C r y s t a l l o q r . ,1985, C A , 3 2 9 . 26 2 A .T .Mohammed a n d U . M B l l e r ! 751. 26 3 B . E b e r l e , H . S o n t a g a n d R . W e b e r , S u r f . S c i . , 1 9 8 5 , 26 4 W . K o l o n d r a , W.Schwarz a n d J . W e i d l e i n , Z . N a t tJ r f o r s c h . , T c i l El, 1985, 872. 265 V . S . D e r n o v a , 1 . F . K o v a l .ew, R .G . K u t l u b a e v , R .G . M i r s k . o v , V . C . C h e r n o v a a n d M.G.Voronkov, I z w . S i b . O t d . Akad. N a u k SSSR S e r . Khirn. Nauk, 1 9 8 4 , 88. J. O r q a n o m e t a l . Chern. D.B . S o w e r b y a n d M . J . B e g l e y , 266 D.M.Wesolek, 1985, c5. A . J e r e z , C . P i c 0 a n d M.A.V e i g a , J.A.Alonso, A.Castro, 26 7 J. Chem. S O C . , D a l t o n T r a n s . , 1 9 8 5 , 2 2 2 5 . M .H ..o -f O r q a n o r n e t a l . Chem., 1985, 26 8 H 33. C .Gornez-Vaarnonde, J.R . M a s a ~ u e r , J.A. 26 9 A . A l v a r e z - V a l d e s , Garcia-Vazquez, 2.anorq. a l l q . Chem., 1985, &,-227. 270 A .Alvarez-Valdes, J.R . M a s a g u e r a n d J.A . G a r c i a - V a z q u e z , 995. Spectrochirn. Acta, P a r t A, 1984, 271 J.M.Kisenyi, J. Chern. S O C . , G.R.Willey a n d M.G.B.Drew, D a l t o n Trans., 1985, 1073. 27 2 A.T.Moharnrned and U . M n l l e r , Z . N a t u r f o r s c h . , T e i l B ,1985,

248

9,

,

&,

29,

24,

.

81,

a,

.

-

24,

.

156,

408,

293,

295,.

a,

408,

562. 273 274 275 276 277 27 8 279 2 80

P . T a y l o r , S.Sunder a n d V . J.Lopata, C a n . J. Chern. , 1 9 8 4 , 6 2 , 2 8 6 3 121. W.Wojdowski, Phys. S t a t . S o l i d i , B , 1985, J. O r q a n o r n e t a l . Chern.,1985,=,133 M.Dr%ger a n d B . M . S c h r n i d t , G.S.H.Chen, J.Passrnore, P.Taylor, T.K.Whidden a n d P.S.White, J . Chern. S O C . , D a l t o n T r a n s . , 1 9 6 5 , 9. M.W.Crofton, R.S.Altrnan, M.F.Jagod and T.Oka, J.Phys. Chern., 3E14. 1985, 48, 1 1 7 . M.P.Conrad and H.L.Strauss, B i o p h y s . J.,1985, V . P.Kochanow, Y u . S . M a k u s h k i n , L.N. O.K.Voitsekhovskaya, S i n i t s a , A.M.Solodov. 0.N.Sulakshina and V.N.Chere~anov. Opt. Spektrosk., 1 9 8 5 , 58, 1 0 1 6 . J. M o l . S p e c t . r o s c . , A.Perrin, J.M.Flaud andC.Carny-Peyret, 153. 1985,

130,

g,

112,

Spectroscopic Properties of Inorganic and Organometallic Compounds

258 281 282 283 2 84 2 85 2 86 2 87 288 2 89 290 291 292 293 294 295 296 297 298 299 300

301 30 2 30 3 304 305 306 307 30 8 309 310 311 3 12 313 314 315 316 317 3 18 319

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17,

89,

130,

-

.

s,

116,

-

24,

27,

118,

Characteristic Vibrations of Compounds of Main-group Elements

259

320

B .L.Khandelwal, A . K . S i n g h , H .B . S i n g h , K.M.Prasad, N.S. B h a n d a r i a n d W.R.McWhinnie, J. O r q a n o m e t a l . Chem.,1985,=,

321

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185.

322 32 3 324 325 326 327 32 8 329 330 331 332 333 334 335 336 3 37 338 339 340

34 1 342 343 344 345 346 34 7

130, 109,

127,

111,

83,

15,

113,

Vibrational Spectra of Transition-element Compounds BY G. DAVIOSON 1

Detailed Studies r e a c t w i t h H20 i n a n A r m a t r i x a t 1 5 K t o f o r m non-

T i and V

Sc,

l i n e a r HMOH,

H/D

shifts.

Vibrational Thus,

a s s i g n m e n t s w e r e made u s i n g l 6 0 / l 8 O

1 4 8 5 . 0 ~ m - ~ ( H ~ ~ 1~0O 7 0) .,0 c m - 1 ( D 2 0 ) , ~ S c 0

and 0 - 0

' 7 1 5 . B ~ m - ~ ( H ~6~9 0~. 4~ ) ,

6 9 8 . 2 ~ r n - ~ ( D ~ .l O ) R e l a t i o n s h i p s between vsM-O,

cm-1(H2180),

and

f o r HScOH, VScH was a t 1 4 8 5 . l ~ r n - ~(H l 6 0 ) , vCO

i n t r a l i g a n d d i s t a n c e were e s t a b l i s h e d f r o m t h e Raman

spectra of

M(acac)3,

where

(r, =

Sc,

W,

C r , Mn,

R h or Ir.

F e , Co,

@ a t i v e ? T - b o n d i n g was t h o u g h t t o p l a y o n l y a s m a l l r o l e i n t h e

160/180

t o t a l bcnding.

isot.opic s h i f t s i n t h e v i b r a t i o n a l

3-

were shown t o b e n o r m a l , 3 previously reported. s p e c t r u m o f V04

P h o t o l y s i s of i n A r matrices at

ref.

data (including,

(for

Cr1602, 915,

adducts,

where M = C r ,

Mn,

Co o r C u ,

Fe,

15K p r o d u c e s n o n - l i n e a r HMOH m o l e c u l e s .

As i n

1, v i b r a t i o n a l a s s i g n m e n t s w e r e made b a s e d o n i s o t o p i c s h i f t

CrF:-

= C r )

Cr160180,

890,

WO3?

M

PI =

for

Cu,

63Cu/65Cu).4

Prolonged photo-oxidat1 6 18 0 0,

w h e r e M = C r o r W, i n A r m a t r i c e s d o p e d w i t h C

i o n o f M(CD),, gave

M/H20

n o t anomalous as

i . r . b a n d s a t 964,

CrI80

respectively

8 8 0 a n d 870cmZ1 d u e t o

9 5 0 a n d 925cm-1

due t o

I,

3 Of bands a t

and ( f o r M = W )

v3 o f a l l t h e i s o t o p i c forms o f

F u l l v i b r a t i o n a l a s s i g n m e n t s were o b t a i n e d f o r C r F i a n d and used i n n o r m a l - c o o r d i n a t e

i . r . s t u d i e s o n C r O F 4 show

1027.7cm-1

and VCr-F(e)

analyses.6

Matrix-isolation

) i s at 1 Chromium i s o t o p i c

( i n N2 m a t r i c e s ) t h a t vCr=O(a

a t 746.3/74l.6cmm1.

f i n e s t r u c t u r e and r e l a t i v e i n t e n s i t i e s suggested a bond angle o f a b o u t 106' H/D

f o r OCrF.

a n d 160/180

7

isotopic

s t u d i e s were used t o i d e n t i f y V

( 6 0 0 ~ r n - ~ a) n d 6 s F e 3 0 ( 3 0 0 ~ m - ~modes ) o f F e 3 0 ( 0 A c ),py:+.' i n C O ~ ( C O ) ~ ~ ( I2. -C2H2) I ~ - ~ ~ i s a t 6 1 9 ~ m - ~ ( 6 0 3 c m o- n~ 1 3 C sub s t i t u t ion).

9

Skeletal-mode NiL:-,

Fe30 as VCO-C~ isotopic

assignments i n NiBr2(H4L),

N i B r (HqL)2 and

where H L = e t h y l e n e d i p h o s p h i n e t e t r a a c e t i c a c i d ,

i d e n t i f i e d by "Ni/"Ni

isotopic

shifts.

w e r e made f o r N i a n d C u d i t h i z o n a t e s ; '

were

lo S i m i l a r assignments

and d i t h i o c a r b a m a t e s

12

Vibrational Spectra of Transition-element Compounds used 58Ni/62Ni

and 63Cu/

65

Cu i s o t o p i c

261

shifts.

F T I R e m i s s i o n f r o m CuH g a v e t h e f o l l o w i n g w 1 9 4 0 . 7 4 6 2 ( 4 1 ) ~ m - ~( 6 3 C u H ) ,

values:

1 9 4 0 . 2 7 4 0 ( 4 7 ) ~ m - ~(B5Cu).13

Raman s p e c t r a w e r e o b t a i n e d f o r

(Me2S)AuX

(X

=

(Me2S)RuCl3 and t h e i r p e r d e u t e r i a t e d d e r i v a t i v e s , modes w e r e a s s i g n e d .

A

normal-coordinate

1.r. and

C 1 or B r ) , and s k e l e t a l

a n a l y s i s suggested t h a t

t h e Me S l i g a n d s t a b i l i s e d t h e Au-C1 b o n d t r a n s t o i t ~ e 1 f . l ~ 2 15 V Z n - N i n [ Z P ( N H ~ ) (~R] e 0 4 ) 2 was f o u n d b y l 4 N / l 5 N s u b s t i t u t i o n .

1.r. s p e c t r a f o r CdAl

C d A 1 4 0 7 , C d A 1 2 0 4 a n d CdGa O 4 w e r e

0

i n t e r p r e t e d u s i n g 106~~/”‘iZd assignment 2o f HgX3Y

isotopic substitution.”

A f u l l

of

,

v i b r a t i o n a l modes was g i v e n f r o m t h e Raman s p e c t r a 17 w h e r e X f Y = C 1 , B r o r I.

A high-resolution

i.r.

study o f

V3

o f 6 2 7 . 7 2 3 8 7 ( 1 1 ) ~ m - ~ .T h e 2 3 5 U / 2 3 8 U b e 0,60379

0.00017cm-

f.

.

where L n = Eu,

o f lanthanide

gave a b a n d c e n t r e

1 18

R e s o n a n c e Raman S p e c t r a . f o r Ln203,

o f 238UF6

i s o t o p i c s h i f t was f o u n d t o

R e s o n a n c e Raman s p e c t r a w e r e r e p o r t e d D y o r Tm.19

T h e r e s o n a n c e Raman s p e c t r a

acetylacetonate derivatives o f

p o r p h y r i n a t o show t h a t t h e M - 0

stretch(sym.)

a,B,y,d-tetraphenyl1 20

.

i s n e a r 370cm-

R e s o n a n c e Raman p r o g r e s s i o n s w e r e o b s e r v e d f o r C r 2 i s o l a t e d i n solid Ar,

Kr o r Xe.

a n d wexe 14.5cm-l.

I n Xe t h e v i b r a t i o n a l c o n s t a n t s a r e w

l y i n g e x c i t e d s t a t e o f C r 2.21 (TTP)CrN,

T h e r e s o n a n c e Raman s p e c t r u m o f

w h e r e TTP = t e t r a - e - t o l y l p o r p h i n a t o ,

met o f V C r r N ,

438~m-~

A n o t h e r p r o g r e s s i o n was a s s i g n e d t o a ;ow-

b u t t h e Mn a n a l o g u e

shows n o enhance-

g i v e s a s t r o n g l y e n h a n c e d vMnEN

X = C1, B r o r I, g a v e t h e f o l l o w i n g g r o u n d - s t a t e h a r m o n i c w a v e n u m b e r s f o r t h e Mo-No s t r e t c h : 3 5 9 . 5 ~ m - ~ ( C l ) , 3 5 0 . 6 ~ m - ~ ( B r a) n d 3 4 0 . 4 c m - l ( I) . 2 3

m o d e . 2 2 R e s o n a n c e Raman d a t a f o r M o 2 X g ( H 2 0 ) $ - , w h e r e

D e t a i l e d e x c i t a t i o n p r o f i l e s w e r e o b t a i n e d f o r v1 a n d 2vl b a n d s f r o m t h e r e s o n a n c e Raman s p e c t r a o f M n O Z -

isomorphously

doped i n t o K C r 0 4 ( e x c i t a t i o n r a n g e 406.7-676.4nm). T h e s e show 2 t h a t t h e e x c i t e d ( 2 T 2 ) s t a t e h a s Nn-0 0 . 0 3 5 a l o n g e r t h a n i n t h e ground (2E)

f o r Mn0;

state.24

R e s o n a n c e Raman r e s u l t s w e r e a l s o g i v e n

i n KC104 a t 5 K 2 5 a n d R e S i . 2 6

Time-resolved

resonance

Raman s p e c t r a f o r t h e e m i s s i v e e x c i t e d s t a t e o f R e 2 C 1 i - s h o w e d t h a t VRe-Re

i n t h e e x c i t e d s t a t e was a t t h e u n e x p e c t e d l y l o w

w a v e n u m b e r o f 2 0 4 c m - l . 27 Raman a n d r e s o n a n c e Raman s p e c t r a f o r Fe(WS and a v a r i e t y of t h e F e ( o r Ag)

13’

4 2 ’ Ag(MoS4)zr e l a t e d s p e c i e s gave u s e f u l i n f o r m a t i o n on

-PIS4

delocalisation?8

262

Spectroscopic Properties of Inorganic and Organometallic Compounds

T h e r e s o n a c e Raman s p e c t r u m o f F e ( s a l e n ) O C 6 H 4 - 4 - M e ,

for iron-tyrosinate proteins, t o t h e Fe-0 s t r e t c h , years,

a model

g a v e a f e a t u r e a t 5 7 0 ~ m - a~s s i g n e d

As i n p r e v i o u s

c o u p l e d t o r i n g modes.29

t h e r e h a v e b e e n a v e r y l a r g e n u m b e r o f r e s o n a n c e Raman development

s t u d i e s o n i r o n - c o n t a i n i n g b i o m o l e c u l e s .30-40 A new

has been t h e use o f picosecond t i m e - r e s o l v e d experiments t o f o l l o w v e r y r a p i d b o n d i n g processes i n such molecules.41942

1.r. a n d r e s o n a n c e Raman s p e c t r a o f C O X P c ( - 1 ) , w h e r e X = 2 and CoX2Pc(2-), w h e r e X = OH, F , C 1 o r B r , Pc =

C 1 or Br,

p h t h a l o c y a n i n a t o , were a b l e t o g i v e v a l u e s f o r vSCoX(a

v

43

as

19

) and

CoX(aZu) wavenurnbers. I n a d d i t i o n t o a r e v i e w c f Raman a n d r e s o n a n c e Raman s p e c t r a

o f l i n e a r c h a i n complexes ( c h i e f l y

o f Pd a n d P t ) , 4 4

h a v e b e e n s e v e r a l new r e p o r t s f o r s u c h s y s t e m s : [pd ( en)X4],

where X

= C1,

1,3-d i a m i n o p r o p a n e ,45 where [Pd"

x

= Br o r

K4

(c 1 0 4 ) 4 ,

( L - L ) , ] [ P ~ I ~ ' ( L . - L ) 2 ~ 1 2 (~c

(p Pt Bands

op ) X

1."H

Kq [Pt

L

wh e r e t n =

X I [ p t I f 1a(7H 2 P

[ P t "(e [Pt(en)2

d i a m inopropane ,48

1,

Pd(tn)Br

Br,

there

[Pd(en)X,]-

L-L

(pop)

= en,

( POP 4X

0 , w h er e po

X = C1,

due m a i n l y t o VCu-S(Cys)

a n d vCu-I\l(His)

2

Scandium,

o r 1,3-

1,2-

1

were i d e n t i f i e d

respect,ively i n single-copper 50 p r o t e i n s from a v a r i e t y o f b a c t e r i a . R e s o n a n c e Raman d a t a f o r Ag2 i n r a r e - g a s

blue

m a t r i c e s were used t o

vAg2 l a y i n t h e r a n g e 1 9 0 - 2 0 3 ~ m - ~ . ~ ~

Yttrium, and t h e Lanthanoids

E a r l i e r r e f e r e n c e h a s b e e n made t o d e t a i l e d s t u d i e s o n HScOH 1 and Sc(acac) ig3' Dy o r T m ) .

w i t h r e s o n a n c e Raman d a t a f o r L n 2 0 3 ( L n = E u ,

A d d i t i o n o f S c 2 0 3 t o s o d i u m s i l i c a t e g l a s s e s g a v e new Raman b a n d s a s s i g n a b l e t o S c 3 + i o n s c o o r d i n a t e d b y Si0;-

tetrahedra. 52

lanthanide oxides Ln 0 2 3 S c ) w e r e a s s i g n e d w i t h t h e a i d o f a c a l c u l a t i o n of

T h e v i b r a t i o n a l s p e c t r a o f :-type ( L n = La,

Gd,

t h e spectrum using a polymer-chain approximation.53 a s s i g n e d f o r Ln(TPP)acac effects

-

vM-0'

was

t h e w a v e n u m b e r was r e d u c e d b y t h e

o f TPP c o o r d i n a t i o n (TPP = t e t r a p h e n y l p o r p h i n a t o ) .

54

The i . r .

s p e c t r a o f Ln2M207 w e r e a s s i g n e d u s i n g 4 6 T i / 5 @ T i a n d 55 98Ru/104Ru i s o t o p i c s u b s t i t u t i o n ( L n = Gd, L u , M = T i , R u ) .

1 . r . a n d Raman d a t a ,

wit,h

'

.2H 0 , 49 Br o r I.

n e a r 400 a n d n e a r 270cm-1

characterise trapping sites.

2°5)4x2'

some a s s i g n m e n t s ,

were p r e s e n t e d f o r

263

Vibrational Spectra of Transition-element Compounds 40CaLa4Ti4015,

44CaLa4Ti4015,

Normal-coordinate L n = Tb,

Dy,

and r e l a t e d s p e c i e s . 56

a n a l y s e s were p e r f o r m e d o n Ln2Cu205 ( w h e r e

E r , Tm,

Wo,

SrLa4Ti4015

Yb,

Lu,

Y,

S C ) . ~ 1.r. ~

o f NaLa(Mo04)2 were i n t e r p r e t e d on t h e b a s i s o f

vLn-0 Ho,

i n LnP5014,

Er,

Y,

n u m b e r o f Ln.

where Ln= La,

Yb or L u ,

Tm,

Ce,

Pr,

Nd,

Sm,

a n d Rarnan s p e c t r a 58 symmetry.

C4h Eu,

Gd,

Tb,

59

1.r. a n d Raman s p e c t r a o f s a m p l e s f r o m t h e LaC13-CuC12 show t h a t b r a n c h e d , LaC13-CuC12-KC1

p o l y m e r i c c h a i n s a r e formed.

system

I n t h e system

t h e r e was e v i d e n c e f o r p o l y m e r i c c h a i n s c o n t a i n i n g

CuC15

(C4,)

a n d LaC16 ( g h ) . 6 0

Ho13,

Lu13,

GdBr3 a n d L u 8 r 3 i n i n e r t - g a s m a t r i c e s .

3

Dy,

increased l i n e a r l y w i t h t h e atomic

Titanium,

1.r. s p e c t r a w e r e o b t a i n e d f o r G d I 3’ 61

Z i r c o n i u m , and H a f n i u m

R e f e r e n c e h a s a l r e a d y b e e n made t o r e s u l t s o n HTiOH,’ 56 ( L n = Gd o r L u ) , ’ ~ a n d C a L a 4 T i 4 0 1 5 .

Ln2Ti207

T h e r e i s Rarnan e v i d e n c e f o r t h e e x i s t e n c e o f T i = 0 2 + i n a c i d i c a q u e o u s s o l u t i o n s , i . e . V T i = O i s a t 9 7 5 ~ m -i ~n 0.08M T i O ( C 1 0 ) i n 2 1 HC104.62 K[Ti(O2)F3I.3H2O h a s V T i 0 2 a t 530 and 610cm- 1 4 d

.

The i.r.

spectrum of

K2TiOF4 c o n t a i n s a b a n d a t

BlOcm-’,

i n g t h a t t h e r e a r e i n f i n i t . e chains -Ti-0-Ti-0-Ti-0-

v

structure.64 [PcTi-O-TiPc]”; V3

of

T i - 0 - T i i s a t 8 2 0 ~ m - i~n t h e i . r . where Pc = p h t h a l o c y a n i n a t o . 6 5

suggest-

i n the spectrum o f

gaseous T i F 4 h a s been observed i n i t s i.r.

spectrum a t

completing t h e v i b r a t i o n a l assignment f o r t h i s

772cn-l,

molecule.66

Phase t r a n s i t i o n s i n MTiF6.6H20,

where M = Mn or Z n ,

and t h e i r d e u t e r i o analogues were observed f r o m changes i n v o f T i F 6 w i t h t e m p e r a t ~ r e . V~ M~C l modes w e r e a s s i g n e d a s f o l l z w s f o r trans-MC12(dmpe)2:

PI = T i

3 3 8 ~ r n - l . ~T~h e r e i s i . r .

3 2 0 ~ m - ~V,

312crnm1,

C r

evidence f o r t h e d i m e r i s a t i o n o f

T i C 1 4 i n a r g o n m a t r i c e s . T h e T i 2 C l g seems t o b e a d o u b l y b r i d g e d system o f v

~

~

(

~

C2h

Raman s p e c t r a o f A 2 A ’ T i C 1 6 , 77K show s p l i t t i n g o f 70 distortion.

w i t h u T i C l t (bu) 5 4 4 ~ m - l ~ ax a~n d ~V e q ( s ) T i C l t (bu) 3 9 0 ~ m - ~ . ~ T h’ e

symmetry,

(a,) ~ ) 4T 5 6 c~m - l C , the t

where A, 29

A’

= alkali-metal

mode d u e t o s t a t i c

ions,

at

4h

T h e FTIR s p e c t r u m o f H 2 a d s o r b e d o n t o Zr02 a t room t e m p e r a t u r e c o n t a i n s b a n d s a t 1 5 6 2 a n d 1371cm-1 respectively,

due t o vZrH,

vZrHZr

showing t h a t d i s s o c i a t i o n o f t h e H 2 has occurred,

71

Spectroscopic Properties of Inorganic and Organometallic Compounds

264

M[ZrO(NCS)3'].2H20, 9 1 6 a n d 615cm-1

o r pyH+, h a v e i . r . b a n d s a t

w h e r e M = CS'

assigned t o two d i f f e r e n t b r i d g e d 0x0-zirconium

modes i n a n o l i g o m a r i c

structure.72

Raman s p e c t r a o f B a F 2 - Z r F 4 -

F e F 2 g l a s s e s show t h a t i n c r e a s i n g t h e f r a c t i o n o f B a F 2 l e a d s t o a n i n c r e a s e i n t h e c o o r d i n a t i o n number o f Z r f r o m 6 t o 7.73 melts containing ZrCli-,

Raman s p e c t r a o f TaC1;

HfCli-,

The

NbClg and

a r e c o n s i s t e n t w i t h r e g u l a r o c t a h e d r a l geometry f o r t h e

anions.

T h e s y m m e t r i c s t r e t c h s h i f t s t o h i g h e r wavenumber

s i z e o f t h e c a t i o n increases.74

as t h e

M-0

s t r e t c h e s were a s s i g n e d f o r 75 ML4, w h e r e M = Z r , T h o r U, L = CHBr C O 2 2' Other s p e c i e s f o r which v i b r a t i o n a l d a t a have appeared are: Ga2Ti05,76

CpTiC12(NHR),

Cp2Ti(l-nor)Cl, 70 1-norbornyl.

w h e r e R = Et,iPr,

Cp2Ti(l-nor)2,

4 Vanadium,

o r Ph,77 a n d

tBu

CpTi(l-nor)3,

where 1-nor

Niobium, and T a n t a l u m

E a r l i e r r e f e r e n c e was made t o H V O H , l

V(acac)3,2

I s o t o p i c l a b e l l i n g e x p e r i m e n t s o n (C5M;5)2V V N ( n i t r e n e ) s t r e t c h i s a t 934cm-1

and V04 3-

.

3

YNPh show t h a t t h e f o r l5N),

(923cm

=

correcting

a n e a r l i e r a ~ s i g n m e n t . ~ 'T h e h i g h w a v e n u m b e r o f t h e VN s t r e t c h i n Me S i - N Z V C l 3 ( 1 1 0 4 ~ m - ~was ) ascribed t o c o u p l i n g w i t h t h e Si-N 3 v M = N modes w e r e a s s i g n e d i n X M=N-TeF5 ( M = V , X = stretch." 3 F or C 1 ) a n d X4M=N-TeF5 ( M = No o r W, X = F o r C 1 ) . 8 1 S k e l e t a l -

mode a s s i g n m e n t s f o r [ V C l include

VVN

V

n e a r 300cm

2 VV=O i n V O ( S 0 3 C F 3 ) 2

(N S2)]

-3 .83

QI,

[VC12(N3S2) . N S C l ]

)3 (1005~rn-~)

( 1 0 2 5 ~ m - ~a) n d VO(S0,CF

show t h a t t h e r e i s n o p o l y m e r i s a t i o n v i a V=O.'j where R = d i - E t - ,

di-Pr,

di-iso-Pr

etc.,

etc.

VO(RNCS2)2,

h a v e vV=O 9 5 0 - 1 0 0 0 ~ m - ~ ,

V V - S 3 9 0 - 3 7 0 ~ m - ~ ,a n d v s V - S 340-380crn-'* A c o r r e l a t i o n was f o u n d as b e t w e e n u V = O a n d t h e b +e3$ b a n d . 8 4 A d e f i n i t i v e v i b r a t i o n a l 2 n a s s i g n m e n t was p r o p o s e d f o r C:rV04 i n t e r m s o f a s i t e - s y m m e t r y

a n a l y ~ i s . ' ~VV04 mode a s s i g n m e n t s f o r MV04 ( N = I n o r T 1 ) 86 ,87 s u g g e s t t h a t t h e V04 g r o u p s a r e n o t c o m p l e t e l y i s o l a t e d .

1 . r . d a t a f o r 2M0.V205, Cu o r Mn, Ca,

S r a n d Co

states, for

w h e r e M = Mg,

were used t o f i n d t h e V O V

Ca,

angle:

S r , Ba,

Zn,

Cd,

Co,

i t seemed t h a t f o r M =

V O V was l i n e a r i n b o t h c r y s t a l l i n e a n d a m o r p h o u s

f o r M = Cd, C u a n d Mn i t i s l i n e a r i n b o t h s t a t e s ,

M = Mg o r Z n

amorphous s t a t e . "

VOV

i s bent i n the c r y s t a l

V(02);

while

but linear i n the

h a s VV02 b a n d s a t 6 0 0 a n d . E 1 3 O c r n - ~ . ~ ~

VV=O is a t 9 8 0 ~ m - i~n V 0 ( 0 2 ) I D A - ,

w h e r e IDA = C 4 H 5 N O Z - . 9 0

w a v e n u m b e r s w e r e a l s o a s s i g n e d f o r V OAs04. 2H 2 0 ,

vV=O

L i o .5V O A s 0 4 . 2H 2 0 ,

265

Vibrational Spectra of Transition-element Compounds a n d L i V OAs04. 2H 20.

vVX

91 w h e r e Cp3* = C5H4Me,

modes w e r e a s s i g n e d i n Cp:VX2,

C5HMe4 o r C5Me5,

i n [(N2S2)(VC15)2]

12, IBr o r I C L ’ ~

Br2,

Xz-= E l 2 ,

a r e a t 390, 93 vanadium.

for six-coordinate

modes

VV-C1

355 a n d 331cm-l,

as expected

O t h e r vanadium s p e c i e s f o r which v i b r a t i o n a l d a t a were g i v e n are:

M C V 0 ( 0 2 ) 2 i + M 2 S 0 4 ( M = NH4,

V205,g4

KVO(S04)2,

py or substitut,ed pyridine,”

VOL2 ( L

< 5 < 3,

0

a n d vRh-H

vNb-H

< y


~

&

-

&,

29,

.

.

..

24,

129

130 131 132 133 134 135 136 137 138 139 140 141

408,

408,

24,

526,

24,

24,

-

97,

142 143 144 145 146 147 148

520,

526,

15,

.

30,

-

24,

10,

Vibrational Spectra of Transition-element Compounds

285

K.Stah1, F . W e l l e r and K.Dehnicke, Z . a n o r q . a l l q . Chem., 1 9 8 4 , 518, 1 7 5 . 1 5 0 W.W.Beers a n d R.E.McCarley, I n o r q . Chern., 1 9 8 5 , 24, 4 6 8 . 1 5 1 P.A.Agaskar, D.R . D e r r i n g e r , G . L . P o w e l l , F.A.Cotton, D.R.Root and T.J.Smith, Inor Chern., 1985, 24, 2786. 152 D.J.Santure, J.C.Huffman andqA.P.SattelbergeC I n a r q . Chem 1 9 8 5 , 24, 371. 1 5 3 N.V . K h = c h e v n i k o v a and P.N.D'yachkov, K h i m . F i z . ,19R4, 3 , 1507. 15 4 P.M.Boorman, V . D . P a t e l a n d J.F . R i c h a r d s o n , K.J.Moynihan, I n o r g .Chern., 1985, 2989. 155 J.Anhaus, Z.A.Siddiqui, H.W.Roesky a n d J.W.Bats, J . Chem. S O C . , D a l t o n T r a n s . , 1 9 8 5 , 2 4 5 3 . 156 K.Stah1, U . M b l l e r a n d K . D e h n i c k e , Z . a n o r q . a l l q . Chern., 1 9 8 5 .. 5 2-7 .- 7 .A.Berg, H.-D.Gross, U.Mfiller and K.Dehnicke, 1 5 7 T.Gode=er, Z. Naturforsch., T e i l B , 1 9 8 5 , 408, 9 9 9 . 1 58 U.Kynast, W.Willing, U.Ml!~ller a n d K.Dehnicke, Z . a n o r g . a l l g . Chern., 1 9 8 5 , 529, 1 2 9 . 1 5 9 D .G .Garnbarov, A .G . G c s e i n o v a n d A .M.Ayubowa, 1 9 8 5 , 30, 5 1 9 . R u s s . J . I n o r q . Chem., 160 C.Y.Kim and R.A.Condrate, J . P h y s . Chem. S o l i d s , 1 9 8 4 , 1213. 16 1 R . L o z a n o , E . A l a r c o n , J.Pornan a n d A . D o a d r i o , Polyhedron, 1 9 8 4 , 3, 1 0 2 1 . 1 6 2 M.Takami a n d H.Kuze, R e z a K a q a k u K e n k y u , 1 9 8 4 , S , 165 140064). (Chem. Abs., 1985, 1 6 3 E.Hey, F . W e l l e r a n d K . D e h n i c k e , Z . a n o r q . a 1 1 q . Chern., 1 9 8 4 , 514, 18. 164 A.Berg a n d K.Dehnicke, Z . N a t u r f o r s c h . , T e i l 8 , 1 9 8 5 , 408, 842. Z. Naturforsch., T e i l B, 1 6 5 R . K a p o o r , R.Sharrna a n d P . K a p o o r , 1984, 398, 1 7 0 2 . 166 C.Shortman and R.L.Richnrds, J.Orqanometa1. Chem.,1985, 286, c3. 16 7 V .M.Nagiew, 5h.M.Efendiev and V .M.Borlakov, Phys. S t a t . S o l i d i , B , 1984, 467. 1 6 8 A . C l e a r f i e l d , A . M o i n i and P.R.Rudolf, I n o r q . Chern., 1985, 24, a 6 0 6 . 169 CN.Lomova, N.I.Vclkova and B.O.Berezin, R u s s . J. I n o r q . Chern. 1985, 30, 3 5 2 . K . W i e ~ h a r d t a n d J.Weiss, 1 7 0 G .Backes-Oahrnann, W.Herrmann, 1985, 485. I n o r q . Chem., 1 71 M.A.Bennett J . O r q a n o m e t a l . Chem., 1 9 8 5 , 290, a n d I.W.Boyd, 165. 1 7 2 M.Dudek a n d A.Samotus, 271. T r a n s i t i o n M e t . Chem.,1985, 173 S.Vasanthi, K.S.Nagara j a a n d M . R u d o l p h , T r a n s i t i o n N e t . Chern., 1 9 8 4 , 9, 382. 174 J.L.Corbin, K.F . m i l l e r , M . P a r i y a d a t h , S.Wherland, A.E.Bruce, Inorq. C h i m . Acta, 1984, 41. and E.I.Stiefe1, 175 A.C . S k a p s k i a n d R . W . W i g g i n s , J.Flanagan, W.P.Griffith, I n o r q . Chirn. A c t a , 1985, L23. 176 E .N.Duesler, 0 . J.McCabe a n d R .T . P a i n e , S.M.Bowen, I n o r q . Chem., 1 9 8 5 , 24, 1 1 9 1 . 177 C.C.Torardi a n d R.E.McCarley, I n o r q . Chern., 1985, 476. 178 X . X i n , N.L.Morris, G .B. Jarneson a n d M.T .Pope, I n o r g . Chern., 1 9 8 5 , 24, 3 4 8 2 .

149

.

24,

45,

102,

125,

24,

10,

90,

96,

24,

Spectroscopic Properties of Inorganic and Organometallic Compounds

286

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179

,

I

_ I

54,

~

.

s,

24,

2,

g,

527,

103,

284,

97,

287

Vibrational Spectra of Transition-element Compounds 208 209 210 211 212

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.@

G,

24,

1797. 213 214

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Cornrn.,

1484, 29, 1479.

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-

222 223 224 225 226 227 228 229 230 231

I

.

-

289,

117,

1985, 295, 223.

235

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232

J.Elle=nn

1985,

233

520,

.
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147,

*,

107,

.

24,

.

.

61,

.

,

K,

279,

294,

.

11,

.

.

24,

-

9-.

.

90,

289

Vibrational Spectra of Transition-element Compounds 26 8 269 270 27 1 272 27 3 27 4

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521,

18,

102,

156, 3@5.

275 276 27 7 27 8 279 2 80 281 282 2 83 2 84 2 85

2 86 2 87 2 88 2 89 290 291 292 293 294 2 95 296 297 296 299

89,

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115,

15, 90,

-

,

24,

529,

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2.

292,

63,

2 90

Spectroscopic Properties of Inorganic and Organometallic Compounds

300

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30 1 30 2 303 304 305 306 30 7 30 8 309 310 311

312 313 314 315

,

,

5,

102,

113,

.

.

11, ,

103,

316 317 318 319 320 321 322 323

4,

.

.

108,

.

15,

Vibrational Spectra of Some Co-ordinated Ligands BY G. DAVIDSON 1 Carbon,

Silicon,and

T i n Donors

spectrum o f L i ( C H ) h a s been o b t a i n e d i n an A r m a t r i x . 6 7 2 2 L i , C 2 H 2 , C2HD, C 2 D 2 a n d 1 3 C 2 H 2 ) show

The i.r.

Isotopic studies ( Li/

t h a t the structure i s probably planar, n-system.

vCC i s a t 1 6 5 5 c m - l ,

shared e l e c t r o n d e n s i t y between C2H2 n-bac k-bonding.

with t h e L i b r i d g i n g the

b u t t h e d e c r e a s e was a s c r i b e d t o and L i ,

r a t h e r t h a n Li-C2H2

1

V i b r a t i o n a l s p e c t r a w e r e r e p o r t e d f o r MC5H5,

o r K,

a n d t h e Raman s p e c t r a o f L i C 5 H 5 ,

where M = L i ,

Na

NaC5H5 i n THF s o l u t i o n .

F r o m t h e pCH w a v e n u m b e r s i t was s h o w n t h a t t h e p o l a r i t y o f t h e M-C5H5

A

i n c r e a s e d o n g o i n g f r o m t h e s o l i d t o a THF s o l u t i c n .

weak Rarnan b a n d ( 1 3 0 - 1 5 0 ~ r n - ~ f) o r t h e L i a n d Na c o m p o u n d s i n s o l u t i o n was a s s i g n e d t o a n a n i o n t i l t i n g m o t i o n i n a t i g h t

ion

pair M+c~H;.~ The i.r.

s p e c t r a o f CpBeX a n d Cp2Be i n s o l u t i o n w e r e c o m p a r e d .

T h e d a t a f o r Cp B e c a n b e s t b e e x p l a i n e d b y t h e f o r m u l a t i o n 2 ( l ) . 3 ( 2 ) a n d o t h e r c o m p l e x e s w i t h t h i s t i n l i g a n d h a v e vSn-N

i n

the range 3 E 5 - 4 C 5 ~ m - ~ . ~

"0 Be

'SiMe 1 3

cu-0-c

(3 bl

(3c)

//O

Spectroscopic Properties of Inorganic and Organornetallic Compounds

2 92

K O modes f o r C 0 2 / t r a n s i t i o n - m e t a l c o m p l e x e s i n l o w - t e m p e r 2 a t u r e m a t r i c e s s u g g e s t t h a t T i , V a n d Cr c o m p l e x e s h a v e a w i t h a n g l e ca.160°;

side-on structure, structure

(3a),

The disappearance of wavenumbers, of V t o

Fe,

VC=C

and s l i g h t

compared t o t h e f r e e l i g a n d ,

C = C i n Cp2VL, w h e r e L

CH2CHCOCH3.6

Ni give t h e

Co and

(3b o r c ) .

w h i l e cu g i v e s e i t h e r

5

s h i f t o f VC=O t o l o w e r show t h e c o o r d i n a t i o n

CH3CH=CHCH0 o r 2 P h o t o l y s e s o f MCp2H3 (PI = Nb o r T a ) o r I\1Cp2(H)C0 = CH

=CHCHO,

p r o d u c e 1 6 - e l e c t r o n c o m p l e x e s MCp2H a n d ( i n t h e l a t t e r c a s e ) s m a l l a m o u n t s o f NCp2(CO). 7

The r e a c t i o n s were f o l l o w e d by i.r.

spectroscopy.

m e t h y l CH s t r e t c h i n g w a v e n u m b e r s

'Isolated' reported for C-H

5

M(CH02)(r) -C5H5)(C0)3,

bond s t r e n g t h s decrease,

o n d i n g i n c r e a s e i n t h e M-C

(vCHiS)

were

w h e r e M = C r , mo or W .

The

C r > No > W , r e f l e c t i n g a c o r r e s p -

bond s t r e n g t h s . '

VEER i n

(OC) M O C E N - N X R R ' , where R,R' = H , Me, E t e t c . , M = Cr or U, 5 a r e 40-50cm-' h i g h e r t h a n i n t h e f r e e ligand. P t ( I 1 ) analogues give a greater (X

= CH,

AsPh2;

increase.'

E R 2 = PPh2, X = NMe,

donor c a p a c i t y

PMe2,

VCO

E R 2 = AsMe2; G f

(4)

i n t h e y l i d e complexes

P(NMe2l2,

X = S,

AsPh2;

X = C=PPh

E R 2 = AsPh2)

3'

the ylides increases i n the series:

H CAsPh OAsPh Te.73 C a r b o n y l

S > Se

t h e e mode s h o w s t h e r e d u c t i o n i n

The s p l i t t i n g of

V (C0)5PR;

vC0 d e c r e a s e s i n

whpre E = S,

s p e c t r a o f VCp(C0)3EMe2,

s t r e t c h e s i n ( q 5 - i n d e n y l ) V (CO),,

-1

a r e much l o w e r

showing t h e i n c r e a s e d T i - t o -

again showing t h e t r e n d t o increased

t h a t vC0 d e c r e a s e s i n t h e o r d e r

cm

M = T i , Z r or H f ,

i n t h e m i x e d - l i g a n d complexes.

T i > Z r 72 back-bonding.

the series

The i.r.

where

Cp2Ti(C0)2,

Mo o r W ,

i n

give the carbonyl stretching

symmetry i n t h e presence o f l a r g e

Smaller cations lead t o i o n pairing,

with dramatic

301

Vibrational Spectra of Some Co-ordinated Ligands effects

where N = C r ,

complexes, CH3,

pattern^.'^

on t h e VCO

CF3,

E = P,

As,

K O b a n d s f o r f i f t y M(C0)5L

No o r W,

L = R2EE1R

o r R 2 E E R i (R,

R1 =

= 5 , Se o r Te), show t h a t t h e d o n o r /

E'

EMe3 > M e 2 E E ( C F 3 ) 2 , > E(CF3)3.86 C O s t r e t c h e s f o r

acceptor r a t i o decreases as f o l l o w s :

>

Me2EE1CF3

(CF3)2EE'Me

L

less t h a n

C4v

No o r W , 87 unit.

where M = C r ,

M(CO)5(R2PTe),

f o r t h e N(CO),

Absolute i n t e g r a t e d i.r.

vC0,vCS X = 0, CSe

Se,

(NiPr2),

and ( Q ~ - C ~ H , ) C ~ ( C O ) ~ ( C X ) , where

are consistent with t h e

> CS >

acceptor a b i l i t i e s

T h e b r i d g i n g c a r b o n y l s i n CpFeM(CO)6P(H)-

w h e r e M = Cr o r W,

g i v e i.r. bands c l o s e t o l B l O ~ m - ~ . * ~

(Ck13SCEH4S)3]

(NMe,)[No(CO)

wavenumber (1775cm-

),

has a very low carbonyl-st,retching

showing t h a t t h e e l e c t r o n d e n s i t y a t t h e

molybdenum atom must b e v e r y h i g h . " b a n d s due t o K O t

a t 1830cm-I

(No),

( 3 8 ) , w h e r e P = PPh3, 1930cm-1

a t 1 7 7 5 ~ m - ~ . '=~- M 0 ( C 0 ) ~ ( 4 , 4 ' - X ~ - b i p y ) , Me,

= L8u, show a s y m m e t r y

i n t e n s i t i e s i n CS2 s o l u t i o n s f o r

a n d vCSe i n C r ( C O ) , ( C X )

S,

R

C02Me o r N O 2 ,

g i v e s o l u t i o n i.r.

(Ru),

has i.r.

a n d t o vCObr

w h e r e X = OMe,

CMe3,

s p e c t r a showing p r e f e r e n t i a l

i n t e r a c t i o n hetween t h e s o l v e n t and e q u a t o r i a l C O l i g a n d s 92

t r a n s t o t h e 4,4'-X2-bipy.

Me

(391

(381 Semi-bridging

g i v e vC0 b a n d s ( K O ) , w i t h 13C0 e n r i c h m e n t a n d

and b r i d g i . n g c a r b o n y l s i n (39)

1.r.

a t 1B60and energy-factored

force-field

c a l c u l a t i o n s , were used t o f o l l o w

p h o t o c h e m i c a l r e a c t i o n s o f W ( 0 l - C 3H 5 )(TI~-C,H,)(CO), Mn(n1-C3H5)

(CO)3

i n inert-gas

gives the carbonyl-stretching

and

m a t r i c e s a t 12K.94

WBr3(CO)i

bands expected f o r

C3"

symmetry.

A v e r y s i m i l a r p a t t e r n was s e e n f o r W B r 4 ( C 0 ) 8 , i n a g r e e m e n t w i t h t h e observed c r y s t a l structure."

T h e r e was i . r .

f o r t.he f o r m a t i o n o f s t r o n g c o n t a c t i o n p a i r s i n ENaW(CO)5CH2CH2CH2PPh2j 96

.

evidence

3 02

Spectroscopic Properties of Inorganic and Organometallic Compounds where L = py,

E x c i t e d - s t a t e d i s t o r t i o n s o f W(CO)5L, piperidine,

a s u e l l a s M o ~ ( C F ~ C O , ) a~n d K 3 C r ( C N ) 5 N 0 w e r e

c a l c u l a t e d f r o m e m i s s i o n s p e c t r a a n d p r e r e s o n a n c e Raman s p e c t r a , using t h e time-dependent spectra,

t h e o r y o f Raman s p e c t r o s ~ o p y . 1 ~ .~r .

i n the carbonyl-stretching

W(C0)5(alkene),

region,

C O a n d a l k e n e loss o n

t h e p r o c e s s e s of

were used t o f o l l o w

U.V.

irradiation of 98

C3H6 o r 1-C5H10.

where a l k e n e = C 2 H 4 ,

,

P r o t o n a t i o n o f Mn2( p-q2-C 0 ) ( C O ) 4 ( d p p m ) f orms Mn2H(U-n 2 - C O ) ( C 0 ) 4 ( d p p m ) i . T h i s p r o c e s s i s a c c o m p a n i e d b y destabilisation

of

t h e formally

4-electron-donating

s h o w n b y a l a r g e i n c r e a s e i n VCO,

group,

c ~ n - ~ . ' ~ Nn,(CO),(SPh);

p-n2-C0

f r o m 1648 t o 1787

s h o w s t w o t e r m i n a l . VCO o n l y .

t h e SPh g r o u p s t a k e p a r t i n b r i d g i n g .

Thus o n l y

100

1.r. s p e c t r a (CO s t r e t c h e s ) were used t o m o n i t o r p h o t o c h e m i c a l r e a c t i o n s o f a number o f c o m p l e x e s o f t h e t y p e

(OC)5MM'(C0)3(a-di-imine), VCO

bands were seen f o r

local C

-S

= Mn or Re.

w h e r e M,M'

t

Mn,(CO),\P,(

Four

3,

BuN),P,(~BuN)

s y m m e t r y f o r t h e &-Nn(CO)4P2

fragment.

showing

183

L o w - t e m p e r a t u r e F T I R a n d Raman s p e c t r a w e r e r e p o r t e d f o r Re2(CO)10,

t o g e t h e r w i t h 13C0 d a t a .

d e t a i l e d assignments,

combinations f o r t h e f i r s t time. agreement w i t h

T h e s e w e r e u s e d t o make

i n c l u d i n g Raman-active overtones and T h e r e was g e n e r a l l y

good

04,

s e l e c t i o n r u l e s , b u t t h e r e was some e v i d e n c e 104 for s l i g h t d i s t o r t i o n i n solution. T h e p h o t o c h e m i s t r y o f C P M ( C O ) ~ R , w h e r e M = F e o r Ru, Me o r E t ,

i n frozen

s t u d i e d i i s i n g i.r.

R =

g a s m a t r i c e s a n d i n s o l u t i o n s a t -3OOC spectroscopy

.Io5

Carbonyl-stretching

(where M = Fe, R u

were a s s i g n e d f r o m t h e i.r.

s p e c t r a o f M(C0)4L

o r O s , L = E P h 3 ( E = P, As,

Sb),

L = SbMef.

i s o m e r i s m was s h o w n t o o c c u r i n

solution,

Axial/equatorial

R u

> Me; P(OCH2)3CMe > PMe3, PPh3. The t r a n s i e n t

Fe(COl5 i n C 0

> 0s > Fe; 106

M = R u or CIS,

Fe3(C0)12

Sb

> As > P;

species formed from t h e f l a s h p h o t o l y s i s o f

was a s s i g n e d f r o m t h e i . r .

Fe(CO)4(C6D6? . ' 0 7 Fe(C0l4,

P(OCH2)3CMe;

with t h e tendency t o give t h e e q u a t o r i a l isomer

being i n the following series: Pb

PMe3,

was

modes

spectrum as

1.r. s p e c t r a r e v e a l e d t h e p r e s e n c e o f and Fe(C0)

Fe(CO)5 o n z e o l i t e s u r f a c e s . l d 8

(1-pentene)

on t h e p h o t o l y s i s o f

T h e i n t e r a c t i o n o f HFeCo3(C0)12

with oxide supports g i v e s a v a r i e t y o f surface metal carbonyl

Vibrational Spectra of Some Co-ordinated Ligands species,

revealed by t h e i r

The i.r.

-x = 1 - 5 ,

spectra."'

i.r.

T h e r e was F T I R

a f t e r t h e i n t e r a c t i o n of

evidence f o r HFe4(C)(C0)i2 HFe4(CH)(C0)12

303

w i t h p a r t i a l l y dehydroxylated alumina.

110

s p e c t r a o f l 3 C O - e n r i c h e d R U ( ~ ~ C O ) , - ~ ( ~ ~ C O w) h~e,r e

i n l i q u i d xenon were r e p o r t e d and e n e r g y - f a c t o r e d

...

f o r c e constants calculated.'"

vCO were o n l y o b s e r v e d i n t h e

t e r m i n a l r e g i o n f n r t h e a d d u c t s Ru3(~-dppm),(CO),(v-A),

A = Ag02CCF3,

H g ( 0 2 C C F 3 ) 2 o r H02CCF3.

where

Thus t h e r e i s no s h i f t o f

t e r m i n a l t o b r i d g i n g C O on adduct formation."'

Quantitative

R U ~ ( C O )a ~d s~o r b e d o n h y d r a t e d A1203 g a v e 113 evidence f o r t h e presence o f several species.

s t u d i e s of

vC0 f o r

T h e c a r b o n y l s t r e t c h i s a t 1902cm-1 where MIX-DME

i n OS(MIX-DME)(CO)~~,

= mesoporphyrin I X dimethyl ester.

i n t h e Ru a n a l o g u e ,

showing t h a t c & ( O S ~ ~ ) + T ~ ( C O )

This i s lower than i s greater

t h a n f o r Ru1'.l14 Normal (non-enhanced)

Raman s p e c t r a were r e p o r t e d f o r C O

m o l e c u l e s a d s o r b e d o n Co a t room t e m p e r a t u r e . s e v e r a l bands from l i n e a r adsorbed species, chemisorbed species.l15

VCO

2-

T h e r e were and 3 - f o l d

modes f r o m Co a n d Rh c a r b o n y l s

i m m o b i l i s e d o n d e r i v a t i s e d i n o r g a n i c o x i d e s u r f a c e s were s t u d i e d b y Raman,

FTIR and p h o t o - a c o u s t i c

FTIR.

The k i n e t i c s o f

C O s u b s t i t u t i o n h y P(OPh)3 i n R h ( a c a c ) (CO)2 were f o l l o w e d b y i.r.

spectroscopy.

117

C a r b o n y l s t r e t c h e s f o r ~ X H ~ C O ( C O ) ~ Lw ]h~e r, e X = C 1 ,

1 o r 2, order:

>

> P(ONeI3 > P ( O E t ) 3 > E t P ( O E t ) 2 > E t 2 P ( O E t ) > P E t 3 > PnBu3 > E t P ( N E t 2 I 2 > P ( N E t 2 l 3 . The

L = Pt B u 3

Et2P(NEt2)

formulation of modes.

B r , fi =

show t h a t t h e t e n d e n c y t o f o r m d i m e r s d e c r e a s e s i n t h e

( 4 0 ) as shown i s r e v e a l e d b y t h e p a t t e r n o f

119

But

I B \ \ p ' OC\O-OC / C \ \ / C 0co -co

'co [CO,,C,(CO),,]~-

'co

g i v e s t h e same p a t t e r n o f c a r b o n y l

s t r e t c h e s as t h e c o r r e s p o n d i n g t e t r a - a n i o n ,

shifted

E.30cm-'

CO

Spectroscopic Properties of Inorganic and Organometallic Compounds

304

120

t o h i g h e r wavenumber b e c a u s e o f t h e l o w e r n e g a t i v e c h a r g e .

E v i d e n c e was f o u n d f o r a b r i d g e d c a r b o n y l b e t w e e n Rh a n d t h e T i 0 2 s u p p o r t when C O i s a d s o r b e d o n a 0.5% R h / T i 0 2 f i l m . 12’ T h e p r e s e n c e o f vC0 a t v e r y l o w w a v e n u m b e r s a f t e r a d s o r p t i o n o f C O o n R h / S i 0 2 c o n t a i n i n g Mn, T i o r Zr i o n s was e x p l a i n e d b y a m o d e l 122 s u c h a s (41).

vC0 v a l u e s i n R h ( 6 - d i k e t o n e ) ( C O ) L , P(OPle)3,

where L = C O ,

show t h a t i n c r e a s e d e l e c t r o n e g a t i v i t y l e a d s t o i n c r e a s e s i n vC0,

on t h e B - d i k e t o n e

d i c a r b o n y l s p e c i e s . 123

PPh3 o r

for substituents

especially for the

The t r a n s i n f l u e n c e o f n i t r o g e n o u s

b a s e s was e x a m i n e d u s i n g v C O o f t r a n s - R h ( C 0 ) ( P P h 3 I 2 L + , py or s u b s t i t u t e d p y r i d i n e . f o u n d b e t w e e n pKa o f

L

A straight-line

and vC0.124

1.r. d a t a ( c a r b o n y l s t r e t c h e s )

f o r R h ( C 0 ) 2 a c a c and i t s 13C0 a n a l o g u e t h e space group P I o f inwersion.lZ5

(;

(421,

f o l l o w i n g uC0 m o d e s : (remaining Cot), solution,

= 2)

were n o t c o n s i s t e n t w i t h

and i n d i c a t e t h e absence o f a c e n t r e

w h e r e t h e b r i d g i n g l i g a n d i s dpprn,

2032crn-1

1872,

where L =

r e l a t i o n s h i p was

(unique C O

1869cm-1

(CObr).1’6

1,

2000,

has t h e

1998crn-1

K[Rh6(C0)14],

i n

has c a r b o n y l s t r e t c h e s i n b o t h t h e t e r m i n a l and

bridging regions c o b a l t analogue.

and appears t o be i s o s t r u c t u r a l w i t h t h e 127

There a r e t w o t y p e s o f C O adsorbed on a n i c k e l c a t a l y s t , l i n e a r ( V C O 2 0 6 0 ~ m - ~ a) n d o n e b r i d g e d ( 1 9 6 0 c m - I ) .12*

one

1.r. s p e c t r a

305

Vibrational Spectra of Some Co-ordinated Ligands were r e p o r t e d f o r C O and

N O adsorbed on p o l y c r y s t a l l i n e N i O

samples.

T h e r e was e v i d e n c e f o r d i p o l e / d i p o l e a n d c h e m i c a l 129 e f f e c t s o n t h e wavenumbers.

C O a d s o r p t i o n o n 5% Pd/A1203 was f o l l o w e d b y i . r . (vC0).

spectroscopy

B a n d s s h i f t e d t o h i g h e r wavenumber o n i n c r e a s e d c o v e r a g e

and on r e d u c t i o n o f t h e s u r f a c e b y hydrogen.130

cis-M(C6X5)2(C0)2, for the first

time.

w h e r e M = Pd o r P t ,

The c a r b o n y l s t r e t c h e s

( 2 1 8 6 ~ m - f~o r Pd,

wavenumbers

n e g l i g i b l e M-CO

X =

ba~k-bonding.’~’

F)

The complexes

X = F or C1,

were i s o l a t e d

a t very high

show t h a t t h e r e i s

S e v e r a l l i n e a r l y b o u n d Pt-C 0

u n i t s w e r e d e t e c t e d f o r C O a d s o r b e d a t 85K o n a s t e p. p. e d P t surface.132

Br,

The v i b r a t i o n a l s p e c t r a o f Pt(C0)2X2,

a r e c o n s i s t e n t w i t h a p L a n a r &c

crystalline state

where X = C 1 o r

c o n f i g u r a t i o n in t h e

b u t a t e t r a h e d r a l f o r m i n t h e gas phase o r i n 133

hydrocarbon s o l u t i o n s . Linear,

b r i d g e d and p h y s i s o r b e d C O m o l e c u l e s a l l gave c h a r a c t -

e r i s t i c C O s t r e t c h e s f o r C O on C u ( l l 1 ) r a n g e 7-77K.134

i n the

temperature

C O c h e m i s o r p t i o n o n r e d u c e d C u/ZnO c a t a l y s t s

g i v e s an i.r.

b a n d a t 1 5 8 0 ~ r n - ~a s s i g n e d t o K O f o r a n u n u s u a l

four-electron

donor c a r b o n y l s p e c i e s

evidence f o r two d i f f e r e n t C u I - C D complex f r o m t h e i.r. catalysts.136

(44),

There i s a l s o

s ~ e c t r ao f C O a d s o r b e d o n C u / Z n o x i d e A

where N

due t o a b r i d g i n g Cu’

( 4 3 ) .135

c o m p l e x e s a n d a Cu1’-C0

N = PhCH=NCH CH N=CHPh,

c a r b o n y l a t 1958cm-

3 .157

g i v e s vCO

0 (bb) P h y s i s o r b e d C O o n S i 0 2 s u r f a c e s c o n t a i n i n g i s o l a t e d OH g r o u p s g i v e vC0 a t 2 1 5 8 a n d 2140cm-1.138

Spectroscopic Properties of Inorganic and Organometallic Compounds

306 3 (45)

Boron-containinq

Donors

i s f o r r n u l a t E d a s shown s i n c e i.r.

u n i d e n t a t e HBH;

bands c h a r a c t e r i s t i c

FeH (H2BH2){CH3C ( C H 2 P P h 2 ) 3 f

w e r e seen.139

of

gives

t h e expected f e a t u r e s f o r a b i d e n t a t e tetrahydroborate 140 ligand.

0

"\

I

P

Me-

(461

(45)

Rh(Me B N M e 3 ) ( L L 1 ) + , where L L ' = d i o l e f i n s o r (C2H412, 3 3 3 h a v e vBN o f t h e c o o r d i n a t e d h e x a m e t h y l b o r a z i n e a t 1 3 7 0 - 1 4 0 0 ~ r n - ~ , compared t o t h e f r e e 2322crn-I,

l i g a n d a t 1407cm-1.141

VBHNi a t 1 8 9 5 c m - 1

(46) h a s v B H t a t

and N O a t 1933,

1909crn-'.

Bands

b e l o w 1 7 0 0 ~ r n - a~r e v e . r y s i r n i l - a r t o t h o s e i n t h e Z n I I a n d C u I The i . r . s p e c t r u m o f ( P h P ) C u B 5 H 8 o n l y h a s VBH 3 2 a b o v e 2 4 0 0 ~ m - ~ T. h u s t h e r e i s n o f e a t u r e w h i c h c a n b e a s s i g n e d 143 t o t h e b e n t CU-H-B b r i d g e . analogues.142

4 4.1

N i t r o q e n Donors

Molecular Nitroqen,

azido,

and r e l a t e d complexes.-

Trans-

C r ( N 2 ) 2 ( d r n p e ) 2 h a s o n l y o n e vN2 b a n d i n s o l u t i o n i n t h e i . r . spectrum (1932crn-l)

cis i s o m e r

-'.

The crn

144

a n d one

ir!

t h e Raman s p e c t r u m ( 2 0 0 1 ~ m - ~ ) .

h a s t w o v N ~b a n d s i n t h e i . r . ,

Mo 0 ( O M e ) 2 ( N N P h ) i -

a t 1920 a n d 1895

h a s i.r. ,bands a t 1631,

a n d 1 5 2 2 c r n - 1 4 c ~ a r a c t e r i s t i c o f vNN f a r a c i s - d i a z e n i d o M c J ( N N P ~ ) ~ +C. p~M~o (~P P h 3 ) ( N 2C 6H 4M e - e ) have two i.r.

1616, 1 5 7 4 unit i n

and r e l a t e d s p e c i e s a l l

b a n d s i n t h e r a n g e 1 6 2 0 - 1 5 5 0 ~ r n - ~ ,d u e t o t h e

a r e n e - r i n g c o u p l e d NN s t r e t c h o f a s i n g l y b e n t a r e n e d i a z o l i g a n d . 14'

MoCl5(NSCl)-

V S C l E.500cm-1,

vasMoNS

gives t h e f o l l o w i n g i.r. 945crn-l,

vsMoNS 438crn-1

features: a n d 6asNSC 1

3 8 ~ c m - ~ , ~ ~ ~ &-W(N

vNN,

at

) (Ph2PCH2PPh ) g i v e s t w o s t r o n g i . r . b a n d s d u e t o 2 2 -12 Trans-W(N2)2(Ph2PCH=CHPPh2)2 has 1 9 3 5 a n d 2000crn

.

Vibrational Spectra of Some Co-ordinated Ligands o n e s t r o n g wN2 b a n d crn’1.148 1980

,

307

a t 1 9 6 5 ~ m - ~w, i t h a weak f e a t u r e a t 2022

) ( P M e 3 l 4 h a s t w o NN s t r e t c h e s , a t 2 2 a n d 1 9 2 0 ~ r n - i~n t h e i . r . , a n d W(N2)(PPle,), h a s one, a t Similarly,

*-W(N

1 9 0 S c m - ~ .C~h ~a r~a c t e r i s t i c l i g a n d modes w e r e a s s i g n e d f o r

(471,

i n c l u d i n g t h o s e f o r t h e b r i d g i n g N2S2 u n i t a t 8 4 0 a n d 8 2 5 cm-l. 150

TC(PR~)~(CO)~(A~N-N’NA~)

( w h e r e R 3 = Me2Ph, A r = e-MeC6H4 A r = E-MeC H 1 g i v e a n i . r . b a n d n e a r 6 4 1 2 6 0 ~ r n - c~h a r a c t e r i s t i c o f a c h e l a t i n g t r i a z e n i d o l i g a n d . 1 5 1

o r p-ClC6H4;

R 3 = Ph3,

vNN a n d vCN w e r e s e e n i n t h e r a n g e s 2 0 1 0 - 2 0 3 0 ~ m - ~ ,2 0 7 4 - 2 1 2 0 ~ m - ~ r e s p e c t i v e l y f o r mer-ReC1(N2)(CNR)[P(OMe)333, tBu o r C6H4Me-4,

where R

and c i s - R e C 1 ( N 2 ) ( C N N e ) ( P P h 3 ) [ P ( O E t ) 3 ~ 2 .

= Me, E t , The

l o w e s t v a l u e s w e r e f o u n d f o r t h e l a s t , w h e r e PPh3 f a v o u r s e l e c t r o n r e l e a s e f r o m R e t o t h e N 2 o r CNR I T - a c c e p t o r s . 1 5 2 R eC l2 ( PPh3)

(NNHC OPh ) ( NH NHC OPh ) h a s UNH 3 1 5 0 - 3 2 3 0 ~ m - ~ ,VNN

1 5 4 0 - 1 6 0 0 c r n - ~ . ~ v~S~C l o f t h e N S C l l i g a n d i s a t 4 5 0 ~ m - i~n t h e i . r . s p e c t r u m o f ReC14(NSC1);. 154 A d s o r b e d N2 o n M - A 1 2 0 3 - K , b a n d s a t 2095,

2157cm-1

1 5 N s u b s t i t u t i o n . 155

2180cma1, v 1 4 d 5 N

(481

w h e r e M = F e or Ru,

( F e ) , 2050,

Matrix i.r.

2169cm-1

spectra o f

a t 2107cm-1.156

(49)

(Ru),

g i v e s i.r. confirmed by

( 4 8 ) show v 1 4 N 2 a t

3 08

Spectroscopic Properties of Inorganic and Organometallic Compounds where pap = 2 - p h e n y l a z o p y r i d -

vN=N i n c c l r n p l e x e s s u c h a s ( 4 9 ) , ine,

a r e a t 1 3 1 5 ~ m - ~ c, o m p a r e d w i t h 1425cm-1

d(Ru)+1~36( p a p ) b a c k - b o n d i n g

i n f r e e pap.

i s significant.157

N S C l l i g a n d modes i n R U ( N S C ~ ) ~ C ~ X ( P Pw~h e~r e) ~ X, = C 1 , CN o r NCS,

shows*-coordination

O S C ~ ( C O D ) ( N ~ H ~Os(COD)(N )~, H

D i f f e r e n c e s between i.r.

c h a i n m o d e l of

Kt

salt,

and OsC1(COD)(NH2NMe2)i

,

characteristic

a n d Rarnan w a v e n u m b e r s of

X = C1,

c o o r d i n a t e d b y t r a n s X,2 161 N f r o m d i f f e r e n t L.

B r or

v

i n

T h e MLX2 c o m p l e x e s ,

I, L =

H NN=CMeCMe=NNH2, 2 s t r u c t u r e , w i t h each M

i m i n o N f r o m t h e same L

T r i a z e n i d o l i g a n d modes i n Cp2MY2,

N,N'-di-e-tolyl-triazenide,

of

were i n t e r p r e t e d i n t e r m s o f a l i n e a r

spectra showing a polymeric

i.r.

41

coupled anion o s c i l l a t o r s

w h e r e M = Co o r N i ,

Br, 158

o f t h e two NSCl ligands.

a l l h a v e vNN i n t h e r a n g e 9 2 0 - 9 4 0 c m 159 unidentate hydrazino ligands. C O ( C N ) ~ N ~ - a, s t h e

Hence

Splitting of the

have

and t w o amino

where N = U o r Th,

Y

=

show t h e u n i d e n t a t e c o o r d i n a t i o n

162

o f Y. 4.2

Amines a n d r e l a t e d 1 i g a n d s . -

'BU

o r Ph,

E. 3 3 0 0 ~ m - VNH ~( ),

ligands at (vCN)

CpTiC12(NHR),

where R

= Et,

iPr,

g i v e bands i n t h e i.r. Some l i g a n d - m o d e

s p e c t r a due t o t h e a m i d o t 1 190cm-1 (R = 8 u ) , 1235cm-1 ( P h )

a s s i g n m e n t s w e r e g i v e n f r o m t h e i. r . 2t e.g. vNH a t 3 2 7 5 , 3 2 2 0 a n d

,

spectra o f trans-Cr(NH3)4(H20)C1

3 1 4 5 ~ m - ~ . ~ ~ ~ ai dds oi rnb eed o n t o p o r o u s W y c o r g l a s s w i t h physisorbed W(CO)5,

f r o m p h o t o l y s i s o f W (CO)6,

forms adsorbed

w i t h r e s o n a n c e Rsman b a n d s d u e t o t h e p y l i g a n d a t

W(CO)5py,

1012 and 1 0 4 2 ~ m - ~

vNH 3325cm-'

modes w e r e a s s i g n e d i n C p M n ( C 0 ) 2 ( a n i l i n e ) ,

at

and 3 2 8 0 ~ m - ~ a , nd i n a s e r i e s o f complexes w i t h

substituted aniline derivatives.

Oxidation t o phenylaminyl

c o m p l e x e s l e a d s t o a n i n c r e a s e i n VNH,

t o about 3 3 4 0 ~ m - ~ . l ~ ~

T h e r e s o n a n c e Raman s p e c t r a o f s i n g l y r e d u c e d F e ( b i p y ) i shows t h a t

i t c o n t a i n s t w o d i s t i n c t chromophores.167

H 2 R ~ 3 ( N H ) ( C O ) Sh a s vNH HRu

(NH2)(CO)10

cm-'

f o r 15N),

a n d 3311cm-1

VNH

a t 3362cm-1

a n d i n H R u (NH (3358,

(3353cm-1

b a n d s a r e a t 3405,

3304cm

s p e c t r u m o f Ru(bipy);+

f:r

)(CO)

f o r 15NO);

3345crn-1 vNH

15N$?168

(3396,

i n 3338

b a n d s a r e a t 3367 T h e r e s o n a n c e Raman

a d s o r b e d o n p o r o u s Wycor g l a s s shows t h a t

t h e ground s t a t e i s s i m i l a r t o t h a t i n aqueous s o l u t i o n

but that

t h e e l e c t r o n i c e x c i t e d s t a t e o f t h e adsorbed complex i s v e r y

309

Vibrational Spectra of Some Co-ordinated Ligands different transfer

from t h a t

i n aqueous solution.169

M u l t i p l e charge-

e x c i t e d s t a t e s o f tris-(2,2'-bipyrimidine)ruthenium(II)

w e r e c h a r a c t e r i s e d b y r e s o n a n c e Raman s p e c t r o s c o p y ,

R ulI1

.

( b p y m - ) 2t 17'

(bpym)

ground and l o w - l y i n g ine)2t

T h e r e s o n a n c e Raman s p e c t r a o f

excited states of R~(NH~)~(4-acetylpyrid-

suggest t h a t t h e charge-transfer

photo-active

e.g.

l i g a n d f i e l d excit.ed s t a t e ,

s t a t e l i e s below t h e compared t o t h e o p p o s i t e

order i n t h e p y r i d i n e a n a 1 0 g u e . l ~T ~h e r e s o n a n c e Rarnan s p e c t r a o f a q u e o u s R ~ ( b i p y ) 4~- a( c e t y l p y r i d i n e ) ; ' modes f o r

both ligands,

gave o n l y

ground-state

d u e t o t h e s h o r t l i f e t i m e o f t h e MLCT

s t a t e . 17* D e t a i l e d a s s i g n m e n t s o f l i g a n d modes w e r e g i v e n u s i n g

) L2', 5i73 pyrazine etc.

SERS f o r R u ( N H py,

I.r.,

O S ( N H ~ ) ~ La~n 'd O S ( N H ~ ) ~ L ~ ' w, h e r e L =

Raman a n d i n c o h e r e n t

s p e c t r a show s t r o n g i n t e r i o n i c a

lq

modes i n [ C o ( N H 3 ) 6 1 L M F 6 1 ,

spectra of

ML(H20)*,

that the L

is

i n e l a s t i c neutron scattering v i b r a t i o n a l c o u p l i n g hetween w h e r e M = F e or A 1 . 1 7 4

The i.r.

=

(50),.show

w h e r e M = Co,

N i o r Cu,

H 1

2 -

c o o r d i n a t e d v i a t h e p y r i - d i n e N a n d t h e a r n i d o N.

I n t e r a c t i o n s b e t w e e n Cu(NH3)Zt

and z e o l i t e Y can be

i n v e s t i g a t e d b y e x a m i n i n g Raman s p e c t r a i n b o t h t h e vNH r e g i o n s . 17'

A

s t r u c t u r e of

2,2'-bipyridine

175

a n d VCUN

s u r f a c e - e n h a n c e d Raman s c a t t e r i n g s t u d y o n t h e adsorbed on a s i l v e r e l e c t r o d e

showed a t l e a s t 4 k i n d s o f b i p y m o l e c u l e a t t h e s u r f a c e . I t 177 o f t h e s e g a v e S E R S v e r y s i m i l a r t o Ag ( b i p y I 2 . T h e r e i s m a t r i x i.r.

One

e v i d e n c e f o r t h e f o r m a t i o n o f 1:l a d d u c t s

between SiF4 o r GeF4 and p y r i d i n e . o f p y r i d i n e modes was s e e n , 1 78 t h e complexes.

Characteristic

perturbation

suggesting strong i n t e r a c t i o n i n

Spectroscopic Properties of Inorganic and Organometallic Compounds

310 4.3

L i g a n d s containinq>C=N'

a t 1 7 0 0 ~ m - ~ i,. e .

h i g h e r t h a n i n a z o m e t h i n e , HN=CHMe.

58cm-1

where M = C r o r W ,

(Sl), cm"

C p 2 Z r ( N = C H M e ) C 1 h a s vC=N

qroups.-

h a v e VNH a t 3280crn-1

M n o r Fe,

substrate/sarnple/Ag, dimers.181

a n d vC=N a t 1 5 7 2

SERS f o r M1'(TPP)C1,

f r o m t h e benzophenoneimine l i g a n d .

where M = C r ,

179

i n t h e l a y e r e d system CaF2/roughened

show t h a t t h e y a r e c o n v e r t e d t o u - 0 x 0

A n u m b e r o f l i g a n d modes w e r e o b s e r v e d a n d a s s i g n e d i n where M = C r o r Mn,

(TTP)MN,

t h e r e s o n a n c e Raman s p e c t r a o f

TTP =

wC aCm a n d VC 6C 6

tetra-e-tolylporphyrinato. The high-wavenumber

modes a r e l o w e r i n t h e C r t h a n i n t h e M n c o m p l e x ,

due t o weaken-

i n g of

r i n g bonds caused by severe d i s t o r t i o n o f t h e 182 macrocycle.

Pro

I

(511 The i . r .

(521

,

s p e c t r a o f C14M[iPrNC(Cl)NiPrl

show t h a t t h e C - C 1

w h e r e M = Mo o r R e ,

amidino l i g a n d i s coordinated as a symmetrical

chelate

( ~ 2 1 . l ' ~R e s o n a n c e Raman e x c i t a t i o n p r o f i l e s f o r

W(CO)4L,

w h e r e L = R-N=CH-CH=N-R

etc.,

were c o r r e l a t e d w i t h

e m i s s i o n s p e c t r a f o r t h e complexes.184 substituted phenyl derivatives,

(EC )5W(N=CHPh),

and

have~N=Co f t h e irnine l i g a n d s

i n t h e r a n g e 1 6 0 5 - 1 6 4 0 ~ m - ~ ,d e p e n d e n t o n t h e e l e c t r o n - d o n a t i n g capacities o f t h e phenyl substituent.

h a v e VC=N,

e x p e c t e d M-N

F e , Co o r Zn, H P = 1 , 2 - h e n z o q u i n o n e 2 a n d vOH b a n d s c o n s i s t e n t w i t h t h e

= Mn,

N(HQ)2, where M I 1 dioxirne,

VN-0

coordination.lB6

Re'NPc

g i v e l i g a n d i . r . b a n d s a t 727cm-1

(6CH o f t h e 1 , 2 - d i s u b s t i t u t e d o f benzene r i n g ) .

185

,

w h e r e Pc = p h t h a l o c y a n i n a t o ,

(yCH),

1070,

benzene r i n g ) ,

1127,

1169cm-1

a n d 1 5 0 3 ~ m - (~ vCC

107

Good agreement

was

found

b e t w e e n o b s e r v e d (Rarran)

c a l c u l a t e d wavenumbers f o r t h e i n - p l a n e i r o n phthalocyanine.

and

v i b r a t i o n a l modes o f

V e r y e x t e n s i v e c o u p l i n g h e t w e e n l i g a n d modes

was i n d i c a t e d , a n d h e n c e t h e r e i s n o j u s t i f i c a t i o n f o r a s s i g n m e n t s o f s p e c i f i c w a v e n u m b e r s t o s i n g l e i n t e r n a l c o o r d i n a t e s . 188

1.r. a n d r e s o n a n c e Rarnan s p e c t r a w e r e r e c o r d e d f o r 20 F e ( T P P ) L L ' complexes t o e s t a b l i s h s t r u c t u r e - s e n s i t i v e

bands.

I n t h e i.r.

311

Vibrational Spectra of Some Co-ordinated Ligands s p e c t r a b a n d I ( 1 3 3 0 - 1 3 5 0 ~ m - ~ )a n d b a n d I11 ( 4 3 2 - 4 6 9 c m - l ) spin-state sensitive, state sensitive. 1545cm-l,

w h i l e band I 1 (790-806cm-l)

bands C

I n t h e r e s o n a n c e Raman s p e c t r a ,

anomalous p o l a r i s a t i o n )

spin-state sensitive,

are

i s oxidation(1498-

and D ( 1 5 4 0 - 1 5 6 5 ~ m - ~ ,p o l . ) a r e

w h i l e band E (376-391cm-l, 189

pol.)

i s

s e n s i t i v e t o s p i n and o x i d a t i o n s t a t e s . R e s o n a n c e Raman d a t a f o r F e ( T P P ) formulation for

support a

d7

Fe(1)

t h e co mp le x b o t h a t r o o m and l o w t e m p e r a t u r e s .

190

Some l i g a n d - m o d e a s s i g n m e n t s were p r o p o s e d f o r ( P ) F e ( R ) , w h e r e R = Ph, C F H , C6F5, P = OEP, TPP, (m-Me)TPP o r (e-Me)TPP. 1 9 1 6 4 W e l l r e s o l v e d Raman s p e c t r a were o b t a i n e d f o r F e a n d Co t e t r a s u l p h o n a t e d p h t h a l o c y a n i n e s a d so rb e d on s i l v e r e l e c t r o d e s , g i v i n g some t e n t a t i v e b a n d a s s i g n m e n t s . 1 9 2

The e l e c t r o c h e m i c a l

reduction o f i r o n ( I I 1 ) tetrakis-(N-methyl-4-pyridiniumyl)porphine, Fe'''(TMPyP),

was f o l l o w e d b y r e s o n a n c e Raman s p e c t r o s c o p y .

The

r e d u c t i o n was shown t o p r o c e e d i n a h i g h - s p i n s t a t e a t b o t h h i g h

S E R S was u s e d t o m o n i t o r t h e r e d u c t i o n a n d l o w pH v a l u e s . lg3 o f iron(II1)

p r o t o p o r p h y r i n a t a s i l v e r e l e c t r o d e . The enhancement

p a t t e r n was s i m i l a r t o n o r m a l r e s o n a n c e Raman s p e c t r a , i . e .

the

molecular e l e c t r o n i c s t a t e s are not a l t e r e d by i n t e r a c t i o n w i t h 194 t h e surface. R e s o n a n c e Raman s p e c t r a a t c r y o g e n i c t e m p e r a t u r e s of p h o t o d i s s o c i a t e d h a e r n o g l o b i n s show s i g n i f i c a n t d i f f e r e n c e s i n p e r i p h e r a l haem s u b s t i t u e n t modes a n d t h e i r o n - h i s t i d i n e s t r e t c h , compared t o t h e c o r r e s p o n d i n g d e o xyg e n a te d f o r m s .

The d i f f e r e n c e s

r e f l e c t d i f f e r e n c e s i n t h e t e r n a r y s t r u c t u r e o f t h e haem p o c k e t bet w een deox yh a e mo g lo b in and t h e LO-bound f or m .

195

M e a s u r e m e n t s w e r e made o f d e p o l a r i s a t i o n r a t i o d i s p e r s i o n c u r v e s and e x c i t a t i o n p r o f i l e s f o r t h e 1375,

1583 a n d 1663crn-1 b a n d s o f

oxyhaernoglobin. These gave d e t a i l e d i n f o r m a t i o n on t h e a c t u a l s y m m e t r y o f t h e haem g r o u p . lg6 D i f f e r e n c e s i n t e r n a r y and q u a t e r n a r y s t r u c t u r e s o f f 1u o r o m e t h y l h a e m o g l ob i n d e r i v a t i v e s w e r e p r o b e d b y r e s o n a n c e Raman s p e c t r a e x c i t e d i n t h e 197 region.

U.V.

T h e Raman s p e c t r a o f h a e m a t o p o r p h y r i n d e r i v a t i v e s ( 5 7 0 - 1 6 4 0

ern-')

i n different

s o l v e n t s w e r e shown t o b e v e r y s o l v e n t

d e p e n d e n t .lg8 Raman s p e c t r a o f o x i d a t i o n b a n d s o f s p e r m - w h a l e m y o g l o b i n (Mb) deoxylvlb,

FeI'INb-CN)

pH v a l u e s a b o v e 6.5 pH,

and s p i n - s t a t e

derivatives

were r e c o r d e d a t d i f f e r e n t

marker

(oxyMb, pH v a l u e s .

A t a l l

t h e d e p o l a r i s a t i o n r a t i o s a r e independent o f

c o n s i s t e n t w i t h t h e l a c k o f a s a l t b r i d g e between His(HC3)B

Spectroscopic Properties of Inorganic and Organometailic Compounds

312 a n d Asp(FG5)B

( w h e r e Asp = a s p a r t a t e ) .

199

R e s o n a n c e Raman s p e c t r a o f h o r s e r a d i s h p e r o x i d a s e c o m p o u n d f r e e of

I

p h o t o r e d u c t i o n a r t i f a c t s show c h a n g e s i n c h a r a c t e r i s t i c r e v e a l i n g l o s s o f an e l e c t r o n from t h e a

p o r p h y r i n modes, n-orbital

of

the porphyrin ring,

2u

i n c o m p a r i s o n w i t h c o m p o u n d 11.

T h e r e s o n a n c e Raman s p e c t r a o f i r o n c h l o r i n c o m p l e x e s

f o r t h e p r o s t h e t i c groups o f green haem-proteins),

200

(models

e.g.

Fe'''(DC),

where OC = d e u t e r i o c h l o r i n I X d i m e t h y l e s t e r , showed e f f e c t i v e s y m m e t r y o f a b o u t C 2 , c o m p a r e d t o Fhh f o r m e t a l l o p o r p h y r i n s . 201 R e s o n a n c e Raman s p e c t r a w e r e u s e d t o s t u d y h a e m - g r o u p

structure

i n i n t e r m e d i a t e s d e r i v e d f r o m haem-enzyme h o r s e r a d i s h

peroxidases.

202

A s s i g n m e n t s w e r e made o f

o x i d a t i o n and s p i n - s t a t e marker bands

i n t h e r e s o n a n c e Rarnar! s p e c t r a o f c y t o c h r o m e o x i d a s e i n t h e 20 3 r e s t i n g , r e d u c e d , pu3 s e d a n d o x y g e n a t e d f o r m s . Time-resolved the reduction of cxidase.

r e s o n a n c e Raman s p e c t r o s c o p y

O2

by both mixed-valence

was u s e d t o s t u d y

and reduced cytochrome

A p h o t o l a b i l e i n t e r m e d i a t e was d e t e c t e d w i t h w a v e n u m b e r s

characteristic

o f o x y g e n a t e d haem was d e t e c t e d . 2 0 4

Similar

e x p e r i m e n t s made i t p o s s i b l e t o m o n i t o r t h e s t r u c t u r e o f t h e haem group f o l l o w i n g

p h o t o l y s i s o f t h e C O complexes o f haemoglobin,

n y o g l o b i n and oxy-haemoglobin. w a v e n u m b e r s a b o v e 1450cm-1

F o r HbCO t h e p o r p h y r i n s k e l e t a l

(sensitive t o core size)

t h a n t h o s e o f deoxyHb w i t h i n 30ps o f p h o t o l y s i s ,

are lower

and c h a r a c t e r -

i s t i c o f a h i g h - s p i n F e I I haern c o m p l e x c o n t a i n i n g a p a i r o f weak-field

a x i a l l i g a n d s . 2 0 5 Nanosecond t r a n s i e n t

s p e c t r a w e r e r e p o r t e d f o r t h e Fe"-CO products o f horseradish peroxidase.

and F e I I I - N O

r e s o n a n c e Raman photolysis

206

T r a n s i e n t Raman s p e c t r a o f p h o t o l y s e d c a r b o x y h a e m o g l o b i n s (CoHbA,

CoHbA(Zurich))

show t h a t t h e b e h a v i o u r a n d g e o m e t r y of

t h e p r o x i m a l s i d e o f t h e haem a r e v e r y n e a r l y t h e same i n e a c h case. ' 0 7

Characteristic

for a transient

l i g a n d modes g a v e r e s o n a n c e Raman b z n d s

intermediate during t h e alkaline isomerisation

r e a c t i o n o f f e r r i c y t o c h r o m e ;.208

The f i r s t

picosecond,

time-

r e s o l v e d r e s o n a n c e Raman s p e c t r u m h a s b e e n r e p o r t e d f o r photolytic

transients

o f myoglobin. These were used t o d i s c u s s 209

some a s p e c t s o f l i g a n d d y n a m i c s .

assignments i n Ni(LH)2, where H L = 1 , 2 - h y d r o x y l 7 a r e c o n s i s t e n t w i t h t h e presence o f an N i N 4 210 planar chelate unit. Ligand-mode

amino-oximes,

Vibrational Spectra of Some Co-ordinated Ligands

313

1.r. a n d r e s o n a n c e Raman s p e c t r a w e r e r e p o r t e d f o r N i ( 2 - F O P ) w h e r e FOP = f o r m y l d e u t e r i o p o r p h y r i n

and Ni(4-FDP), ester.

A l l i n - p l a n e a n d many o u t - o f - p l a n e

I X dimethyl

p o r p h y r i n modes

and

i n t e r n a l C H O modes w e r e a s s i g n e d . F o r m y l s u b s t i t u t i o n a t t h e 2 and 4 - p o s i t i o n s similar

gave v e r y s i m i l a r s p e c t r a ;

perturbations of the electronic 211

hence t h e r e a r e v e r y

structure of the

macrocycle.

L i g a n d modes w e r e a s s i g n e d f o r t h e s y m m e t r i c c h e l a t i n g

( C 1 )CNiPr]

.212

carbodi-imide

c o m p l e x C 1 4 P [iPrNC

4.4

Isocyanides, and r e l a t e d 1 i q a n d s . -

Cyanides,

( 2 , 6 - ~ y l p l i s o c y a n i d e ) h a s VCN a t 1 9 6 5 c m - 1 n-back-donation

1.r.

t o t h e isocyanide ligand.

spectroscopy

(77-293K)

a n d Cr(CN)5(H20)2-.214

presented for calculation.

(OC)5CrCNCOPh,

;13

was u s e d t o s t u d y t h e r e a c t i v e

species i n p o l y v i n y l alcohol films. Cr(CN)g-

Cp2V (n1-C3H5)-

showing s u b s t a n t i a l

Thus C r ( C N ) i -

goes t o

F u l l i n f r a r e d a n d Raman d a t a w e r e together w i t h a force-field

T h e r e s u l t s show t h a t t h e b e n z o y l i s o c y a n i d e l i g a n d

i s similar t o CO i n i t s interaction with Cr. electron delocalisation i n the

There i s extensive

C:N-C=O

The f o l l o w i n g

C E N s t r e t c h i n g a s s i g n m e n t s w e r e r e p o r t e d f o r K 8 1 M o 5 (CN)123.4H20:

2093cm-l(t2), (e).216

uCN

Mn(CNR)z+,

2 1 0 0 ~ m - (al), ~

2112cm-1

(t,)

a n d tlu) w e r e a s s i g n e d f o r M n ( C N R ) i a n d (alg, e 9 w h e r e R = v a r i o u s a l k y l a n d a r y l g r o u p s . T h e wave-

n u m b e r s w e r e g e n e r a l l y h i g h e r f o r Mn" Re(SR)3(NCR')2,

e x p e c t e d . 217 s i n g l e VCN i.r.

band,

,

= Me o r t 8 u ,

and r e l a t e d l i g a n d s ,

as

HSR = give a

T h e i.r. CMe3,

CgHll,

218

((==JqN'

s p e c t r u m o f t h e new b i n u c l e a r i r o n c o m p l e x

c o n t a i n s a band due t o v C N ( b r i d g i n g ) R = CHMe2,

I

c o n s i s t e n t w i t h trans-(NCR ' ) 2 l i g a n d s .

(NC), Fe-NC-Fe(CN)4

The i.r.

t h a n f o r Mn

where R '

2,4,6-tri-iso-propylbenzenethiol

Z055cm-1.219

4 k1 a n d 2122cm

(53)

a t 2115~rn-~w , i t h vCNt

s p e c t r a of M ( C N R ) i + ,

at

w h e r e M = R u o r Os,

a l l g i v e YCN a s a v e r y s t r o n g b a n d n e a r

2 2 0 0 ~ m - (tlu ~ mode); t h e p r e s e n c e o f a v e r y i . r . f e a t u r e n e a r 2 0 3 5 c m - I was e x p l a i n e d b y s l i g h t n o n - l i n e a r i t y 220 units.

o f t h e M-C EN-C

Spectroscopic Properties of Inorganic and Organometallic Compounds

3 14

D e t a i l e d assignments o f w h e r e M = Rh o r I r

C E N s t r e t c h i n g ttiavenumbers f o r

Table 1 M

C N h a v e b e e n p r o p o s e d f o r MH

5'

( T a b l e 1).221T h e c o m p l e x e s R h ( L ) ( C O ) ( P P h 3 ) 2 ,

=

al bl e

w h e r e L = CH2=CHCN,

Rh

Ir

2147

215 2

2 12 7

2125

2119

2117

CH2=CMeCN,

cis- a n d

MH (CN);

(/cm-')

trans-MeCH=CHCN

or

C H =CHCH C N , a l l g i v e i n c r e a s e d vCN, b u t a l m o s t u n s h i f t e d vC=C 2 2 compared t o t h e f r e e l i g a n d s . Thus c o o r d i n a t i o n has o c c u r r e d v i a

N and n o t t h e r - s y s t e m o f t h e o l e f i n i c g r o u p i n L.222 same c o n c l u s i o n was r e a c h e d f r o m t h e i . r . IrH2(L)(CO)(PPh )+ C H 2=CHCH 2C N 2 2 z 3 2 '

.

(54) vCObr

h a s vCN

where L =

cis- o r

a t 2 1 0 5 ~ m - ~ uCNbr ,

Exactly the

spectra of

trans-MeCH=CHCN o r

a t 1730,

1695 and 1590c1n-~,

a t 181Scm-1t224

An i n c r e a s e , o f 31cm-', i n VCN on g o i n g f r o m f r e e b e n z o n i t r i l e t o [Cu(C13C0)2(PhCN)]2, s h o w s t h e p r e s e n c e o f a C U - N C b o n d . 225

E v i d e n c e has been f o u n d t h a t b o t h qauche and t r a n s c o n f o r m e r s o f s u c c i n o n i t r i l e on copper s u r f a c e s c o o r d i n a t e t o t h e Cu v i a t h e . r r - s y s t e m o f o n e o f t h e t w o CZN g r o u p s . 2 2 6

SERS r e s u l t s f o r

m a l o n i t r i l e a t copper e l e c t r o d e s u r f a c e s p o i n t t,o e x a c t l y t h e same f o r m o f c o o r d i n a t i o n h e r e a l s o . 2 2 7 benzonitrile

l a t t e r f o r m s a n Ag-NC 'face

on'

SERS r e s u l t s f o r

a n d b e n z y l c y a n i d e i n a s i l v e r sol show t h a t t h e bond b u t t h a t t h e former 228

i s adsorbed

t o t h e surface.

Raman s p e c t . r a w e r e u s e d t o f o l l o w t h e c o m p l e x a t i o n o f H g ( C N ) by CN-

i n l i q u i d ammonia. T h e b a n d a s s i g n m e n t s p r o p o s e d a r e 229 s u m m a r i s e d i n T a b l e 2,

2

Vibrational Spectra of Some Co-ordinated Ligands

Table 2

315

vCN a s s i g n m e n t s f r o m H g ( C N ) * t CN-

i n liquid

ammonia (/cm-’)

4.5

Nitrosy1s.-

d i f f e r e n t vNO

Two f o r m s

wavenumbers:

of

Cp2V(NO)I have been r e p o r t e d ,

1590crn-’

a n d 1670crn-I.

with

That w i t h lower

vNO h a s e i t h e r a b e n t V N O g r o u p o r a l i n e a r VNO w i t h a l o n g N-0 bond;

t h i s predominated a t low temperatures.

T h e h i g h e r vNO

c o r r e s p o n d s t o a l i n e a r VNO,

and t h i s f o r m i s t h o u g h t t o h a v e a t 230 l e a s t o n e Cp l i g a n d w i t h a h a p t i c i t y l e s s t h a n 5 . NO o n r e d u c e d V 2 0 5 / A 1 2 0 3 d u e t o b o t h mono-

vNO i n C p C r ( N O ) ( L ) X P(OPh)3 o r P ( O E t ) 3 , 20-40cm-1 VNO,

c a t a l y s t s g i v e s VNO b a n d s i n t h e i . r . 231 and t o a n i t r j t e s p e c i e s .

and d i n i t r o s y l s

X =

( w h e r e L = PPh3,

I)

X = C1, B r o r

I;

occurs as a s i n g l e sharp i.r.

l o w e r t h a n i n CpCr (CO) ( N 0 ) L .

L = band

The o r d e r o f d e c r e a s i n g

> P ( O P h ) 3 > P ( O E t ) 3 > PPh3, i s c o n s i s t e n t w i t h t h e

CO

known e l e c t r o n - d o n a t i n g

power o f t h e s e l i g a n d s . 2 3 2

b o t h s h i f t t o h i g h e r wavenumbers t o t h e corresponding dications,

on g o i n g f r o m a s e x p e c t e d (R

vCN

a n d vNO

C r ( N C ) ( C N R ),(L-L)+

= Me,

CMe3,

L - L = dppm, d p p e ) . H o w e v e r , o n l y one C N s t r e t c h i n g b a n d i s s e e n f o r t h e d i c a t i o n , a g a i n s t 3 f o r t h e m o n o c a t i o n . The r e a s o n f o r t h i s i s n o t known.

233

The c o m p l e x ( 5 5 ) h a s t w o s t r o n g i . r . t h e geometry i s

&,

a s shown.234

b a n d s due t o vNO,

i.e.

T h e same c o n c l u s i o n was

d r a w n f o r t h e t w o n i t r o s y l g r o u p s i n S2MoS2MoBr2(NO)- 235 T h e 2’ VNO b a n d s f o r I W B r 2 ( N O ) 1 c o r r e s p o n d t o C selection rules for f o r t h e s t r u c t u r e (56).

33a

T h e Raman s p e c t r u m o f K2[Fe(CN)5NO] s t a t e shows wNO a t 1 8 3 5 c r n - l ,

i.e.

i n t h e M+NO

CT e x c i t e d

1 0 5 ~ m - ~l o w e r t h a n

i n the

g r o u n d s t a t e ( 1 9 4 0 ~ m - ~ ) .T h i s shows t h a t a c h a n g e i n g e o m e t r y for

FeNO f r o m l i n e a r t o b e n t h a s o c c u r r e d . 2 3 7

h a s VNO 37cm-’ 238

complex

.

[(Me5C5)Fe(N0)J2

lower t h a n i n t h e c o r r e s p o n d i n g C5H5

Spectroscopic PKoperties of Inorganic and Organometallic Compounds

316

(55)

(56)

T h e NO s t r e t c h i n g w a v e n u m b e r s f o r T a b l e 3.

(P)Fe(R)NO

T h e s e show t h a t a l l a r e t e r m i n a l

b e t w e e n t h o s e e x p e c t e d f o r l i n e a r Fe-NO'

are l i s t e d i n

nitrosyls,

w i t h values

a n d b e n t Fe-NO-.239

N i t r o s y l s t r e t c h i n g wavenumbers f o r (P)Fe(R)NO

Table 3

(/cm-l)

OEP

T PP

-

1670

1699

Me

1766

1789

P = R

-

"6 u Ph

1764

1795

1790

vNO v a l u e s w e r e a s s i g n e d i n a w i d e r a n g e o f c o m p l e x e s ( 5 7 1 , where R a n d R ' t h e &c

are v a r i o u s a l k y l groups,

analogues.240

R u3(CO)

p2-NO)

together with those for

H R U ~ ( C O ) ~ ~ ( ~ ~h-aNs OvNO ) a t 1550crn-1

and

a t 1 5 2 4 a n d 1 5 0 8 ~ m .241 -~

157) vNO

C2F5,

( ~ . 1 8 0 0 c m - ~ )i n I r ( 0 2 C R ) 2 ( N O ) ( P P h , ) 2 ,

where R

= CF3 or

i s a t v e r y d i f f e r e n t wavenurnbers f r o m t h a t i n

IrX2(NO)(PPh3)2, structure,

where X = h a l i d e .

T h i s suggests a d i f f e r e n t

and indeed t h e c a r b o x y l a t o complexes a r e e s s e n t i a l l y

317

Vibrational Spectra of Some Co-ordinated Ligands trigonal-bipyramidal, o f t h e h a l o complexes. T h e r e is i n f r a r e d

compared t o t h e t e t r a g o n a l - p y r a m i d a l 242 e v i d e n c e t h a t Ni2+-N0

surface n i t r o s y l s are

1.r. d a t a a l s o

f o r m e d b y NO a d s o r p t i o n o n p u r e N i O o r N i O / M g 0 . 2 4 3 show t h a t NO2 a d s o r b e d o n P t / S i 0 2 species.244 species,

which i s d e f i n i t e l y

s t u d i e s were a l s o made o f Pt/A1203,

linear

gives 3 d i s t i n c t

a n d one b e n t . 2 4 5

1.r.

NO c h e m i s o r b e d a t 298K o n p r e - r e d u c e d

Mo03/A1203 a n d Pt/A1203/Mo03.246

5 Complex

dissociates t o give Pt-NO

when a d s o r b e d o n P t / S i 0 2 ,

NO i t s e l f ,

one o f

form

Phosphorus and Antimony Donors

( 5 @ ) h a s vNP3 bands a t

871(i.r.

)/873(Raman)cm-l

and

@ 1 3 ( i . r . ) / 8 1 5 ( R a r n a n ) ~ r n - ~ .U~C~O~ w a v e n u m b e r s w e r e a s s i g n e d a n d Cotton-Kraihanzel CF3),

(60)'

force

constants calculated f o r 248

(59;

R = CH 3 '

and r e l a t e d species.

(58) [(OC)5MPPh

(591 (60) ] 0, w h e r e M = C r , No o r W, a l l h a v e v a s a n d vsPOP

more t h a n l O O c ~ - ' l o w e r t h a n i n t h e f r e e d i p h e n y l p h o s p h i n i c anhydrides.249

vP03 i s a t

'.

868cm-1

i n fRCr(C0)2[P(OR

= Me o r E t ,

acid

t ) 3 1 $2 ,

w h e r e R = T ~ - C H Me,

A'

b a n d a t 497cm-

A l a r g e n u m b e r o f l i g a n d modes w e r e a s s i g n e d

f o r t h e new c o m p l e x e s

(611,

w h i l e &PO3 c o n t r i b u t e s t o a

where M = C r ,

No o r W . w S b 3

and bSb3

modes w e r e l a r g e l y u n s h i f t e d w i t h r e s p e c t . t o t h e f r e e l i g a n d 251 values.

Spectroscopic Properties of Inorganic and Organometallic Compounds

318

v P 0 i n ( 6 2 ) i s a t 1031crn-1.252

Axial substitution at the iron

is r e v e a l e d b y t h e c h a r a c t e r i s t i c p a t t e r n o f i . r . ( 6 4 ) , w h e r e Y = OMe or NMe2, a n d r e l a t e d b a n d s d u e t o vCO. 2 5 3

atom i n (63)

s p e c i e s g i v e i.r.

b a n d s d u e t o t h e PPh3 l i g a n d s a t 1 0 9 0 ,

1430

and

ph3

Ph,P’

3

0

\\ \

Y

(63)

(64)

(65)

PPh3 l i g a n d modes w e r e s e e n a t 1 4 3 5 ,

7 6 5 , 7 4 5 a n d 700cm-1

i n [Rh(PPh3)3(MeCN)1 (BF4) .255

U n i d e n t a t e c o o r d i n a t i o n o f PF-6 i s r e v e a l e d b y t h e p r e s e n c e o f f o u r VPF b a n d s ( 8 8 0 , 810, 256 7 3 4 and 488cm-I).

i n (65)

The f o r m a t i o n

i.r.

o f Ag(AsPh3)3C1 g i v e s o n l y s l i g h t changes i n

b a n d s d u e t o t h e AsPh3 l i g a n d , The i.r.

ligand.257

compared t o t h e f r e e

s p e c t r u m of T h P 3 F 7 s h o w s t h a t i t c a n b e

f o r m u l a t e d a s Th4F4(U-L)3, (PF2):-.258

Cp3U(PPh2)

Ph g r o u p s ,

w i t h vPC a t

L =

where

cyclic,

g i v e s t h e u s u a l i.r. 1435cm-1.259

D e t a i l e d assignments were proposed f o r H3PGaX3,

where X = C 1 or

PhnPH3-D.GaC13,

-

where

VPH

fi =

1 or 2 ,

compared t o t h e f r e e - l i g a n d 6 6.1

tetradentate b a n d s d u e t o Cp a n d

P H 3 modes o n

a n d 6PH modes i n

a r e i n c r e a s e d i n wavenumber 26 1

values.

Oxyqen D o n o r s

M o l e c u l a r oxygen,

peroxo,

aquo,

modes w e r e a s s i g n e d f o r t h e L i - H

2

and r e l a t e d complexes.-

2O

0 complex i n a k r y p t o n m a t r i x .

T h e r e were s m a l l wavenumber s h i f t s

b u t g r e a t changes i n i n t e n s i t y 26 2 M ( = N g , Ca, S r o r B a ) compared t o H 0 a l o n e i n a K r m a t r i x . 2 a n d H 0 i n a r g o n m a t r i c e s f o r m M.0H2 a d d u c t s . C o m p l e x f o r m a t i o n

2 is s h o w n b y

s h i f t s t o l o w e r wavenumber o f t h e v 2 H 2 0 b e n d i n g

mode. 2 6 3

1.r.

Mg o r Ca,

R = Me o r E t ,

800cm-1

s p e c t r a o f Pl(ROH)6X2 a n d M(ROH)4X2, X

= C 1 or B r ,

where M =

show t h a t ROH modes a b o v e

a r e n o t much s h i f t e d b y c o o r d i n a t i o n 264 move t o l o w e r w a v e n u m b e r s .

b u t t h a t pOH modes

319

Vibrational Spectra of Some Co-ordinated Ligands )F $ 3 H 2 0 h a s v00 b a n d s a t 9 0 0 a n d 8 6 0 c m - l i n b o t h 2 3 a n d Raman s p e c t r a , c o n s i s t e n t w i t h C 2 v s y m m e t r y f o r t h e

K[Ti(O i.r.

N[VO(O

Ti02unit.265

p e r o x i d e s bound t o V

8

)2].M2S04,

w h e r e M = NH4,

i n triangular,

bidentate

Na o r K,

(cZv)

contain 266

fashion.

v00 o f t h e c o o r d i n a t e d O 2 i s a t 9 2 0 ~ m - i ~n [ V O ( 0 2 ) ( I O A ) l ’ , w h e r e IDA = C4H5NOZ-.267

f o r t h e Na’

a n d Kt

E q u i v a l e n t modes a r e f o u n d n e a r 8 5 0 ~ r n - ~ 2i s vO-0 i n N b F 5 ( 0 2 )

s a l t s o f V(02)i.268

~155cm-l.~~’ I n e l a s t i c n e u t r o n s c a t t e r i n g o f chromous a c i d , t h a t VasOHO

[Cr4(CO),2(v3-OH)4~4analogue),

CrOHO,

shows

i s a t 2 0 5 0 ~ m - ~a n d y O H O a t h a s VOH a t 3695cm-1

(2720cm-1

a n u n u s u a l l y h i g h v a l u e f o r v 3 - O H . 271

s p e c t r u m o f K 2 ~ M o 0 ( 0 2 ) 2 ( c i t r a t o ).hH ~ t h e m o l y b d e n u m p e r o x o u n i t a t 875cm-

i n t h e OD

T h e Raman

0 .3H20 c o n t a i n s v0-0 o f

3 .272

I n f r a r e d a n d o t h e r s p e c t r o s c o p i c d a t a show t h a t [ R e ( C 0 ) 3 ( 0 H o n s i l i c a is h y d r o g e n - b o n d e d i s o l a t i o n i.r.

of

f o r Fe(TPP)(CO)(O c o t o 02. 274

Me

t o s u r f a c e OH g r o u p s . 2 7 3

F e ( T P P ) c a r b o n y l c o m p l e x e s were r e p o r t e d , t h e r e was e v i d e n c e o f a - d o n a t i o n

)I4

Matrixe.g.

from

5

R e s o n a n c e Raman s p e c t r a were r e p o r t e d f o r d i o x y g e n a d d u c t s of

( 6 6 ) , w h e r e R = H o r Me.

When R = Me, V O O is a t 1 1 4 8 ~ m - ~ ,

t y p i c a l of

six-coordinate Co(salen)(base)O

R = H,

i s a t 1095cm-’,

close t o

2

- t y p e complexes.

‘base-free’

When

Co(salen)02.The

r e s u l t s show t h a t t h e p e n d a n t m e t h o x y p h e n y l g r o u p is c o o r d i n a t , e d t o the a x i a l position,

not-275

whereas t h e h y d r o x y p h e n y l group i s

T h e l o w v a l u e o f V 0 2 i n Co(TPP)(SPh)O;

(1602 1 1 2 2 ~ m - ~ ,

Spectroscopic Properties of Inorganic and Organometallic Compounds

320

1802 1 0 5 8 ~ m - ~i)s a t t r i b u t e d t o t h e p r e s e n c e o f t h e l o n e p a i r of electrons on t h e t h i o l a t e ligand,

d e n s i t y t o O 2 v i a r - o v e r l a p . 276

which d o n a t e e l e c t r o n

R e s o n a n c e R a m a n s p e c t r a were

r e p o r t e d for a l a r g e number of c o b a l t p o r p h y r i n complexes w i t h nitrogenous base axial l i o a n d s , as dioxygen complexes.

It is

p o s s i b l e t o get r e s o n a n c e enhancement of s o l v e n t bands whose wavenumbers match t h o s e of v

O

~

(. 6 7 ~) h ~a s ~v O O

of t h e hydro-

p e r o x o l i g a n d a t 813cm-’.

T h e a s s i g n m e n t was c o n f i r m e d b y 1 8 0 2 278 s u b s t i t u t i o n (band s h i f t e d t o 7 6 6 ~ m - ~ ) . v H 2 0 m o d e s f o r C U ( H C O O ) ~ . ~ H ~c O r y s t a l s show t h a t t h e r e a r e s t r o n g i n t e r a c t i o n s b e t w e e n C u a n d H20. 279

0

2

adsorbed on a

s i l v e r e l e c t r o d e i n a n a q u e o u s NaOH s o l u t i o n g i v e s t w o Raman bands i n solution:

ca.700,

~ . 8 5 0 c m - l . Their relative intensities 2 80

depend upon t h e e l e c t r o d e p o t e n t i a l . A v a r i e t y of

crn’1.281

VO-0

s a l t s c o n t a i n i n g U02(02)F:-

i n K[BF3(00H)]

h a v e vO-0

837cm-1.282 VO ( p e r o x o ) i s a t 8 6 0 ~ m - i ~n B ( 0 2 ) F z cm -1 i n B2(02)3:z-.283 [tBu2Sn(OH)X]2 crystals.

For X

X = C 1 or Br, 3450cm-l,

i.r.

Co o r N i ,

dimers form hydrogen bonds,

= F t h e s e a r e s t r o n g , w i t h vOH

on t h e o t h e r h a n d ,

and at 850

-0-H..

.X,

i n

a t 3 0 6 0 ~ m - ~ f; o r

t h e y are weak,

w i t h vOH a t a b o u t 2 84 value.

almost u n s h i f t e d from t h e free-hydroxyl-group

6.2 Carboxylato of the

n e a r 860

a p p e a r s a s a weak i n f r a r e d b a n d a t

and r e l a t e d complexes.-

A comprehensive a n a l y s i s

a n d Raman s p e c t r a o f M(CH3C00)2.4H20,

w h e r e M = Mg,

s u g g e s t s Fermi resonance between acetato-group

fundamentals and two-phonon molecules.285

modes a s s o c i a t e d w i t h H 0 2

D i b r o m o a c e t a t o c o m p l e x e s (CHBr2CO;

= L ) ML4 a r e

shown t o c o n t a i n b o t h c h e l a t i n g and b r i d g i n g l i g a n d g r o u p s , M = Ti,

Zr, T h o r U. F o r ML3 (M = F e o r Al),

o n l y c h e l a t i n g l i g a n d s are p r e s e n t .

where

S n C 1 2 L 2 a n d SbC12L3

2 86

1.r. s p e c t r a s h o w t h e p r e s e n c e of b o t h u n i - a n d b i d e n t a t e c a r b o x y l a t o groups i n Cr02(00CR)2,

CHC12.287

[Cr20(00CR)31C1, u n i d e n t a t e CF3CO;

i.r.

w h e r e R = Me, E t ,

P r or

O n l y b r i d g i n g c a r b o x y l a t o g r o u p s were d e t e c t e d f o r w h e r e R = Me, E t o r P r . 288 ligands

Bands due t o

were s e e n , a t 1 7 2 0 , 1 6 E O c m - l ,

i n the

s p e c t r a o f C H 2 C 1 2 s o l u t i o n s o f M o ( C O ) ~ (P M e 3 ) 3 ( C F 3 C O O ) 2 . 2 8 9

Several i.r.

bands a s s i g n a b l e t o ann2-carbonato

g r o u p were s e e n

321

Vibrational Spectra of Some Co-ordinated Ligands I J J ~ ( O ~ C R ) ~w ,h e r e R = Me o r t B u , w i t h hidentate carboxylate bridging, 1485cm-1

h a s o x a l a t o i.r.

MnF3(C204)'-

(Me).291

rather than chelating ligands: 1 292 1 3 2 0 ~ r n - ~ K, O , , 7 8 0 , 750crn-

bridging 1360,

have i.r. spectra i n accord -1 t vasC02 1472cm ( Bu),

.

The i n f r a r e d carboxylates,

s p e c t r a of

of

unidentate. 293

bands due t o 1670cm-1 ,vSCO2,

p e n t , a c o o r d i n a t e d Fe"' w h e r e L = OEP o r TPP,

(L)Fe(02CR),

show vas-vSCO

VasC02,

356-409cm-l,

i.e.

porphyrin

R = Me,

E t o r Ph,

t h e carboxylate groups are

q u i t e d e t a i l e d ligand-mode

assignments were

p r o p o s e d f o r [ R U ( C O ) ~ ( ~ J - ~ O C E ~a) s] ~d, i o x a n o r MeCN a d d u c t s , [Ru(CO)~(OOCE~)]

n

. The

and v

bidentate b r i d g i n g carboxylates. T h e r e is i . r .

evidence f o r

species a t t h e surface

v i a a carbamato-like

and

v a l u e s were c o n s i s t e n t w i t h

t h e formatior,

i n t h e CO/H2

Rh o r R h / M n c a t a l y s t s . 295 Co,

CO 234

o f a c e t a t o and a c e t y l

r e a c t i o n on Si02-supported

A n o v e l mode o f C 0 2 c o o r d i n a t i o n t o derivative,

was i n f e r r e d f r o m t h e i . r . 296

s p e c t r u m o f C O ( N O ) ~ ( L ) C ~w, h e r e L = ( 6 8 ) .

0 (69)

(681

L i g a n d - m o d e a s s i g n m e n t s i n t h e i . r . a n d Rarnan s p e c t r a o f Pd 11: a n d C u'' his-( 2 , 4 - p e n t a n e d i o n a t o ) c o m p l e x e s show t h a t t h e t w o l i g a n d s v i b r a t e almost 1 7 7 0 ~ m - (n_ ~

i n d e p e n d e n t l ~ . ~ ' (~6 9 ) h a s VC=O b a n d s a t 298 or 1 7 2 0 c m - 1 (1 = 3 ) .

= l), 1 7 4 0 ~ m - (1 ~ = 2)

(Ph P ) Cu(02CH) h a s i.r. b a n d s due t o b i d e n t a t e f o r r n a t o 3 2 w h i l e (Ph3P)$u(02CH) and (triphos)Cu(02CH) c o n t a i n

groups,

u n i d e n t a t e forrnato g r o u p s . 299 Cu(HCO0)

.2H

The i.r.

2 2 o f t w o i n d e p e n d e n t f o r m a t e i o n s . 300

Me,

Et,

Pr,

a n d Raman s p e c t r a o f

0 a n d i t s d e u t e r i a t e d a n a l o g u e show t h e p r e s e n c e

PhCH2 o r C H 2 C 1 ,

For C U ( R C O ~ ) ~ ( L )w , here R =

L = acetone,

d(dioxan)

carboxylate ligands are bridging bidentate, 301 v i a t h e o x y g e n atom.

o r THF,

the

with L coordinated

Spectroscopic Properties of Inorganic and Organometallic Compounds

322

I

I

Ph (7 11

Ph (7 0)

va s

( 7 0 ) and ( 7 1 ) h a v e c h a r a c t e r i s t i c

a n d vSCO2 b a n d s f o r

t h e a c e t a t o g r o u p s t r a n s t o N o r Ph r e s p e c t i v e l y .

These bands

a r e a l l seen i n t h e complex w i t h t w o a c e t a t o groups c o o r d i n a t e d 30 2 t o t h e gold. Cd(HC00)2(NH3)2 i s suggested t o have u n i d e n t a t e f o r m a t o g r o u p s o n t h e b a s i s o f i t s i..r.

spectrum. 303

c a r b o n a t o l i g a n d s were i d e n t i f i e d

M(C03)i-,

where M = La,

very complicated,

Eu,

E r or Yb,

3t

Gd o r Ho.

salts of

All t h e s p e c t r a were

s h o w i n g t h e l o w e f f e c t i v e symmetry

l i g a n d ~ . ~ T' h~e i . r .

Sm,

Srn,

1.r. b a n d s due t o

i n t h e Co(NH3I6

spectra for

Ln(CF3C00)3.3H20,

show t h a t t h e y h a v e d i m e r i c

b r i d g i n g trif l u o r o a c e t a t o groups.

of the

where L n =

structures,

with

305

B i d e n t a t e b r i d g i n g c a r b o x y l a t o groups were a l s o i d e n t i f i e d i n M[UO,(OAc),]

Zn.306

and M[U02(02CCF3),~,

Co o r

w h e r e M = Mg, B a ,

I n f r a r e d a n d Raman s p e c t r a o f U 0 2 ( C 2 0 4 )(Bu3PO)

consistent with a polymeric structure, 307 oxalato groups.

are

containing quadridentate

1.r. s p e c t r a of Me2Si0 A 1 (01Pr)4 complexes w i t h cinnamate, 2 2 dihydrocinnarnate or s a l i c y l a t e suggest t h a t t h e r e i s c h e l a t i o n o f t h e carboxylato group t o A L ~ " thallium(1)

T h e Raman s p e c t r a o f a q u e o u s

f o r m a t e s o l u t i o n s showed t h e p r e s e n c e o f b r i d g i n g

formato groups i n concentrated solutions, 309

a s seen i n t h e

c r y s t a l l i n e state.

vC=O b a n d s w e r e a s s i g n e d f o r a l k y l t i n i s o - o c t y l t h i o g l y c o l l a t e s ,

.

R 2Sn ( IOTG ) 2 , R 2SnC 1( I O T G ) e t c 310 C a r b o n y 1- s t r e t c h i n g b a n d s f o r Ph3Te[RCOCH=C(0)R'],

or 2-thienyl, 6- d i k e t onates.

where R

= CH 3 , * C F 3 or P h , R '

show u n i d e n t a t e g - c o o r d i n a t i o n

311

= CH

of the

3 9

CF3,

Ph

323

Vibrational Spectra of Some Co-ordinated Ligands 6.3

Keto,

alkoxy,

Lic104*312 t o Lit

,

Shifts

K O C modes

e t h e r and r e l a t e d complexes.-

w e r e a s s i g n e d i n t h e i.r.

s p e c t r a o f crown-ether

complexes o f

T h e r e i s Raman e v i d e n c e f o r t h e c o o r d i n a t i o n o f DMF Mg2+ a n d A 1 3 + i n N , N - d i m e t h y l f o r m a m i d e / H 2 0 s o l u t i o n s . 3 1 3

i n VCXO

i n d i c a t e d Mg-0

c o o r d i n a t i o n i n Mg(N03)2.4CO(NH2)2 314

a n d M g ( N 0 3 ) 2 . 6 ( m e t h y l e n e d i u r e a ) .315 C a - 0 c o o r d i n a t i o n was 316 d e t e c t e d s i m i l a r l y f o r CaC12 .4CO (NH2 12.

vC=O modes i n a c e t o n e c o m p l e x e s C P ( C O ) ~ L M L " L = PPh3;

L = PPh3 o r C O ;

M = W,

L'

( w h e r e M = Mo,

l i e i n t h e range

= acetone)

1 6 4 0 - 1 6 6 9 ~ m - ~T.h~e ~c~a r b o n y l s t r e t c h d u e t o t h e c o o r d i n a t e d DMF i n (TPP)MnlllBr(DMF) l i g a n d ) . 318

i s a t 1658cm-'

(1675cm-1

i n the free

T h e i . r . a n d Raman s p e c t r a o f M X 2 ( a m i d e ) n ,

where

N i , C C J , Cd, Hg, Pd o r P t , a m i d e = f o r m a m i d e , N - m e t h y l f o r m a m i d e (NMF) o r DMF, X = C 1 o r B r , g a v e a c o m p l e t e M = Mn,

Fe,

assignment

Co,

of

A l l were g - c o o r d i n a t e d ,

l i g a n d modes.

NiC12(NMF)4,

NiC12(DMF)2 and C u C 1 (DNFI2,

evidence for

N - c o o r d i n a t i o n also.319

S e v e r a l d i a g n o s t i c bands

d u e t o t h e OMe l i g a n d w e r e a s s i g n e d f o r

D,

where X = H ,

C 1 , B r o r I. 320

APPY = Ph3PCHCOCH3,

ReX(OMe)(CO)(NO)(PPh3)2,

T h e VCH o f t h e b r i d g i n g OMe

g r o u p i n Rh2(p-OMe) ( C O ) 2 ( u-dppmI2

i s a t 2 8 0 3 c m - l .321

w h e r e L = PPh3,

Pd(C6F,)L2(APPY)',

except f o r

w h e r e t h e r e i s some

PnBu3,0r

g i v e VC=O n e a r 1520cm-',

L2 = bipy,

showing ylide.

u n p r e c e d e n t e d Pd-O c o o r d i n a t i o n o f t h e k e t o - s t a b i l i s e d The n e u t r a l c o m p l e x P d ( C 6 F 5 ) ( C l ) ( t h t ) ( A P P Y ) , tetrahydrothiophene,

h a s VC =C a t 1 6 5 5 ~ m - ~ s, h o w i n g t h e n o r m a l

c o o r d i n a t i o n . 322

Pd-C

The i.r.

nTHF,

where

n

6.4

= 1, 2 o r 3, 324

L i q a n d s c o n t a i n i n q 0-N where M'

o r 0-P bonds.-

groups,

spectra o f A1C13.

1.r.

where M = L i - R b ,

= Mg, Ca o r B a .

ure i s a long-chain polymer,

N'

The i.r.

a r e c o n s i s t e n t w i t h A1-0

b e e n r e p o r t e d f o r N[O,P(OR),], M'L02P(OR)212,

gave

s p e c t r u m o f TmC12.2THF

a s s i g n m e n t s f o r some THF m o d e s . 3 2 3

coordination.

where t h t -

When M = L i ,

w i t h bridgl.ng,

M = C s o r Rb a r e monomers, 325

spectra have R = 2-ethylhexyl, the struct-

b i d e n t a t e P ( O!O

w i t h b i d e n t a t e P(O)O,and

= Mg i s a g a i n a p o l y m e r .

Zr(Cp)2PhCON(Ph)NO]gives

i.r. bands a t 1345,

9 2 8 ~ r n - ~t ,y p i c a l o f t h e h [ O N ( R ) N b I 02PC1;

modes i n NbOC14(02PC1

coordination

one oxygen.

12'

1295, 1 2 1 8 and

c h e l a t e ring.326

The

are consistent with unidentate

327

Trans-[Cr(cyclam)(N03)]N03.2H20

,

where c y c l a m = 1,'-1;8~11-

Spectroscopic Properties of Inorganic and Organometallic Compounds

3 24

tetra-azacyclotetradecane,

h a s b a n d s due t o t h e c o o r d i n a t e d

1.r.

n i t r a t o g r o u p a t 1515 a n d Cr(D2PF2)3.HP02F2,

a n d 2 new f o r m s o f F e ( O 2 P F 2 l 3

spectra o f

w h e r e M = Mn,

N(02PF2!2.HP02F2,

Co o r N i ,

Fe,

a l l show t h e b a n d s e x p e c t e d f o r l i g a n d ~ . ~ vC=O ~ ' a n d vP=O

bidentate b r i d g i n g difluorophosphate

b a n d s f o r M o 0 2 C 1 2 [ ( 1 P r O ) 2 P ( 0 ) C H 2 C ( 0 ) N E t 2 ' ] a r e a t l o w e r wawenurnbers than i n the free 3 30

ligand,

i.e.

b o t h C = O a n d P=O a r e c o o r d i n a t e d t o

the metal.

The i.r.

s p e c t r a o f N(pacO)(H,O),,

w h e r e pac0'-

=

pyridine-2,6-dicarboxylate E - o x i d e i o n , M = Mn, Co, Zn,

d o p o t show t h e e x p e c t e d d e c r e a s e i n VN-0

due t o t h e c - c o c r d i n a t i o n ,

b r e a k d o w n of

Cu o r

(from the free ion)

which i s found by X-ray

T h i s may b e d u e t o a s i m u l t a n e o u s

Mi,

diffraction.

i n c r e a s e because o f t h e

t h e hydrogen bonding found i n t h e f r e e ligand.

Fe(salen)(N03)

[Fe(salen)ONO

exists

as t w o isomers,

One is a d i r n e r ,

spectroscopy.

'1

Fe(salen)C2NO:

w i t h

characterised by i.r.

unidentate nitrates,

t h e o t h e r i s a monomer, "N-substitution

331

w i t h bidentate nitrate,

was u s e d t o i d e n t i f y NO3 b a n d s

1.r. b a n d s

( s a l e n = ~,~'-ethylenebis(salicylideneaminato)).3 3 2

i n d i c a t i v e c f u n i d e n t a t e p h o s p h a t o (lZ3v s y m m e t r y ) w e r e s e e n f o r 333 ~h ( N H 3 ) p o 4 . Assignments the trans-nitro Me2Ph,

were g i v P n f o r v s , vasN02, complexes Pd(N02)2(PR3)2,

Ph2 o r E t 3 ;

6N02 a n d pN02 f o r w h e r e R 3 = MePh2,

t h e s e were c o n f i r m e d b y 1 5 N s u b s t i t u t i o n .

A l l o f t h e b a n d s w e r e c o n s i s t e n t w i t h Pd-N b o n d i n g , numbers o f b a n d s c o n f i r m e d t h e t r a n s bands a t 1375,

1315,

c o c r d i n a t e d ON(Ph)NO

and t h e

(72) has i.r.

1 2 7 5 2 n d 910cm-1, 335

characteristic o f the

ligand.

vP=O i n E u ( O I K ) 2 ( N 0 3 ) ( P h 3 P O ) 2 i s s b i f t e d t o l o w e r w a v e number c o m p a r e d t o t h e f r e e l i g a n d , v i a 0 (DIK = v a r i o u s 6 - d i k e t o n a t e

i.e.

i t i s coordinated

l i c ~ a n d s ) . ~ ~ ~

325

Vibrational Spectra of Some Co-ordinated Ligands U(N03)4L2, have i.r.

where L = p i p e r a z i n e cr s u b s t i t u t e d d e r i v a t i v e s ,

bands of

chelating,

a n d Raman s p e c t r a o f

( 7 3 ) . 3 3 8 T h e i . r . a n d Raman s p e c t r a o f t h e a d d u c t

OPO b r i d g e s

r e v e a l t h e c o o r d i n a t i o n o f t e r m i n a l 0 atoms o f

P203C14.2SbC15 P 2 0 3 C 1 4 t o Sb resDectively.

(74).

V

339

as

vSPOP a r e a t 980,

POP,

440cm-1

(731

6.5

(74)

L i q a n d s c o n t a i n i n q 0-S,

W (S03CF3)3,

W 0(SO3CF3),

0-Se, o r 0 - T e

a n d WO(S03CF3),

v

1

v3 8 8 5 , 8 6 0 c m - l ,

825cm-l,

bonds.-

1.r. d a t a f o r

a l l suggest b r i d g i n g

S e 0 4 modes w e r e a s s i g n e d f o r

h i d e n t a t e b o n d i n g f o r S03CF3. 340

W112Se0i:

1.r.

b i d e n t a t e n i t r a t o only.337

U02(P02F2)2 suggest a c h a i n s t r u c t u r e w i t h

v 4 440,

4 2 0 c r n - ~ . B~a~n d~s

due t o u n i d e n t a t e SO4 l i g a n d s were a s s i g n e d i n [ f l o , E l 8 ~ ( S O 4 ) , , a t 1275,

1.r.

10130, 6 4 5 a n d 6 1 5 ~ r n - l . ~ ~ ~

1250,

s p e c t r a w e r e r e p o r t e d f o r R u ( S O ~ F ) a~n d Ru(SO~F);,

which have both u n i -

and b i d e n t a t e l i g a n d s ,

w h i c h o n l y c o n t a i n s u n i d e n t a t e l i g a n d s . 343 (SO:-

modes) of

M2CuS04,

t h a t t h e n a t u r e o f Cu-SOn

Rb,

Cs o r T 1 ,

show

c o o r d i n a t i o n i s d e p e n d e n t o n M.

5Te \

344

TeFs O--Ag-OO

I

F5T/

K,

w h e r e M = Na,

a n d f o r Ru(SO3F);-, The i . r . s p e c t r a

0-Ag-O

I 'TcF,

(75) Ag(OTeF5)

h a s VTeO a t

815cm-'(i.r.

consistent w i t h the structure U02X04(DMS0)2.H20,

)/812,

845cme1(Raman),

( 7 5 ~ 1 .T h~e ~i .~r .

where X = 5 ,

spectra o f

S e o r C r , show b i d e n t a t e , 3 46

b r i d g i n g c o o r d i n a t i o n b y t h e X04 u n i t s .

Spectroscopic Properties of Inorganic and Organometallic Compounds

326 6.6

L i q a n d s c o n t a i n i n q 0-C1 bonds.-

FTIR s p e c t r a were o b t a i n e d

f o r t h e v a p o u r s a b o v e NaC103 a n d L i C 1 0 3 a t 360OC. F o r NaC103 t h e most s t a b l e i o n p a i r h a s t e r d e n t a t e g e o m e t r y . (more t h a n 5 0 % ) of

A h i g h percentage

d i m e r s were p r e s e n t i n each case.347 T h e r e

was Raman e v i d e n c e f o r

ion-pair

formation for alkali-metal 34 8

p e r c h l o r a t e s i n DMSO/H20 s o l u t i o n s . The i.r.

s p e c t r a o f Nb(C104)5,

NbO(C104)3 and Nb02C104

c o n t a i n b a n d s c h a r a c t e r i s t i c o f b o t h u n i - and b i d e n t a t e C104 ligands.

I n Nb(C1O4);

a n d Nb(C1O4);-

there are only

l i g a n d ~ . ~ B~a’n d s d u e t o u n i d e n t a t e C 1 0 4

unidentate

and f r e e C l O ,

were seen for[RuL3(ClO4)]C1O4,

w h e r e L = Ph PCH2PPh2, 330 2AsPh 2 . Ph 2A s (CH 2 ) 2 A s P h 2 o r Ph2P(CH

PPh2,

A n h y d r o u s N(ClO,),, prepared.

w h e r e M = Co,

The v i b r a t i o n a l

N i o r Cu,

have been

s p e c t r a were a n a l y s e d i n t e r m s o f

t r i d e n t a t e p e r c h l o r a t o l i g a n d s f o r M = Co o r N i of bidentate ligand for proposed f o r

ion Ph2P(CH2)2-

M =

CoL(C104)4.3H20,

and t w o t y p e s

Ligand-mode

assignments were 35 2 where L = benzo-15-crown-5.

1.r. a n d Raman s p e c t r a w e r e r e p o r t e d a g a i n f o r N i ( C 1 0 4 ) 2 ( s e e 35 3

r e f .351).

7 The i.r.

Sulphur Donors

s p e c t r a o f MX4L,

dithio-oxamide, oxamide.354

where M = T i o r Z r ,

a l l show M - 5

1.r.

X = C1. o r B r ,

d a t a show b i d e n t a t e d i t h i o c a r b a m a t e

CpTi(S2CNHR)C12 a n d CpTi(S2CNHR)C1, CSH5N2SC12 o r C g H 7 N 2 S . 3 5 5

L =

coordination for the dithiowhere R

ligands i n

= C 8H 5 N2 5 ,

S i m i l a r r e s u l t s f o r CpTi(S2COR)C12,

CpTi(S2COR)2C1 a n d CpTi(S2COR)3,

w h e r e R = Me,

Et,

Pr,

8u

a n d C5Hll,

shcw t h a t a l l a r e n o n - e l e c t r o l y t e s w i t h h i d e n t a t e 356 xanthato ligands.

1 . r . b a n d s o f VO(RNCS2)2, i

Bu2,

piperidine,

where R = E t 2 ,

p y r r o l i d i n e etc.,

(1480-1515~m-~a ) n d VC-S

i

Pr2,

Bu

2’

w e r e a s s i g n e d t o VC=N

(1130-1150~m-~3 ) .5 7

r a n g e 5 8 0 - 6 0 0 ~ m - ~i n Nb2X4S3,

Pr2,

vS-S

where X = C 1 o r B r ,

l i e s i n the and t h e i r

a d d u c t s w i t h S - d o n o r s o r NeCN.358 V S - S i n M o ( S 2 ) C 1 i s a t 6 1 2 -1 32w i t h very s i m i l a r values i n [ X 4 N o ( ~ - S 2 ) 2 M ~ X 4 j 35 9 where X = C 1 o r B r . M O C ~ ( N O ) [ P S ~ ( O R ) ~ ] ( S ~ C N R ~w) h, e r e R = E t , iP r , A ’ = Me o r

cm

,

Et,

h a v e vPS a t 7 7 0 - 8 0 0 ~ m - ~( i . e .

,

unidentate dithiophosphorus

l i g a n d ) a n d vCN a t 1 5 1 5 - 1 5 8 0 ~ m - ~( b i d e n t a t e d i t h i o c a r b a m a t o 36 0 ligand).

327

Vibrational Spectra of Some Co-ordinated Ligands 1.r. b a n d s i n t h e s p e c t r a o f MoCXL2, w h e r e X = F , C l , HL = 4 - m o r p h o l i n o - d i t h i o c a r b o x y l i c

acid,

6 r o r I,

are consistent with the

d i t h i o c a r b a m a t e a c t i n g as a u n i v a l e n t , b i d e n t a t e ligand.361

a r e 15-17cm-'

The

R = Me o r E t ,

v C N b a n d s i n M O ( C O ) ~ ( S ~ C N R ~ ) ~wXh-e, r e X = F o r N3,

l o w e r t h a n i n M o ( C O ) ~ ( S ~ C N R ~T )h~i s. i s due t o a n

increase i n t h e c o n t r i b u t i o n f r o m (76) 36 2 the ligands.

rather than (77) i n

(7 6) M o ( S 2 C N E t 2 ) i d o e s c o n t a i n No"

-

c o n f i r m e d by t h e presence o f

a t h i o u r e i d e b a n d a t 1 5 0 7 ~ m - ~ i ,n t e r m e d i a t e b e t w e e n t h e v a l u e s f o r k n o w n No'" bands,

a n d Nov1 s p e c i e s . 3 6 3

n e a r 1000cm-l,

60Ocm-'

S p l i t t i n g s o f v s and vas(CS)

respectively,

Mo6019 s u g g e s t a c o m p l e x mode o f

i n [Mo(S2CNEt2)432-

b o n d i n g b e t w e e n t h e No a n d t h e

5 ) ~ 2 2 (S2CNEt2l4 d i t h i o c a r b a m a t e . 3 6 4 No4 ( ~ ~ - (p-S2CNEt one YC=S i . r . b a n d , presence of

showing b i d e n t a t e c o o r d i n a t i o n ,

different

t y p e s of

l i g a n d was r e v e a l e d b y t h e p r e s e n c e

o f t w o b a n d s a t 5 6 5 , E ~ 5 I . c m - l . ~ K~ ~O f o r shows many b a n d s ,

has o n l y but the

(OC),W[S=C(Ph)H]

due t o t h e p r e s e n c e o f b o t h ql-

and q 2 - i s o m e r s ,

( 7 8 ) and (79).366

(OC)5w-s+

S

CH I

(79)

(78)

X a n t h a t e a n d V C O modes w e r e a s s i g n e d f o r SCO,(CO)~(S,CON~). CO'~(S~CNRR');,

where R ,

R'

= Me,

Et,

a b o u t 2Ocm-I h i g h e r t h a n i n t h e Co'" s p e c t r a of

HRhL2.H20,

H3RhL3.2H20

CH SO Na, c o n t a i n no vSH 2 3 36 9 s u l p h u r atoms.

(NC),NiS:a t 460, (S2CO)

has i.r.

bands,

etc.,

Ph o r CH2Ph, analogues. 368

h a v e VC-N The i . r .

w h e r e H 2 L = HSCH2CH(SH)-

showing c o o r d i n a t i o n v i a b o t h

bands t e n t a t i v e l y

3 9 3 a n d 385cm-1.370

a s s i g n e d t o wSS

S o l i d CO=PPh2CH2CMe(CH2PPh2)jNi-

h a s vC=O f r o m t h e c h e l a t i n g d i t h i o c a r b o n a t o l i g a n d .

No c a r b o n - s u l p h u r

36 7

s t r e t c h i n g was d e t e c t a b l e . 371

328

Spectroscopic Properties of Inorganic and Organometallic Compounds A d e t a i l e d a s s i g n m e n t o f l i g a n d modes was p r o p o s e d f o r ML2,

w h e r e M = N i o r Cu,

L = (80;

was h i g h e r f o r

VC=-N

X = CH2,

0 , S,

NH,

NMe,

NPh). 37 2

t h e N i t h a n f o r t h e Cu complexes.

S

(Ph P I Cu' 3 2 (80)

\PS-%4

(81)

3-

vS-S modes i n C U ~ ( S ~g )i v ~e Raman f e a t u r e s a t 4 2 5 ,

,

4 6 9 ~ m - I . (81) ~ ~ ~a n d ( t r i p h o s ) C u ( S 2 C t l ) dithioforrnates

respectively,

give very s i m i l a r

a n d n o t v e r y d i f f e r e n t f r o m t h o s e of internal electronic

with b i -

d i s t r i b u t i o n i s almost

5 2 0 ~ r n - ~ a, n d VSS a t 476cm

.375

modes,

Hence t h e

unchanged on

A u C l ( 5 N ) h a s vSN a t 1 0 5 2 ,

c o o r d i n a t i o n . 374

ligand

S2CH-.

free

435 a n d

and u n i d e n t a t e

Au ( d t a ) 4 ,

696cm-l,

6SN

s.

where d t a =

d i t h i o a c e t a t o , h a s v C S 2 a t 1160cm-fi a n d vsCS2 a t e99cmm1, as consistent w i t h t h e multinuclear, completely bridged structure revealed

by X-ray

benzoato,

has V

diffraction.

Au(dtb),

C S 2 a t 1039cm-l,

as 6 5 6 ~ m - l i~n a g r e e m e n t 376 ligand. where X

=

a n d 6CS2 a t

with a f u l l y chelated d i t h i o b c n z o a t c

T h e r e i s a marked change i n VY-H GaX3.HYEt,

where d t b = d i t h i o a t 911cm-1

VsCS2

on c o o r d i n a t i o n t o f o r m

B r o r I, Y = 0 , 5 , Se, s h o w i n g t h a t t h e r e

i s a s t r o n g i n t e r a c t i o n b e t w e e n t h e Ga a n d t h e c h a l c o g e n o l . A

n u m b e r o f l i g a n d modes w e r e a s s i g n e d f o r

P h GeS P ( 0 M e ) and 3 2 37 8 showing t h a t t h e y a r e u n i d e n t a t e l i g a n d s .

Ph2GelS2P(OMe)232, The i.r.

s p e c t r a o f MeSb(S2CNR2)2,

-(CH2)20(CH2)2-,

where R

= Me

L-L = N , N ' - d i s u b s t i t u t e d

= Et,

'Pr,

"Bu

dithiornalonates

or Cy),

and l o w e r wavenumbers,

C N and

have

respectively,

T h i s i s c o n s i s t e n t w i t h S,S-donation. 8 P o t e n t i a l l y Ambident

8.1 C y a n a t e s ,

Thio-

N[Zr@(NCS),].2H20, Zr-NCS

or E t ,

R2 =

are a l l c o n s i s t e n t with symmetrical b i d e n t a t e

c o o r d i n a t i o n o f t h e d i t h i o ~ a r b a n a t e s . ~ ~S'b C 1 3 ( L - L ) ,

(R

377

CS s h i f t e d t o higher

compared t o t h e f r e e l i g a n d s . 3 80

Liqands

and S e l e n o c y a n a t e s , and t h e i r w h e r e M = Cs'

coordination.381

V-NCS

where

RHNC (S)CH2C ( S ) N H R

or pyH',

Is0 A n a 1 o q u e s . -

have NCS bands c o n f i r m i n g

c o o r d i n a t i o n was d e t e c t e d i n t h e

329

Vibrational Spectra of Some Co-ordinated Ligands same way f o r a n d W-NCS

C5HNe4 o r C5Me5,

C P * V ( N C S ) ~ , w h e r e Cp+( = C 5 H 4 Me, ( 8 2 ) .383

coordination i n

oc

1*NCS

SCN

(8 2) In the

1.r.

vCS(N)

vCN(S),

a n d Raman s p e c t r a o f 0sCl5(1\JCS)

2 1 9 0 ~ r n - ~( ~ X V ~ C N O ) ,2110cm-1

vCN

has f u l m i n a t e bands a s f o l l o w s : ( v ~ C N O ) . The

w i t h vasNCO

at

a n d vsNCO a t 1 3 1 8 ~ r n - l . ~ ~ ' of

= CN,

show Co-NCS

of

L2N(NCS)2(NCSAg)2,

= NCS o r L = NCS,

where L = L '

NCS i n ( C 5 H 4 M e ) C o ( C O ) L L ' ,

L'

etc.,

and OsC15(SCN)2-

(vaSCNO) a n d 1087crn-1

c o m p l e x i s o m e r i s e s i n s o l u t i o n t o W(NCO)(CO);, 2235cm-1

2-

a n d GNCS a r e a t h i g h e r w a v e n u m b e r s t h a n V C N ( N ) ,

(CO); a n d c ~ S C N . ~W(CN0) ~ ~

VCS(S)

382

c o o r d i n a t i o n i n e a c h c a s e . 386

N i o r Cu,

w h e r e M = Co,

1.r.

spectra

L = urea,

thiourea 3 87 a l l show t h a t t h e y h a v e monomeric b r i d g e d s t r u c t u r e s .

The i.r. s p e c t r a ,

c h i e f l y vCN,of

PPh3 o r o t h e r a r y l p h o s p h i n e s ,

Pd(SCN)2L2,

where L =

a r e c o n s i s t e n t w i t h Pd-S

c o o r d i n a t i o n . 3 8 8 T h e r e i s i.r.

evidence t h a t Pt(bipy)(SCN)2 has

P t - S E N c o o r d i n a t i o n a t r o o m t e m p e r a t u r e , but, o n h e a t i n g a b o v e 3 89 13OoC c o n v e r t s i t t o t h e P t - N C S f o r m . Raman a n d i . r .

s p e c t r a o f s p e c i e s f o r m e d b y CuSCN t SEN-

s o f t donor s o l v e n t s were r e p o r t e d .

Cu(NCS);

has vCN

i n

a t 2075cm-1

( i . r , ) / 2 0 8 6 ~ m - ~ ( R a m a n ) a n d VCS a t 7 9 1 ~ r n - ~ . I t i s t h e r e f o r e !-bonded, i . e . Cut i s a c t i n g as a h a r d c a t i o n t o w a r d s SCN-. 390 The f u l m i n a t o c o m p l e x Au(PPh3) (CNO)

has a c h a r a c t e r i s t i c

The i . r .

s p e c t r a o f MeSiH2X,

i.r.

s u b s t i t u t i o n ) .391

b a n d a t 2 1 5 6 ~ m - (~s h i f t e d t o 2 1 1 9 ~ m - o~n

where X = NCO,

N C S o r NCSe,

show

t h a t a l l a r e Si-N-bonded. 392 The p r e v i o u s l y d e s c r i b e d 'F5Se-NCO' h a s now b e e n s h o w n t o b e F Se-OCN, ( s ) .593 bands a t 2 2 9 0 ~ r n - ~ (as), 1 1 0 4 ~ r n - ~ 8.2

Infrared results for

L i g a n d s c o n t a i n i n g N a n d 0 atoms.-

IMPH2 = i n o s i n e - 5 ' - m o n o p h o s p h a t e

Mg(IMP).5H20,

where

s u g g e s t Mg-N7

coordination,

together

w h e r e M = Ng o r Zn,

1-nitroso-2-naphthol

M'

= Li,

or 8-hydroxyquinoline,

u n b r i d g e d oxygen atoms a r e p r e s e n t .

acid,

w i t h i n d i r e c t metal

phosphate and m e t a l c a r b o n y l i n t e r a c t i o n . 3 9 4 M(acac)2M'L,

a s i t h a s vOCN

395

The i . r .

Na o r K ,

spectra of

HL =

show t h a t b r i d g e d a n d

Spectroscopic Properties of Inorganic and Organometallic Compounds

330 VOCl(L)

where H2L = t h i o - S c h i f f

a n d V02L3,

c o n d e n s a t i o n of s a l i c y l a l d e h y d e

,

bases from t h e

2-hydroxyacetophenone

o r benzyl)dithiocarbazates, h a v e i . r .

w i t h S--(methyl

etc.,

spectra

c o n s i s t e n t w i t h t r i d e n t a t e c o o r d i n a t i o n v i a t h i o l S,

azomethine

0.396 R e - i n v e s t i g a t i o n o f t h e i . r . s p e c t r a o f

N and p h e n o l i c

b i s N-(2-mercaptoethyl)salicylideneaminato

oxovanadiurn(1V)

shows

t h a t t h e OH g r o u p o f t h e l i g a n d i s c o o r d i n a t e d t o t h e m e t a l , 397 contrary t o earlier reports. C r L 2 C 1 a n d MLC1,

where M = C r ,

v i a t h e 0 atoms of [ML21X

Mn,

Fe,

Co,

have t h e L-

dihydrobis(succinimidyl)borate,

N i o r Cu,

Co,

X = C1;

=

1.r. d a t a f o r

t h e succinirnide r i n g

[where M = C r ,

L-

as a bidentate l i g a n d

M = Dy,

Gd o r Sm,

X = NO3;

HL = o-HOC6H4N=CHC(0)R]

show t h a t t h e L i s c o o r d i n a t e d b y t h e 39 9 t h e l r n i n o N a n d phenoxo 0 atoms.

c a r b o n y l 0,

Ligand-mode

assignments f o r M n ( I 1 ) complexes w i t h c y s t e i n e ,

h o r n o c y s t e i n e a n d p e n i c i l l a m i n e a l l show c o o r d i n a t i o n v i a NH 2 400 a n d COOH g r o u p s .

H

I

R

(83) The i . r .

(84)

b a n d a t 1660cm-1

i n Ru~C~(C,H,NO),(C~H~NO)

t h e presence o f t h e k e t o form o f t h e 2-hydroxy-pyridine

( 8 3 ) . 4 0 1 vC=O(amide) Ph,

E t or Pr,

i n Os3(CO),o(~-H)(NHCOR),

always g i v e s j u s t

one i . r .

band,

consistent w i t h t h e presence o f t h e unit’ ( 8 4 ) . Assignments were proposed f o r n i t r o - l i g a n d

M = Co,

Me,

1570-1597~m-~, 402 modes f r o m t h e

spectra o f CO(OH)~(NO~)A a n d C O ( D H ) ~ ( N O ~ ) X -w, h e r e 403 d i r n e t h y l g l y o x i m e , A = a m i n e , X = I,B r , C N , NCS e t c . w h e r e guH = g u a n i n e ,

ligand

where R = H,

i.r.

M(guH)C12,

shows

C u o r Zn,

OH2 =

have i.r.

spectra

c o n s i s t e n t w i t h c o o r d i n a t i o n o f one o r more r i n g n i t r o g e n s t o vC=N

modes i n a l l o f t h e f o l l w i n g a r e c o n s i s t e n t w i t h

C = N - C o c o o r d i n a t i o n : CoL2.2H20, = 2-fury1,

or 2-HO

w h e r e H L = 2 - H O C C H N=C(CH3)R, 2 6 4 CoL’C12.2H20, where L ’ =

SC H N=CHC(O)R; 3 6 4

R

33 1

Vibrational Spectra of Some Co-ordinated Ligands RC(=O)-CH=NC,H4N=CHC(

=O)R;

02NC6H3N=CHC(=O)R.405

1.r.

Z n or Hg,

and FeL2C1 406 N a n d k e t o n e 0.

El2,

where L"

s p e c t r a o f ML2,

-N - ( d i m e t h y l a m i n o m e t h y 1 ) i s a t i n Cu,

CoL;

and

= 2-Cl-4-

where HL =

8-thiosemicarbazone,

M =

Co,

Ni,

show c o o r d i n a t i o n v i a 5 , h y d r a z i n e

S h i f t s i n vC=O a n d r i n g v i b r a t i o n s show t h a t 1 , e - n a p h t h y r i dine-2,7-dicarboxylate

coordinates by the r i n g N

t o N i i n Ni2(2,7-dc-1,8-napy)3

'-.

and c a r b o n y l 0

A d e t a i l e d assignment o f

407

l i g a n d modes was p r o p o s e d f o r b i s ( s a l i c y l a 1 d o x i m a t e s ) (85) has

and P d ( I I ) . 4 0 8 a l d e h y d e C-H..

.Pt

of Ni(I1)

vC=O a t 1 6 8 2 ~ m - ~c, o n s i s t e n t w i t h a weak

interaction.

409

(-&) c HO--Pt c 12

I

PEt,

(85)

(86)

v s C 0 2 a n d vasC02 a s s i g n m e n t s f o r C u ( I 1 ) c o m p l e x e s o f a v a r i e t y o f amino a c i d s were used t o a s s e s s t h e c o v a l e n t c h a r a c t e r of

t h e C u - 0 bonds.410

D i n u c l e a r c o p p e r ( 11) c o m p l e x e s

s u c h a s ( 8 6 ) h a v e VC=O a t 1650cm-1 411 t h e s u b s t i t u t e d CONH g r o u p .

from

w h e r e DPAAP = 4 - ( 2 ' , 4 ' - d i h y d r o x y p h e n y l -

I n Ln(DPAAP)2(N03), azo)antipyrine,

a n d VNH a t 3 2 5 0 c m - l ,

L n = La,

P r , Nd,

Sm,

Gd,

Tb,

Dy,

Ho or Y ,

the

n e u t r a l b i d e n t a t e l i g a n d i s a t t a c h e d b y t h e c a r b o n y l 0 a n d one of

t h e a z o N atoms.412

lanthanide,

T h e i.r.

s p e c t r a o f M2L3.6H20,

H L = phthalylsulphathiazole, 2

i s bidentate,

where M =

show t h a t t h e l i g a n d 413 v i a t h e c a r b o x y l 0 a n d s u l p h o n a m i d o N atoms.

Spectroscopic Properties of Inorganic and Organometallic Compounds

332 The i.r.

s p e c t r a of

U02L3X2,

where X = C 1 ,

b a s e s d e r i v e d f r o m f u r f u r a l a n d H2NC6H4R, R

o r e-Me

etc.,

,

m-Cl,

0-,2-

show c o o r d i n a t i o n v i a t h e f u r a n r i n g 0 a n d t h e

a z o r n e t h i n e N.414 variety

L = Schiff

SCN,

= H

L i g a n d modes f o r UO;’

a n d Th4’

chelates with a

h e t e r o c y c l i c S c h i f f b a s e s show t h a t t h e l i g a n d s 415 c o o r d i n a t e b y t h e C=N n i t r o g e n a n d p h e n o l i c o x y g e n . of

SiC12L2,

3-,

4-,

w h e r e H L = L-H

o r 5-C1,

5-CH3

NSO C H N=CHC H R - g - O H , and R = ti, 6 3 2 2 6 4 h a v e i . r . s p e c t r a w h i c h show t h a t L

c o o r d i n a t e s b y t h e i m i n o N a n d p h e n o x y 0 atoms.416

Schiff-base

c o o r d i n a t i o n b y t w o o x y g e n a t o m s was s u g g e s t e d f r o m t h e i . r . where X

SnX2.ML,

= C1,

Br,

NCS,

-o-HOC 6H 4 (CR)=NCH 2C H 2 N=C(R)C6H40H-o R2SnL2 a n d R2(L)SnOSn(L)R2, L-leucine,

DL-alanine

of

M = N i or Cut H L =

2

(R

.417

= H o r Me)

where L = N - p h t h a l o y l

or L - p h e n y l a l a n i n e ,

R

= Me,

In

derivatives of Et,

n B ~o r

with a d d i t i o n a l 418 p a r t i c i p a t i o n o f t h e i m i d o C=O i n complex f o r m a t i o n . n-C8H17,

there are bidentate carboxylates,

CI

The i.r. t o Sb,

8.3

s p e c t r u m of

( 8 7 ) s h o w s t h e c o o r d i n a t i o n o f C=O 419 lower t h a n i n t h e f r e e ligand.

s i n c e vC=O i s 90cm-1

1.r.

L i g a n d s c o n t a i n i n g N a n d S atoms.-

d a t a show t h e

c o o r d i n a t i o n o f d i t h i o c a r b a z a t e v i a amino N and t h i o c a r b o x y l a t o

S a t o m s i n NOL2.2H20 dithiocarbazic cm”

acid.

( N = Zr o r V ) a n d UO L .2H 0, w h e r e H L = 420 212 2 V N 2 S 2 i s a t 858cm a n d 6N2S2 a t 450

3-

i n t h e new c o m p l e x ( u - N ~ S ~ ) ( V C ,~ w~ i )t h~ V - N

coordination

(88). 421

(881

(89)

333

Vibrational Spectra of Some Co-ordinated Ligands M(pfth)2,

= (891, M = M n ,

where p f t h -

F e , Co,

Ni,Cu

or Zn,

i n v o l v e c o o r d i n a t i o n v i a azomethine and p y r i d i n e n i t r o g e n atoms, as w e l l a s t h i o l S.422 i n (90)

Characteristic

l i g a n d modes were a s s i g n e d

4 2 3 a n d (91).424

+

-N E iMe3l2

S, HN

rco13

1.r.

spectra o f Co(I1)

2 (1H ) - t h i o n e a n d Co(HL);+,

,

(H L )

complexes o f 4 , 6 - d i m e t h y l p y r i m i d i n e -

i. e . C o ( H L ) 2 ( H 20);f,

a l l reveal N,L-chelation

Co(H L ) 2 N 0 i ,

r i n g n i t r o g e n and t h e e x o c y c l i c sulphur.425

R = 5-methylpyrazol-3-y1,

RCH=NNHC ( S ) N H P h ,

Co(H L ) 2 S C 4

v i a t h e non-protonated CoL;,

where H L =

and r e l a t e d species,

w e r e s h o w n t o h a v e l i g a n d c o o r d i n a t i o n b y p y r a z o l y l N, N and S atoms.426

i n v o l v e d i n c o o r d i n a t i o n i n MLC12, RNHPRNRC(S)NHR, [FeLC1,3C1.427

R

= gtolyl,

M =

Co,

w h e r e L = RNHPPhNPhC (S)NHPh, Ni,

Cu or Zn,

AgL(N03)

Ni,

2-thione.

Zn, Cd, 428

T h e i.r.

where M =

L = 5-methyl-l-phenylhexahydro-l,3,5-triazine-

s p e c t r u m o f Nig(MPDMA)12

w h e r e MPDMA = -S(CH2)3NMe2, ligands are present, however,

and

C o o r d i n a t i o n o f t h e l i g a n d by t h e s u l p h u r atom

was i n f e r r e d f r o m i . r . a n d Raman r e s u l t s o n ML2C12, Co,

azomethine

Phosphazene N and t h i o c a r b o n y l S atoms a r e

involves

N-

w i t h 5-coordination

only.

Pd(MPDMA)2C12,

a n d L - c o ~ r d i n a t i o n . 1:l ~ ~ ~a n d 1:4

a l l y t h i o u r e a l P d complexes o n l y n i t r o g e n atom.430

and r e l a t e d species,

shows t h a t b r i d g i n g m e r c a p t o a m i n e

involve coordination by the

L i g a n d modes d u e t o b r i d g i n g N2S2-

a s s i g n e d i n [M(S2N2)(PPh3)J2, Raman s p e c t r a o f P d ( I I ) ,

w h e r e M = Pd o r

Pt(II),

Cu(I),

Cu(I1)

were Resonance

and H q ( I 1 )

d i t h i z o n a t e complexes i d e n t i f i e d v i b r a t i o n s a s s o c i a t e d w i t h t h e

Spectroscopic Properties of Inorganic and Organometallic Compounds

334

chrornophoric azo group. coordinated,

The P d ( I 1 ) and P t ( I 1 )

w i t h a trans,

square-planar

complex c o n t a i n s a s t r o n g bond t o 5 , s u l p h u r atom on an a d j a c e n t l i g a n d ,

1.r.

structure.432 i n CuL

R'

complexes a r e

configuration;

N,S-

t h e Cu(1)

a n d weak b o n d s t o N,and

a

t o give a polymeric

d a t a were used t o suggest L , N , g - c o o r d i n a t i o n

[where H2L = RC(0)CH2C(R')=NR";

= Ph, R = PhNH; R f l

R'=

R

Me,

= Me,

PhNH e t c . ; 433

= 5-mercapto-3-methyl-l,2,4-triazol-4-yl].

SERS was u s e d t o s t u d y a d s o r p t i o n o f t h i ~ a c e t a m i d eo~r ~ ~

-N , N - - d i m e t h y l t h i o f ~ r r n a m i d e ~ ~o~n

C u o r Ag e l e c t r o d e s .

I n both cases

coordination t o the metal occurred v i a 5 . where H L = 2 - m e r c a p t o b e n z o t h i a z o l e ,

RHgL,

R

= Me o r

Ph,

have

YC=N n e a r 1 5 6 0 ~ m - ~ Some . o t h e r t e n t a t i v e assignments were The i.r. s p e c t r a o f t h e t h i o s e m i c a r b a z i d e

g i v e n . 436

complexes

Sb(CH N S ) X 3 , w h e r e X = C 1 , B r o r I, show t h a t S a n d N ( h y d r a z i n e 5 3 4 37 t e r m i n a l n i t r o g e n ) a r e c o o r d i n a t e d t o t h e S b ( 111).

8.4

L i q a n d s c o n t a i n i n g S and 0 atoms.-

463cm-l,

c o o r d i n a t i o n has t a k e n place.438 No o r W,

have vSO

-0 - c o o r d i n a t i o n grounds.

ZrC14.9DMS0

a s s i g n e d as an S=O d e f o r m a t i o n ,

a t 940cm-1

(W),

( N = N o ) o r 910cm-1

2-2-

where M =

CpPl(CO)3(Ph2SO)t,

by the sulphoxide ligand,

has a band a t

showing t h a t

showing

a s e x p e c t e d on s t e r i c

4 39

The i . r .

s p e c t r u m o f t h e r e a c t i o n p r o d u c t o f Mn(PPhMe

S O 2 shows t h a t c o o r d i n a t e d ,

b r i d g i n g SO2 i s p r e s e n t

2

) B r 2 and

(stoichio-

m e t r y N n L 6 r 2 . $ S O 2 ) . 4 4 0 V i b r a t i o n a l s p e c t r a were r e p o r t e d a n d a s s i g n e d f o r Mn(S03F)3,

Cs2CNn(S03F),1,

N(CO),S03F

( R = Mn o r R e )

SO F . There were s i g n i f i c a n t d i f f e r e n c e s i n SO F 4 3 3 modes f o r u n i - a n d b i d e n t a t e c o o r d i n a t i o n , e x e m p l i f i e d b y t h e M n ( C O ) 5 a n d M n ( C 0 ) 4 d e r i v a t i v e s . 44 1 and Nn(C0)

vP=S

( n e a r 6 5 0 ~ r n - ~a)n d v P - S

f o r Cp#Fe(CO)2L, ql-SP(S)(OR)

,R

u h e r e Cp*

= C H

= E t o r iPr.4225'

and 1 2 2 0 ~ m - ~ ~ Ru(H,O)(PPh,),(tos),, i n

(near 540cm-l)

were a s s i g n e d

C5H4Ne o r C5Ne5,

L =

vS0 b a n d s w e r e s e e n a t 1 1 5 0 where t o s = p--tcluene-

sulphonato, i.e. t h e l i g a n d i s g-coordinated. 443 The c o m p l e x e s 6 ( q - ~ - c y m e n e ) O s ( N e 2 S O ) X C 1 , w h e r e X = C 1 o r Me, h a v e vSO a t 1 0 5 8 ~ m - (Me) ~

o r 1 1 2 0 ~ m - ~ T. h e l a t t e r i s n o r m a l l y i n d i c a t i v e o f

-0 - b o n d i n g ,

b u t t h e c r y s t a l s t r u c t u r e shows t h a t i t i s t h e s u l p h u r 444 atom w h i c h i s bonded i n b o t h cases. The b r i d g i n g SO2 group i n Ir4(CO)S(p2-C0)2(/U2-S02)

bands a t 1265 and 1096 cm-l.

h a s YSO

T h i s c o m p l e x r e a c t s w i t h OMe- t o

335

Vibrational Spectra of Some Co-ordinated Ligands f orm I r 4 ( C O ) 8 ( U 2 - C 0 ) 3 ( S 0 2 0 M e ) - ,

w i t h an 2-bonded m e t h o x y s u l p h o n y l

group:

v

672cm-

P t ( R SO)2C14 a n d t r a n s - P t ( R 2 S 0 ) 2 C 1 2 , w h e r e R 2 2 a l l h a v e a n S - 0 s t r e t c h i n g mode a t 1130-1155crn-1,

or E t ,

.f!”

S=O 1 2 2 7 ~ r n - ~vsS=O , 1090cm-1,

C=N a t 1 5 3 0 c m -

= Me

.

(9 3)

(92)

i.r.

9 7 5 ~ r n - a~n d 6 0 S O

t e r m i n a l l y S - b o n d e d s ~ l p h o x i d e . ~ T~h e ~ complex 1-447

d i a g n o s t i c of (92) has

vS-0

I n S 0 2 2 3*2H20’ I n 2 S 2 0 3 . InOH .2H 2 O a n d I n 2 S 2 0 3 . 21nN03. 2H 2 O s u g g e s t I n - 0 c o o r d i n The

s p e c t r a of

a t i o n i n each case.448

the thiosulphates

1.r. e v i d e n c e p o i n t s t h e p r e s e n c e o f

b i d e n t a t e x a n t h a t e l i g a n d s i n G e O ( S 2 C O R ) 2 . ~ H 2 0 . 4 4 9 1.r. a n d ( 9 3 1 , w h e r e R = H , Me o r E t , R ’ = MeSO 2 Or c o n t a i n t h e expected bands f o r b r i d g i n g methane450 s u l ph i n a t o o r m e t h a n e s u l p h o n a t o l i g a n d s

Rarnan d a t a f o r MeS03,

all

.

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-

24,

527,

526,

290,

107.

24,

282,

-wan

Vibrational Spectra of Some Co-ordinated Ligands 45 46 47 48 49

50 51 52 53 54 55 56 57 58 59 60 61 62 63 64

65 66 67 68 69 70

W.L.Parker, A.R.Siedle a n d R.M.Hexter, J. Arner. Chern. S O C . , 1 9 8 5 , 107, 2 6 4 . F.J.GaXa A l o n s o , A.Htlhn, J.Wolf, H . O t t o and H.Werner, Anqew. Chem., I n t . Ed. E n g l . , 1 9 8 5 , 24, 4 0 6 . q a n o m e t a l . Chem. , 1 9 8 5 , 282 ,C31 W.A.Herrmann a n d C .Weber, J . O r g J . O r q. a n o r n e t a l . Chern., 1 9 8 5 , L . D a h l e n b u r g a n d N.Hllck, 129 H . H o b e r g , K . S h m e r m a n n a n d A . M i l c h e rr ee ii tt ,, J. Or9 O r q anomet a 1 Chern., 1 9 8 5 , 2 8 8 , 237. D . W a l D e r , E . D x u s , H .Gllrls, J . S i e l e r , 0. L i n d s v i s t a n d J. O r g a n o r n e t a l . Chern. , 1 9 8 5 , 286, 1 0 3 . L.Andersen, K.R . P b r s c h k e , R . M y n o t t , K.A n o e r r n u n d a n d C .Kr\lraer, 199. Z. Naturforsch., T e i l B , 1 9 as’, E.Hernandez, I . S a e z a n d P.R o y o , J. O r q a n o r n e t a l . Chem. 9 1 9 8 5 , 293, 249. T .P.Beebe, M.R . A l b e r t a n d J . T . Y a t e s , J. C a t a 1 . , 1 9 8 5 , 96, 1. G . W a s a p o l l o , C .F . N o b i l e a n d A.Sacco, J. O r g a n o r n e t a l . Chem., 1985, 435. M . O n i s h i , K . H i r a k i , Y .Ohama a n d A . K u r o s a k i , J . O r g a n o m e t a l . Chern., 1 9 8 5 , 284, 4 0 3 . I n t . Ed. E n q l . , H.Ebner, H.Otto and H.Werner, Anqew. Chern., 1 9 8 5 , 24, 5 1 8 . G .Facchin, R .Campostrini and R .A.Michelin, J. O r g a n o m e t a l . Chern., 1 9 8 5 , 294, C21. H.M.Ceder and J.Sales, J. O r q a n o m e t a l . Chern., 1 9 8 5 , 294, 3 8 9 M.A.Bennett and A.Rokicki, Orqanometallics,l985, 4, 1 8 0 . J. Chern. TOC., C.R.Langrick, P.G.Pringle a n d B.L.Shaw, D a l t o n Trans., 1985, 1015. 1. A . U a v i e s , C . S . H a s s e l k u s , C.N.Scirnar, A.Sood a n d W.Uma. J. Chern. S o c . D a l t o n T r a n s : , 1 9 8 5 , 2 0 9 : J.S.Thompson and R.M.Swiatek, I n o r q . Chern., 1 9 8 5 , 24, 1 1 0 . L.Naldini, F.Dernartin, M.Manassero, M.Sansoni, G.Rassu a n d M.A.Zoroddu, J . O r q a n o m e t a l . Chern., 1 9 8 5 , 279, C42. J.W i c e n t e , M.T .Ch i c o t e , J. A .C a y v e l a s , J . F e r n a n d e z - B a e z a , P.G.Jones, G.M.Sheldrick and P.Espinet, J . Chem. S O C . , D a l t o n T r a n s . , 1 9 8 5 , 1 1 6 3 . E7 0 . F i s c h e r a n d M.Bbck, J. O r q a n o r n e t a l . Chem., 1 9 8 5 , 2 8 7 , 2 7 9 M. L . P a t t e r s o n , J. P h y s . Chern., 1 9 8 5 , 8 9 , 5 0 4 6 a n d M.J.Weaver, J. Ph s. Chern., 1 9 8 5 , 89 5 0 4 0 . P. Gao a n d M.J.Weawer, 1 9 8 4, H . L a n g e a n d D.Naumann, J. F y u o r i n e Chern., 435. K. K a r n i e n s k a - T r e l a , H. I l c e w i c z , H . B a r a n s k a a n d A.Labudzinska, B u l l . P o l . Acad. S c i . , C h e r n . , l 9 8 4 , 32, 143. T.S.Dory, J.J.Zuckerrnann a n d M.D.Rausch, J.OrqanoGta1. Chern., 1985, C8. A .A .Tsyganenko, L. A . D e n i s e n k o , S .M. Zwer ew a n d W N .F i l i r n o n o v , J. Catal., 1 9 8 5 , 94, 10. L.B . K o o l , M.D.Rausch, H .G.Alt, M.Hereberhold, 8.Wolf and J. O r q a n o r n e t a l . Chern., 1 9 8 5 , 297, 1 5 9 . U.Thewalt, U.Belforte, F . C a l d e r a z z o and P.F.Zanazzi, Gazz. C h i r n . I t a l . , 71. 1985, R.M.Kowaleski, D.O.Kipp, K.J.Stauffer, P.N.Swepston a n d F.Basolo, Inor Chern., 1985, 24, 3750. K . I h r n e l s a n d D ? R e h d e r , O r q a n o r n x a l l i c s , 1 9 8 5 , 4, 1 3 3 4 . K. I h r n e l s a n d D.Rehder, O r g a n o r n e t a l l i c s , 1985, 1340. F .Calderazzo, M.Castellani, G . P a r n p a l o n i a n d P.F . Z a n a z z i , J. Chern. SOC., D a l t o n T r a n s . , 1 9 8 5 , 1 9 8 9 . P.H . B i r d , A . A . I s m a i 1 and I . S . B u t l e r , I n o r q . Chern., 1 9 8 5 , 24, 2 9 1 1 .

284,

.

*,

72 73 74 75 76 77

76




h o e s s b a u e r s p e c t r a of At 2 9 8 K t h e

0.951, h a v e b e e n recorded243.

s p e c t r u m c o n s i s t e d of a n a s y m m e t r i c d o u b l e t w h i c h w a s f i t t e d t o a f e r r o u s s i n g l e t , t w o f e r r o u s d o u b l e t s , a n d a f e r r i c singlet. 4.2K,

h o w e v e r , a l a r g e n u m b e r of u n r e s o l v e d

The room-temperature

At

lines w e r e obtained.

spectra were related to a model of the defect

s t r u c t u r e of wuetite.

T h e M o r i n t r a n s i t i o n in n a t u r a l h a e m a t i t e h a s b e e n e x a m i n e d

No specific-heat

244

.

anomaly due to the Morin transition was found,

a l t h o u g h t h e e x p e c t e d c h a n g e s w e r e s e e n i n t h e M o e s s b a u e r spectra. T h e r e s u l t s w e r e c o n s i s t e n t w i t h t h e c o e x i s t e n c e of t w o p h a s e s and a spread of a b o u t 4 0 K o v e r w h i c h t h e t r a n s i t i o n s t a k e place. S u b m i c r o n p o w d e r s o f h a e m a t i t e and m a g h e m i t e h a v e b e e n studied.

242

T h e e f f e c t s of s m a l l a l u m i n i u m s u b s t i t u t i o n s i n h a e m a t i t e h a v e been examined245.

C h a r a c t e r i s t i c M o e s s b a u e r t e m p e r a t u r e s and

i n t r i n s i c isomer s h i f t s w e r e d e t e r m i n e d u s i n g t h e D e b y e a p p r o x imation,and

a m a x i m u m w a s f o u n d in b o t h p a r a m e t e r s at 4 mol.%

substitution.

A1

A d i a m o n d a n v i l c e l l h a s b e e n used in a M o e s s b a u e r

e f f e c t and X - r a y d i f f r a c t i o n s t u d y o f F e 2 0 3 at p r e s s u r e s up t o

60 GPa246.

Although two components were found in the high-

pressure Moeesbauer

a p e c t r a , t h e X - r a y d a t a c o u l d n o t be e x p l a i n e d

by t h e c o r u n d u m structure.

A simple high-spin to low-spin

t r a n s i t i o n could n o t , t h e r e f o r e , be c o n s i d e r e d f o r t h e 5 5 G P a p h a s e t r a n s i t i o n i n Fe203.

Two independent studies have been

p u b l i s h e d o n Co-doped

delta-Fe203.

In the first, an emission

s t u d y , it w a s found that s o m e of t h e c o b a l t a t o m s d i f f u s e d i n t o t h e

378

Spectroscopic Properties of Inorganic and Organometallic Compounds

delta-Fe

0

hour247.2

l a t t i c e a f t e r h e a t t r e a t m e n t at 300°C :he

for one

s e c o n d s t u d y d i s c u s s e d t h e c o e r c i v e f o r c e and

M o e s s b a u e r s p e c t r a in t e r m s of t h e d e g r e e of p e n e t r a t i o n of C o 2 + A M o e s s b a u e r and m a g n e t f s a t i o n

i n t o t h e o x i d e lattice248.

of f i n e l y d i s p e r s e d a n t i f e r r o m a g n e t i c A1 0

2 3 matrix has been reported

249

study

g r a i n s of F e 2 0 3 in a n

.

A Moessbauer emission study250 has been made o n the system Lal-zSrxCol-yTiy03

= 0 or

(for

2)

over the temperature

No h y p e r f i n e s p l i t t i n g e w e r e observed e v e n at 77K.

r a n g e 77-800K.

D i f f e r e n c e s i n b e h a v i o u r b e t w e e n t h e t w o s y s t e m s w e r e e x p l a i n e d by t h e g e n e r a t i o n of d i f f e r e n t v a l e n c e and s p i n s t a t e s of c o b a l t w i t h increasing

x.

Other systems which have been studied are Cr-doped

n i c k e l f e r r ~ a l u m i n a t e ~ ~Slr?0 * 5 . 6 F e 2 0 3 doped w i t h barium b o r a t e or kaolin252, and S c 2 0 3 - 2 wt.% Fe203. 2 53

M a g n e t i t e and S p i n e l - t y p e Oxides. been studied254.

Ultrathin Fe304 films have

T h e s e f i l m s are s u p e r p a r a m a g n e t i c a t low

t e m p e r a t u r e s and p a r a m a g n e t i c at r o o m temperature.

The room-

t e m p e r a t u r e s p e c t r a c o n s i s t e d of t h r e e d o u b l e t s w h i c h w e r e a s s i g n e d t o F e 3 + in t h e

A

site

and Fe2.5+

and F e 2 + in the

site.

M o e s s b a u e r s p e c t r a of h y d r o u s s p i n e l iron o x i d e c o l l o i d s and t h e i r e v o l u t i o n w i t h t h e r m a l t r e a t m e n t h a v e b e e n i n t e r p r e t e d by u s i n g a modified Weiss local field

Interparticle interactions

w e r e found t o o v e r c o m e t h e s i n g l e - p a r t i c l e

a n i s o t r o p y energy.

In

a n o t h e r p a p e r t h e s p e c t r a l and p h y s i c o c h e m i c a l p r o p e r t i e s of s u b m i c r o n p o w d e r s of Fe304 w e r e r e l a t e d t o its M o e s s b a u e r spectra. 2 4 2

A s t u d y of c o v a l e n c y e f f e c t s and t h e p r e s s u r e

d e p e n d e n c e of the M o e s s b a u e r isomer s h i f t s f o r s p i n e l - t y p e f e r r i t e s has b e e n described256.

Although

the cubic lattice parameter was

the d o m i n a n t i n f l u e n c e o n the p r e s s u r e d e p e n d e n c e of t h e isomer s h i f t , c o n s i d e r a t i o n of c o v a l e n c y e f f e c t s w a s a l s o r e q u i r e d t o i n t e r p r e t t h e spectra.

Electron

l o c a l i s a t i o n in f e r r o s p i n e l s w i t h

a m i x e d - v a l e n c e t e t r a h e d r a l s u b l a t t i c e h a s b e e n i n v e s t i g a t e d using Moessbauer spectroscopy257.

T h e b e s t i n t e r p r e t a t i o n of t h e

s p e c t r a a s s u m e d c o m p l e t e l y localised

e l e c t r o n s at r o o m t e m p e r a t u r e

w i t h t h e p r e s e n c e o f s o m e , 4-17%, m i x e d - v a l e n c e

i r o n d u e t o fast

e l e c t r o n r e l a x a t i o n s a b o v e 440K.

i n t e r a c t i o n s in

Superexchange

fluorosubstituted ferrites have also been studied

258

.

Mossbauer Spectroscopy

379

T w o papers have been published o n Mo-bearing ferrites259,260 F r o m X P S and M o e s s b a u e r s p e c t r a it w a s s u g g e s t e d t h a t F e 2 M o 0 can be described as

-

M o e s s b a u e r s t u d y o f F e 3-xMz04

(M = A l , Gal h a s b e e n

describedz6'.

[Fe2+Mo4+IoctO4.

4

A

Measurements m a d e at low temperatures using

a p p l i e d m a g n e t i c f i e l d s w e r e used t o s t u d y t h e c a t i o n distribution. T h e formation kinetics of mechanically

a c t i v a t e d NiFe204 h a v e

b e e n s t u d i e d as a f u n c t i o n of t h e m e c h a n i c a l a c t i v a t i o n intensity262.

The effects of oxygen loss o n t h e crystallographic

and m a g n e t i c p r o p e r t i e s of CuFe204 h a v e b e e n e x a m i n e d and t h e r e s u l t s of d i f f e r e n t h e a t t r e a t m e n t s described263. Gaf+ f n d ",S

content264.

Cation distributions were deter-

mined at r o o m t e m p e r a t u r e and 4.2K

4

and f e r r o u s ions w e r e f o u n d i n the Moessbauer effect reported. 265 ' 266 Li0.5Fe2.5-zCrz04,

i n an e x t e r n a l m a g n e t i c field,

sites.

of l i t h i u m f e r r i t e , Li0.5Fe2.504,

and t h e e f f e c t s of z i n c s u b s t i t u t i o n

C h r o m i u m - s u b s t i tut ed 1 i th ium f e r r i t e s , h a v e b e e n s t u d i e d f o r 5 = 0-2. 26 7 , 2 6 8

c o n c e n t r a t i o n s o f up t o 5 = 1.2,and occurred w h e n

x

=

The thermal decomposition

has been studied265 with

S i x - l i n e s p e c t r a w e r e o b t a i n e d f o r both

increasing

Ferrimagnetic

O4 h a s b e e n s t u d i e d as a f u n c t i o n of t h e

G a S n Fe3,x

1.6.

4

and

B

sites with chromium

a ferromagnetic relaxation

T h e d e c r e a s e in i n t e r n a l m a g n e t i c f i e l d w i t h

w a s q u a l i t a t i v e l y e x p l a i n e d by c o n s i d e r i n g a d i p o l a r

f i e l d , zero-point

s p i n d e v i a t i o n terms,and a s u p e r t r a n s f e r r e d

hyperfine field,while the relaxation effect was explained o n the b a s i s of d o m a i n w a l l d i s p l a c e m e n t s . Manganese-zinc igations. 269-272

f e r r i t e s h a v e b e e n t h e s u b j e c t of t w o i n v e s t T h e e f f e c t s of s i n t e r i n g and c a t i o n

d i s t r i b u t i o n s w e r e examined.

Paramagnetic clusters found after

a n n e a l i n g w e r e a t t r i b u t e d t o n o n - r a n d o m o r d e r i n g c a u s e d by local c h a r g e c o m p e n s a t i o n n e a r c a t i o n v a c a n c i e s 269'270.

In the other

s t u d y , e l e c t r o n e x c h a n g e b e t w e e n i r o n and m a n g a n e s e w a s s t u d i e d a s a f u n c t i o n of c o m p o s i t i o n 2 7 1 and t h e d i f f e r e n c e s b e t w e e n t w o The magnetic 2 73 p r o p e r t i e s of Z n x M g l - x F e 2 0 4 h a v e b e e n s t u d i e d at 77K b a t c h e s o f d i f f e r e n t q u a l i t y w e r e examined272. and 2 9 8 ~ ' ~ ~ . F o r x

-


-SnCl~(dmso)~ trans-SnC 14( dmf ) 2 ci~-SnCl~(dmf)~

0.57

tran~-SnBr~(dmf)~

0.66

0.83

c i s - Sn B r ( dm f )

0.66 0.38

0.44 0.78

0.38

0.45

trans-SnC14(dma) >c

- Sn C 1

( dm a )

2

complexes

halides

'translAtrans

1.5 1.4 1.4

1.9

1.7

Spectroscopic Properties of Inorganic and Organometallic Compounds

400

h

In

c .-

C

3

I

1

-4.32 -2.16

I

0

I

2.16

1

4.32

V e l o c i t y / mm s-1 Figure 2

M o e s s b a u e r s p e c t r a o f ( a ) SnC14(tht)2,

(c) SnC14(dmso)2,

( d ) SnC14(dmf)2,

u p p e r s p e c t r u m of e a c h p a i r c o r r e s p o n d s t o t h e ( R e p r o d u c e d b y p e r m i s s i o n f r o m J. C h e m .

1 9 8 5 , 1281)

( b ) SnBr4(dmf)2,

a n d ( e ) SnC14(dma)2.

Soc.,

Cis

The

isomer.

D a l t o n Trans.,

Mossbauer Spectroscop,y

40 1

The interaction of SnC14 and SnBr4 with a series of cyclic and aromatic ethers in solution and in the solid state was determined by a combination of Moessbauer spectroscopy and infrared and n.m.r.

data.

The data for nine SnC14L2 complexes were

found to be consistent with octahedral tin geometry and transcoordinated liganda in the solid state471.

Variable-temperature

Moessbauer spectroscopy was used along with other techniques to study a range of new complexes of tin(1V)

halides with 2,2'-azo-

All of the new complexes have 1:1 stoichiometry with tin

pyridine.

in distorted octahedral sites with four bonds to halogen atoms, one to a ligand azo-group N atom, and one to a ligand ring 4 72 nitrogen. The possible use of the Sn(IV)

complex of potentially

tridentate dianionic molecules (L) as extractants for tin was studied.

As part of the study, compounds of the type SnL2 and

SnC12L2 were prepared and characterised by Moessbauer spectroscopy.

The best extraction was obtained with L = 2-(2'-hydroxy473

phenyl)-8-quinoliriol

The tin(1V)-cyanide

.

derivations SnC12CN(Me3SiCN)

and

solvated SnC12XCN compounds (X = Br, I) have been prepared and characterised by Sn-119 Moessbauer s p e c t r o ~ c o p y ~ ~The ~. quadrupole splitting of SnC13CN(Me3SiCN)

is essentially

temperature independeni in the range 77-291K,but the isomer shift decreases linearly with temperature at the rate of 3 . 0 4 x -1 K - l because of second-order Doppler shifts. The slope

mm s

of the d(lnA)/dT

graph is -1.0 x

K-I, and this is in the

range expected for a polymeric tin-containing structure. Two papers 465'476 published during the review year dealt with compounds containing Sn-transition-metal bonds.

A study of the

temperature dependence of the recoil-free fractions in the range 77-300K was carried out on complexes of tin halides with platinumgroup metals.

It was suggested that the temperature dependence of

the fraction depended upon the strength of the bonds to Sn and so the normal vibrations of the Sn atom vibrations could be calculated.

The change

in the temperature dependences between

the complexes was explained in terms of an increase in the number of low-frequency vibrations in the order Br < C1 < F. 475

Sn-119

Spectroscopic Properties of Znorganic and Organometallic Compounds

402

Moessbauer data were used476 to confirm the presence of the stannandiyl moiety in the compound ( 3 ) , which reacts with thf to give ( 4 ) .

The following tin-containing materials with Moessbauer resonance lines in the Sn(IV) in this chapter:

region of the spectrum were mentioned earlier

oxide,410 indium tin oxide,424 chloride,4 1 1

~ u l p h i d e ,and ~ ~ tin ~ in glass surfaces,413 passivation f i1m,446

in hydroxide

in electroplating sludges ,449

in alloy

oxidation products,434-436 and in substituted diphosphonic acid 4 53 solutions. Organotin(1V)

Compounds.-The

Moessbauer data for trimethyl- and

triethyl-organotin oxide compounds are listed in a recently published part of

'Gmelin Handbook of Inorganic Chemistry' 477

The methylstannanes SnMe4

-E

H

n

.

( E = 1-31 react with fluoro-

sulphuric acid at -9OOC to produce SnMe3-nH+ species.

Sn-119

Moessbauer data were used to show that these species decomposed at higher temperatures4".

The spectra for the decomposed sample

from solutions of SnMeH2+ show a tin(I1)

resonance with shift

and splitting data of 4.42 and 0.6 mm s-l that are similar to Sn(S03F)2

and a tin(1V)

resonance with shift and splitting data

of 1.86 and 5.22 mm s-l respectively that are similar to those of SnMe2(S03F)2, suggesting the following decomposition reaction:

Mossbauer Spectroscopy

403 2SnMeH2+

SnMeq2+

+

4HS03F

+ Sn2+ + H2S04 + SO2 + 2HF + 2H2 + 2S03F-

The spectra obtained from heated solutions of SnMe2H2 and SnMe H in fluorosulphuric acid contain one resonance 3

-

a Sn(IV)

spectrum with parameters similar to those of SnMe2(SO3FI2. The gamma-resonance data were included in a study of the spectroscopic and thermal-decomposition behaviour of the glycylglycine complexes RSnCl (H glygly). 478 The isomer shifts 3 2 show the expected trends in that they have lower values for the complexes than for the parent monoorganatin trichlorides.

These

shifts. are also lower than those of the corresponding diorganotin dihalide complexes,and this is consistent with the expected increase in the use of tin 2-electrons when chloride is replaced by an alkyl group.

The shift data for the diorganotin complexes

R2C12(H2glygly) (R = Me, n-Bu, n-Oct,and Ph) suggest that the bonding between the tin atom and the glygly ligand is relatively weak.

P-31, C-13 and proton n.m.r.

spectra have been used along

with Sn-119 Moessbauer data in studies on mono-, di-,and triorganotin(1V)

d i a l k y l t h i o p h o ~ p h a t e s ~ ~ The ~ . n.m.r.

data are

consistent with tetrahedral tin sites in triorganotin(1V)

compounds

the Moessbauer spectra do

such as Me3Sn[SSP(OEt)2],although

suggest five- rather than four-coordinated tin.

The Moessbauer

isomer-shift data suggest weak Sn-S bonding to the ligand. The structures of the alkyltin iso-octylthioglycollates (IOTG) R2SnC1n(IOTG)2-Q

(n

= 0 , 1) and RSnn(IOTG)3-E

have been investigated with n.m.r. with gamma-resonance data480.

(1 = 0-2)

and some of the results compared

Isoactylthioglycollate and

isocretyl maleate derivatives were also included in a Moessbauer study of the degration of organotln-stabilised PVC411.

The

Moessbauer effect was used to show that the organic groups in diorganotin halideadducts with 2,2'-azopyridine are in trans472

positions in a s i x - coordinated Sn site

.

The temperature dependence of the recoil-free fraction for thirteen phenyl- and eleven cyclohexyl-tin compounds has been

Spectroscopic Properties of Inorganic and Organometallic Compounds

404

investigated481.

The compounds chosen either had known crystal

structures or had structures that could easily be inferred from other data.

The phenyl compounds that were known to consist of

non-interacting monomers all had large values for the temperature dependence of the recoil-free fraction C(1.37

-

2.8) x lo'2K-1]

that reflected the relative vibration freedom of the tin atoms in each case.

The phenyltin compounds that were known to be polymeric

fell into two groups with temperature dependences of about 1.1 x 10-2K-1 and 1.8 x 10-2K-1 respectively.

The values for the

second group fell in the range normally associated with non-polymeric systems.

In order to interpret the data, the authors defined

the polymers in terms of three layers of complexity:

the primary

structure, is related to the monomer from which the polymer is built, its coordination number, geometry, stereochemistry, etc.; the secondary structure, is used to describe the dimensionality of the polymer, one-, two-dimensional, chain, sheet, etc.;

and the

term tertiary structure, which covers the three-dimensional disposition of secondary structure.

While the primary and secondary

structures play a major role i n defining the characteristics of the polymer, they do not alone necessitate a restriction in the vibrational motion of the atom

incorporated into the polymer, as

evidenced by the data for the second group of phenyltin polymers. The Moessbauer variable-temperature role of the polymer's structure has therefore to be considered more fully.

of tertiary structure were identified,% with linear Sn-X-Sn linkages,

tertiary

Four classes

(1) rod-like structures

(2) zig-zag structures with bent

Sn-X-Sn linkages where X is a simple group such as a halide or hydroxide,

( 3 ) zig-zag structures with bent Sn-X-Sn linkages where

the X group is larger and forms a more flexible S-shaped bridging link,and ( 4 ) structures with very flexible X groups that can form a helical polymer.

In terms of the variable-temperature Moessbauer

data, the lattice rigidity decreases (a) with decreasing strength of the Sn-X bridging bond and (b) with increasing displacement of the bridging mass away from the Sn...Sn

vector, i.e.

in the order

rod-like structures, zig-zag structures, S-shaped structures and helical structures.

Compounds with the latter two structures show

the highest values for the temperature dependence of the recoilfree fraction,while the most rigid of the structures, the rod-like structures, have the lowest values.

The variable-temperature

Moessbauer data for the cyclohexyltin compounds were interpreted in

M ossbau er Spectroscopy

405

a similar fashion to those of the phenyltin compounds in that monomers [such as Sn(C6H11)3BrI

and weakly polymeric

compounds [such as Sn(C6H11)3(02CMe)]

have the highest

values of temperature dependence of f while rod-like polymeric materials [such as Sn(C6H11)3C1]

have low values.

A number of new complexes of diorganotin(1V)

compounds with

nucleosides have been prepared and characterised using a number of 482 spectroscopic techniques including Moessbauer spectroscopy

.

The gamma-resonance parameters were also discussed in a study of the antitumor activity of di- and tri-organotin complexes with 483 amino acids

.

The crystal structure of dimethyltin(1V) thioate has been determined. was found to be 137.3O

bispyrrolidinecarbodi-

The Me-Sn-Me angle in the structure

in contrast to that of 123.5O predicted

from the Moessbauer parameters of this compound

.

484

Sixteen compounds of general formula R2SnL2 and R2(L)SnOSn(L)R2(where

L is an N-acetylamino acidlhave been prepared and

characterised.

The data for the R2SnL2 have been interpreted

in terms of the presence of distorted trans-octahedral tin sites, while those for the R2(L)SnOSn(L)R2

compounds were said to be

consistent with 5-coordinated tin sites with bridging oxygen atoms 485 and nearly linear C-Sn-C groups. The chemical isomer-shift data for the compounds R3SnX (R = alkyl, phenyl, X

= F,

C 1 , OH, OR1, C N , NCS, NC0,or N g ) have been

correlated with partial atomic charges on the tin.

A

unique shift-

partial atomic charge relationship was obtained for all five coordPartial quadrupole splitting values inated R SnL species486. 3 were used to suggest the coordination of the tin atoms in a series of 2 2 organotin compounds (Rn-3Rt3Sn)2X489.

Harrison et al.

have characterised two trimethyltindipeptide methyl ester complexes488, and the Sn-119 Moessbauer ef fect has been used to help in the description of the bonding in organotin(1V)

esters of

tetramethylenedithiocarbamic acid489.

Eleven n e w complexes of

Ph3SnC1 with t j - a l k y l s a l i c y l i d e n e i m i n e s

have been prepared and

characterised with infrared, n.m.r., data490.

and Moessbauer spectroscopic

The data are consistent with trigonal-bipyramidal tin

Spectroscopic Properties of Inorganic and Organometallic Compounds

406 environment ( 5 )

in which the Sn is bonded to the ligand through the

phenolic oxygen atoms.

Both Sn-119 Moessbauer and Sn-119 n.m.r.

data have been

collected for a series of sterically hindered tetraorganotin(1V) derivatives491.

The most unusual spectra obtained were for

tetra-adamant-1-yltin, Sn(ad)4

(see Figure 3 ) .

101.0 100.5

-e

100.0

n 0

99.5

C

.-

.-:99-0

E, 2

98.5

t-

9 8.0 97.5

9 7.0

Figure 3

Sn-119 Moessbauer spectrum of Sn(ad)4

(Reproduced by permission from J. Chem. S O C . ,

at 80K Dalton Trans.,

1985, 169) At 80K the spectra show evidence for two tin sites, one with a large quadrupole splitting (2.7 mm s - l > and one with a small quadrupole splitting ( 0 . 7 6

mm s”)

.

The variable-temperature

data also show the two sites over the temperature range studied. From the ratio of the resonance lines the site with the larger

Moss bauer Spectroscopy

407

s p l i t t i n g m u s t a c c o u n t f o r t w o - t h i r d s of t h e S n a t o m s in Sn(adI4. M o l e c u l a r m o d e l s showed t h a t f o u r ( a d ) g r o u p s around a t i n a t o m w i t h n o r m a l Sn-C d i s t a n c e s w o u l d r e s u l t i n an e x t r e m e l y s t e r i c a l l y h i n d e r e d s t r u c t u r e , a n d it is likely t h a t at least o n e Sn-C bond would be longer than the others

(6)

or that a n effectively three-

c o o r d i n a t e d t i n s t r u c t u r e w o u l d be f o r m e d w i t h t h e f o u r t h ( a d ) g r o u p b a l a n c i n g t h e c h a r g e in t h e l a t t i c e coordinated structure would be formed

(7)

(8).

o r that a five(6),

Site

the

. ad ad-

(6)

distorted

(7)

t e t r a h e d r a l 5ite,could

low q u a d r u p o l e s p l i t t i n g , w h i l s t

account for the resonance with the t h e f i v e - o r three-coordinated

could a c c o u n t € o r t h e r e s o n a n c e w i t h t h e larger splitting. isomer s h i f t s f o r b o t h of t h e s i t e s in Sn(adl4 s

-1

a r e a b o u t 1.6

and a r e t h e l a r g e s t y e t r e c o r d e d f o r SnR4 compounds.

high s h i f t s w e r e said to be due t o t h e e l e c t r o n - d o n a t i n g

of t h e ( a d ) g r o u p s , a l l o w i n g m o r e :-electron

sites The mm

The properties

density to remain o n

the tin atoms.

T h e M o e s e b a u e r s p e c t r u m at 80K f o r q u e n c h - f r o z e n a l s o b e e n obtained4’l.

S n P h 4 has

T h e s p e c t r u m c o n s i s t s of a s i n g l e t w i t h a

l a r g e l l n e w i d t h w h i c h n a r r o w s o n a n n e a l i n g at 1 9 3 K t o g i v e a n a r r o w line.

T h e a u t h o r s s u g g e s t e d t h a t t h e m o s t l i k e l y e x p l a n a t i o n of

t h i s e f f e c t i s t h a t d e f e c t s caused

in t h e s t r u c t u r e d u e t o c r a c k i n g

and i n t e r n a l s t r e s s could g e n e r a t e t h e w i d e l i n e and t h a t a n n e a l i n g would r e m o v e t h e defects.

M a n y o t h e r c o m p o u n d s of t h e t y p e

SnR3R‘ that contain potentially sterically hindering groups bonded

t o t i n a l s o h a v e broad

preted

in t h e s a m e w a y as t h e d a t a f o r SnPh4.

s i n g l e t r e s o n a n c e s that c a n b e i n t e r -

Spectroscopic Properties of Inorganic and Organometallic Compounds

408 6

OTHER ELEMENTS

This section reviews the data for elements other than iron o r tin. In each of the three main subsections (main-group elements, transition-metal elements, and lanthanide and actinide elements) the isotopes are discussed in order of increasing atomic number. Main-Group Elements.-

Antimony (Sb-121).

The Sb-121 Moessbauer and

Raman spectroscopic data for a number of antimony compounds are 492 presented and discussed in a thesis

.

Variable-temperature gamma-resonance data in the temperature

-

region 4.5

150K for polycrystalline antimony were used493 to

obtain a Debye temperature of 180K for the element.

T h e isomer

shift for Sb at 1OOK was measured as -11.4 mm 8 - l from a BaSnO

3

source cooled to 100K,and no quadrupole broadening of the single resonance line was detected.

Variable-temperature Moessbauer data

have also been obtained for InSb over the range 11-16OK and for 3 methylpyridinium t e t r a b r o m o a n t i m o n a t e ( I I I ) ,

2-chloropyridinium

t e t r a b r o m o a n t i m o n a t e ( I I I ) , and Me SbC12 over the range 11-1OOK. 3 There is n o evidence from the data of large anharmonicity effects

or temperature dependence of the characteristic Moessbauer temperature for any of the compounds over the temperature ranges studied.

The Debye temperature determined for InSb using the thin

absorber approximation was 1 6 0 2 5K.

494

The Moessbauer effect has been used to study the electronic configurations of Sb present both as a component of and a s an added impurity to 111-V and 11-VI semiconductors.

The impurity effects

were studied by measuring the emission spectra from implanted Moessbauer Xe-121, which decays via Te-121 to ~ b - 1 2 1 ~ Antimony ~ ~ . spectra have also been used to study the vitreous products obtained in the glass-forming region of the T 1 S-Sb2S3 system, that is 2 over the composition range 60-95 mole % Sb2S3. The Moessbauer spectra were interpreted in the light of the measured glass transition

temperature^^'^.

In another study of antimony

sulphides, Moessbauer spectroscopy was used to determine the 49 7 oxidation state of the Sb atoms present

.

Moessbauer spectra have been obtained for the antimony(II1)

Mossbauer Spectroscopy catecholatohalides

409 (C6H402)SbX,and

the data are said to be

consistent with a trigonal-bipyramidal distribution of electron pairs around Sb. 498

A crystal-structure determination of

(L = catechol, phen

CSbL(phen)21BPh4

=

1,lO-phenanthroline)

showed that the antimony atom is part of a complex catecholatoantimony(II1)

unit chelated by two phenanthioline Ligands.

The

three Ligands coordinated to the Sb are arranged s o that space is left for a sterically active non-bonding electron pair. Moessbauer parameters of [SbL(phen)21BPh4 499 terms of the crystal structures

.

The

are discussed in

The infrared spectra and Moessbauer parameters of P 0 2 3' 2SbC15 are consistent with complex formation between SbCl 5 molecules and the terminal 0 atom of the P 2 0 3 group5''. The Sb-121 data for the Sb(V)

compounds Sb02F, SbOFC12,

Sb5O7Cll19 and CSbCl (OPMe )] have all been shown to be 4 2 consistent with the presence of octahedrally coordinated 501 antimony ( V )

.

The synthesis of SbC15-doped polyacetylene has been described502.

The doped polymer samples containing molar

compositions of 0.005-0.125

SbC15 were characterised by a number

of techniques including Moessbauer spectroscopy.

The gamma-

resonance data for samples doped with less than 0.005 moles of SbC15 unequivocally demonstrate only the presence of SbCl 3' while samples doped with >0.07 moles SbC15 show resonance lines from both Sb(II1) and Sb(V) Tellurium (Te-125).

502

.

A value of A R / R

of 0.76 x

was obtained

for the 35.4 keV Te-125 isotope from emission and conversionelectron studies on 1-125 implanted in the metal matrices C u , Sn, P t , T e , Au,and Zn503.

A uniform charge distribution of 1.2 x

A l l 3 fm was assumed. The phase transitions in Te02 with pressure were studied on single-crystal and polycrystalline samples over the pressure range 12-50 kbar.

A second-order transition from tetragonal to

orthorhombic was identified at about 9 kbar,and the material 504 becomes brittle at about 12 kbar.

410

Spectroscopic Properties of Inorganic and Organometallic Compounds Moessbauer effect studies have been carried out on nucleogenic

Te-125 monomers formed by the decay of Te-125m embedded in solid Ar505.

The Te-125 spectrum consisted of two components: (1) a

quadrupole split component with shift and splitting values of 0.35 -1 mm s (from ZnTe) and 9.2 mm s - l respectively and (2) a singlet with shift 0.15 mm s-’. attributed to a Te(0)

The quadrupole sub-spectrum was

species and the singlet to a Te(-l)

species.

A novel single-line absorber, Mg3Te06, with a high recoil-free fraction was developed for Te-125 emission experiments.

The data

obtained were used, along with relativistic Dirac-Slater calculations, to produce a new isomer-shift calibration curve for Te-125.

The calibration consisted of a non-linear relationship

between shift and the number of p-holes in the closed-shell 5e25p6 configuration. The change in the mean-squared charge 2 radius A(E ) for Te-125 calculated from the calibration was 3.4 x

fm2.

Iodine (1-127 and 1-129).

Moessbauer effect studies were carried

out on the nucleogenic 1-129 monomers formed by the decay of Te-129m in solid Ar505.

The spectrum from this dilute rare-gas

matrix-isolated ion-implanted sample was a single quadrupole split resonance peak with a shift 0.75 mm s-l from a ZnTe source and a splitting -685(20)HMz

that was attributed to an I ( 0 ) species.

A

new single-line absorber, Na5106, with a high recoil-free fraction for Te-129m emission studies was developed. The change in 2 the mean-squared charge radius A ( L ) obtained for 1-129 from the calibration data for isomer shifts was 19.9 x 10m3fm2. The 1-127 Moessbauer data for a series of CuI complexes listed have been obtained. 506

The most striking feature of the spectra

is that none of them displaysany resolvable quadrupole coupling. In fact, the linewidths of the spectra obtained by assuming a zero quadrupole splitting in one fitting procedure are comparable with that found for CuI in which the tetrahedral coordination of the Cu should mean negligible quadrupole coupling. values for the coupling constante

The maximum possible

( a zfor zthe )

CuI complexes

are shown in Table 3 and are in the r a z e 410-690 MHz.

These

values can be compared with the coupling constants of up to 3,000 MHz found for the covalent interactions of iodine bonded to maingroup elements in non-cubic configurations.

The authors, therefore

M ossbauer Spectroscopy

41 1

concluded that for the Cu(1)-iodine-containing

compounds

either

there is very little distortion of the electronic environment from the spherically symmetrical valence configuration of the purely ionic iodide ion and that the Cu(2)-I

bond is ionic or that in the

Cu(I1-I bonding electrons are withdrawn nearly equally from the three 5 ~ - o r b i t a l sof iodine.

The authors favoured the former

explanation but they did not consider the possibility that any and I could involve molecular

covalent interaction between Cu(1)

orbitals populated essentially by Cu electrons.

Table 3

1-127 Moessbauer parameters for complexes of CuI, assuming (i) single lines, (ii) quadrupole split sites

Complex

Isomer shif tl -1 mm s from KI

e

127

Q&/

MHz

cCuI(PPh3)31

(i) (ii)

-0.12(6) -0.03(6)

[(CUI)~(PP~~)~I

(i) (ii)

-0.10(6)

-0.04(6)

-450(50)

[{CuI(PPh3)141

(i) (ii)

-0.12(3) -0.65(9) +O. 4 2 ( 12 1

-620( 70) 690(60)

(i) (ii)

-0.06(6) +0.01(6)

-41 O( 6 0 )

[ICUI(PH~P~)~)~I

lnI CKCUI)~(S~P~ ~)

-0.09( 3 )

CUI

-0.03 (6 1

-

-470 (60)

Resonance Raman and 1-129 Moesebauer spectroscopy were used in a study of I-doped polythienylenes prepared by polymerisation of dibromothiophenes.

The iodine species identified in the polymers and I 2 units,and this

were polyiodides consisting of I3

-

means that the I must have been reduced by taking electrons from the polymer in the doping process.

The result was said to b e

consistent with an increase in the electrical conductivity of the 507 polymer o n doping it with iodine

.

The hyperfine interactions in the Te-V system were followed in V3Te4, V5Te8,and A

VTe2 by the Te-129 Moessbauer emission.

transferred magnetic hyperfine field at the daughter 1-129 aites

Spectroscopic Properties of Inorganic and Organometallic Compounds

412 in V2.6Te4, at 16K.

which has a Ngel temperature at 52K, was observed

The isomer shift decreases with decreasing V content and

the ionicity calculated was said to be in agreement with earlier 508

.

results on Cr-Te and similar systems Transition-Metal Elements.-The

isotopesRu-99, Ir-193,and Au-197

were included in a study of intermetallic compounds designed to provide an interpretation of Moessbauer isomer shifts Nickel (Ni-61).

41

.

Both the Ni-61 and the Fe-57 Moessbauer effects

were used to study a partially ordered sample of Ni3Fe.

The

calculated occupation probabilities of Ni neighbours were used to estimate the changes in the magnetic hyperfine field at Ni due to 509 the presence of one F e atom in the first coordination sphere. Zinc (Zn-67).

Ikonan et

used the 9 3 keV Zn-67 isotope in an

investigation of coherent transient effects arising from phase modulation of the gamma-radiation.

In studies of Zn-67 in Z n O

transient experiments with Zn-67 mechanical displacements of about 10-13m were resolved a n d , as an extension of the study, the recoil-free fractions of both the Ga(67):ZnO enriched ZnO were determined as 0.0212(16)

source and the Zn-67and 0.0213(18)

respectively. The 93.3 keV Moessbauer resonance in Zn-67 involves a gamma transition between a 512 ground state and a 112 excited state. Since the excited state will not split under the interaction of an electric-field gradient tensor, the quadrupolar hyperfine spectrum is comparatively simple and easily interpreted.

The spin of the

ground state, on the other hand, is high enough to allow a separation of the field gradient

!.! ZZ

from the asymmetry parameter

in cases where the symmetry is lower than axial.

Furthermore,

the resonance linewidth is extremely narrow o n account of the rather long half-life of the 93.3 keV excited state.

Thus field

gradients can be measured with an accuracy characteristic for microwave resonance methods. Since ZnF2 is the most ionic zinc compound, the point-charge model would be expected to provide an appropriate description of the hyperf ine parameters.

Potzel and K a l v i ~ s ~ ~have, ' however,

Mossbauer Spectroscopy

413

shown t h a t i t i s n o t t h e c a s e b e c a u s e n e i t h e r t h e s i g n o f t h e e.f.g.

n o r t h e asymmetry p a r a m e t e r a r e c o r r e c t l y p r e d i c t e d by t h e

p o i n t - c h a r g e model.

They u s e d t h e s p e c t r u m o f

( Z n - 6 7 ) F 2 t o show

how much m o r e e l a b o r a t e c a l c u l a t i o n s a r e r e q u i r e d t o e x p l a i n t h e experimental r e s u l t s .

T h e s p e c t r u m o f ZnF2 c o n s i s t s o f t h r e e

l i n e s a t t h e p o s i t i o n s -86.07,

-56.25,and

-40.23

pm s

-1

from a

During t h e experiment a s i n g l e c r y s t a l of

(Ga-67)ZnO s o u r c e .

ZnF2 w a s a l s o a l i g n e d s u c h t h a t t h e 5 - a x i s o f c e l l w a s p a r a l l e l t o t h e d i r e c t i o n of

its rutile unit

t h e gamma-rays.

In this

o r i e n t a t i o n o n e of t h e q u a d r u p o l e l i n e s i s n o t o b s e r v e d a n d t h e s p e c t r u m c o n s i s t s of t w o l i n e s s e p a r a t e d b y 4 . 8 0

pm s-’.

The

2 4

i s o m e r s h i f t f o r ZnF2 o b t a i n e d f r o m t h e s p e c t r u m w a s - 6 . 4 pm s

-1

, a n d t h e second-order

s h i f t a r i s i n g from t h e d i f f e r e n t

D e b y e t e m p e r a t u r e s of ZnO a n d ZnF2 w a s 3 . 5 t e m p e r a t u r e o b t a i n e d f o r ZnF2 w a s 2 9 4 e.f.g. an

1.

P o t z e l and K a l v i u s =

(EkSl2

pm s-’.

2 13K.

The Debye

To d e t e r m i n e t h e

considered t h e energy eigenvalues f o r

5 1 2 s t a t e , a n d from t h e r a t i o of t h e energy s e p a r a t i o n s

-

-

E+312)/(E,312

c a l c u l a t e d as 0.24 numerically.

E+112) t h e asymmetry p a r a m e t e r was

5 0.05 by s o l v i n g t h e corresponding e q u a t i o n

Using t h i s v a l u e f o r t h e asymmetry parameter,

2

q u a d r u p o l e f r e q u e n c y 2 v z z Q was d e t e r m i n e d as +100.5+1.5 s-’,

from which t h e

yzz

- value

was derived.

Ruthenium (Ru-99).

T h e Ru-99

i n niobium hydrides,and density a t ruthenium 0.7-1.0).

511

of +(2.09

f

0.23)

x 1 0 1 7 V/cm

2

i s o t o p e h a s been u s e d a s a p r o b e atom

t h e r e s u l t s showed t h a t t h e e l e c t r o n

decreased with increasing

i n NbH

-

The Ru-99 M o e s s b a u e r e f f e c t w a s a l s o u s e d o :

t h e p r o p e r t i e s of

the

pm

(5 =

study

s i n g l e c r y s t a l s grown by c h e m i c a l v a p o u r

t r a n s p o r t i n t h e system Ti02-Ru02.

The r e s u l t s showed t h a t a l l

Ru o x i d a t i o n s t a t e s f r o m V + t o I I I + w e r e p r e s e n t i n t h e s o l i d 512

solutions obtained Tantalum (Ta-181).

.

The T a - 1 8 1 M o e s s b a u e r s p e c t r a w e r e m e a s u r e d i n

t h e same s a m p l e o f TaS2 b e f o r e a n d a f t e r t h e i n t e r c a l a t i o n o f h y d r a t e d Na i n a s t u d y o f

t h e c h a r g e - t r a n s f e r induced change

a r i s i n g from t h e i n t e r c a l a t i o n 5 1 3 .

The i n t e r c a l a t i o n compound

Na0.33(H20)2TaS2 h a s a s i n g l e Moessbauer r e s o n a n c e l i n e w i t h a h i g h e r s h i f t t h a n t h e p a r e n t T a S 2 , a s would b e e x p e c t e d because of

t h e l o w e r v a l e n c y o f Ta i n t h e N a - c o n t a i n i n g

compounds.

Spectroscopic Properties of Inorganic and Organometallic Compounds

414

The quadrupole interaction in TaS2 is smaller after intercalation, in agreement with perturbed angular correlation data.

The

2H-TaSe2 phase has also been studied514 using the Moessbauer effect and, because of the high resolution possible with the Ta-181 resonance, it was found that the splitting between the +5/2-23/3 and 2 7 1 2 -2512

energy levels could be resolved.

In another study

of selenides and sulphides, the 6.2 keV Ta-181 resonance was used to study the derivatives T13TaX4 ( X

=

S or Se).

The isomer

shifts for T1TaS4 and T1TaSe4 from Ta metals were found to be -10.16 and +3.85 mm 8-l respectively, values which are about 2 5 mm

8-l

lower than the values for the shifts in the 515

corresponding Cu TaE4 series 3 Iridium (Ir-193).

.

The Ir-193 Moessbauer effect waa used in two

studies of its parent nucleus 193~s.516,517

An (08-193).

O s 0 ~ 0 8 F e 0 ~ 9 2source was used in one of the studiee516 of the effect of the orientation of the 08-193 ground state o n the substate populations of the 73 keV 1 / 2 + Moessbauer state.

The

different Moesebauer spectra obtained at high and low temperatures arising from different populations are shown in Figure 4 . The gamma-ray distribution coefficients combined with a quadrupole alignment measurement from the literature lead to a value for the ground state of +0.48(6)b.

9

(0s-193)

The magnetic

moment of the ground state of Os-193(3/2-) has also been reported as -0.75(3)uN. The Ir-193 isotope has been used as a probe atom in niobium hydrides,and the results obtained showed that the electron density 511 at Ir decreases with increasing x in NbH ( x = 0.7-1.0).

-

Gold (Au-197).

Gamma-resonance measurements carried out on bi- and

tri-nuclear Au( I) complexes containlng P h PAu+ units bridged 3 with a halogen or an oxygen atom showed that the spectra consisted of one doublet and that the parameters were almost identical to 518 those obtained for monomeric Au(I) compounds

.

The first dithiocarboxylate derivatives of gold have been obtained.519

The compounds have the compositions Au(CH3CS2),

-l/Z

112

-

- 1312 12

:3

Low temperature 211

I -14

,

-10

,

-5

I

l

l

0

5

10

L

159

14

1 -14

1

-10

v (mm s-')

Figure 4

1

1

1

1

I

-s

0

s

10

14

v I mm 5")

Calculated Ir-193 Moessbauer spectra assuming different populations of the parent 08-193

levels compared to experimental spectra obtained with a polarised source at high and low temperatures.

At high temperatures the

*-*>

spectrum is symmetrical about zero velocity.

and the

*+*>

equal and the spectrum is not symmetrical (Reproduced by permission from J. Phys. G ,

substate populations are equal and the

At low temperatures the substate populations are not

1985,

11,2 8 7 )

416

Spectroscopic Properties of Znorganic and Organometallic Compounds

Au(PhCS2),and Au(PhCS2)(PH2CCS2).

T h e Au-197

parameters

f o r Au(CH CS ) a r e I.S. = 1 . 4 0 mm s - ’ ( r e l a t i v e t o Au i n P t 3 2 m e t a l ) a n d Q . S . = 6 . 1 3 mm s-’. T h e s t r u c t u r e o f Au(CH3CS2)

(9)

consists

of

a t e t r a m e r of

g o l d a t o m s b r i d g e d i n p a i r s by

CH3CS2 g r o u p s .

T h e Au-Au t h o s e of

distances,

288.4

a v e r a g e 301.3

are long compared w i t h

pm,

pm f o u n d i n t h e m e t a 1 , b u t

it is s t i l l s u r p r i s i n g

t h a t t h e Moessbauer parameters provide no evidence of i n t e r a c t i o n b e t w e e n t h e Au a t o m s o f

Addition of

a b i d e n t a t e l i g a n d (L) [ w h e r e L = 1 , l O - p h e n a n t h r o l i n e

or 2-phenylenebis(dirnethy1arsine)l tetrahydrothiophene

(X

= C1 or

contain five-coordinated products, of

t o solutions of

Br)

Au(II1).

Au(C6F5)X2.

leads to products that could The Moessbauer s p e c t r a of

the

h o w e v e r , were shown t o b e c o n s i s t e n t w i t h t h e f o r m a t i o n

square-planer

A u ( I I 1 ) c o m p l e x e s w i t h o n l y weak i n t e r a c t i o n s

one a x i a l position

Au-193

direct

t h e tetrarner.

520

.

in

h a s b e e n u s e d a s a p r o b e atom i n NbHx,and i t h a s b e e n

-

x

s h o w n t h a t t h e e l e c t r o n d e n s i t y a t t h e Au i n c r e a s e s w i t h

over t h e

range 5 = 0 . 7 - 1 . 0 ~ ~ ~ .

The M o e s s b a u e r s p e c t r a h a v e b e e n o b t a i n e d f o r Au-197 which h a s t h e CsC1-type b a r and 27,

30,

and 4 0 kbarS2’.

c h a n g e t o a s t r u c t u r e of kbar.

s t r u c t u r e , a t 4.2K

i n CsAu,

and a t p r e s s u r e s of 1

Evidence w a s found f o r a phase

lower symmetry a t a p r e s s u r e j u s t below 2 7

T h e 1 b a r s p e c t r u m f o r CsAu s h o w e d t h e p r e s e n c e o f a s m a l l

amount of

a n i m p u r i t y Au s i t e , b u t

t h e main s i n g l e t s p l i t a i n t o a

q u a d r u p o l e d o u b l e t a n d s h i f t s t o lower e n e r g y t o g i v e t h e

Moss ba uer Spectroscopy parameters

I.S.

417

= 6.95

mm s - l , Q.S. = 1.51 mm s-'.

The

presence of a phase transition at about 27 kbar is also indicated by an increase in the Debye temperature from 72K at 1 bar to 79K at 2 7 bar.

The changes in the gold Moessbauer data were taken by the

authors to suggest greater covalency in the bonding in the hightemperature phase. Lanthanide and Actinide Elements.-During

the past year papers have

been published on Moessbauer effect studies using isotopes of europium, gadolinium, dysprosium, erbium, thulium, ytterbium, and neptunium.

The last year has seen a large number of papers

published o n the Eu-151 Moessbauer spectra of europium 1:2:2 compounds. Europium (Eu-151).

Line-broadening due to paramagnetic relaxation

has been noted in Moessbauer spectra of Eu2+ in frozen glassy solutions522.

This broadening was used as an indicator of the

degree of dispersion of europium.

Two papers have used the Eu-151

Moessbauer effect to identify the valence states of europium in the europium-doped phosphors

K , R b , Cs).

ABeF3523 and AF-AlF3524

(A

=

Na,

Both systems contained Eu3+ in addition to Eu2+.

Structural, magnetic,and Moessbauer data have been reported for the europium dihalides

EuX2 (X = C l , B r , I). 525

A linear

correlation between the Moessbauer isomer shift and the saturation hyperfine field was found and interpreted in terms of changes in bond ionicity which result in increasing 6s-electron and spin densities with decreasing ionic character.325

Samples of the non-

stoichiometric mixed-valence compound EuBr3-x have been examined by Moessbauer and other methods526.

These results, together with

those from an earlier study o n EuC13, were consistent with a thermally activated mixed-valence process in which 44f-electron

is

promoted into the 5cJ6s-conduction band for a characteristic time of about


6 . 3 keV.

D e t e c t i o n of e l e c t r o n s at l a r g e a n g l e s leads t o

a d r a s t i c c o n t r a c t i o n o f t h e w e i g h t f u n c t i o n t o w a r d t h e surface.

Weight functions for internal conversion Moessbauer effect, c o m p u t e d f r o m M o n t e C a r l o s i m u l a t i o n of e l e c t r o n t r a n s p o r t , h a v e b e e n t e s t e d f o r s c a l i n g properties586.

E n e r g y s c a l i n g is f o u n d

426

Spectroscopic Properties of Inorganic and Organometallic Compounds

t o hold w i t h h i g h a c c u r a c y f o r a w i d e r a n g e o f m a t e r i a l s and e l e c t r o n e n e r g i e s , and m a s s s c a l i n g f r o m F e t o o t h e r m a t e r i a l s is 58 7 a d e q u a t e e x c e p t f o r low-atomic-number materials. M e y e r e t al. h a v e c a r r i e d o u t zero-field M o e s s b a u e r m e a s u r e m e n t s b e t w e e n 1.9 3 0 K and at r o o m t e m p e r a t u r e o n a A u - 3 at.% d e f i n e d c h a n g e of r e g i m e w a s o b s e r v e d at m e a s u r e d c u s p t e m p e r a t u r e (16.4K) t e m p e r a t u r e r e g i o n b e l o w 19.5K

F e sample. 19.5K

and

A quite well

well above the

f o r t h e sample.

In the

t h e s p e c t r a h a v e b e e n d e s c r i b e d in

t e r m s of a s t a t i c i n h o m o g e n e o u s l y b r o a d e n e d field distribution,and at h i g h e r t e m p e r a t u r e s t h e s p e c t r a w e r e c o m p a t i b l e w i t h r e l a x a t i o n broadening.

It h a s b e e n shown588

t h a t t h e c o m b i n a t i o n of a

grazing incidence total external reflection geometry with conversion-electron

detection produces surface-sensitive Moessbauer

s p e c t r a w h i c h a r e s e l e c t i v e f o r the f i r s t f e w n a n o m e t r e s of t h e solid.

This approach has been shown to be a simply implemented

m e t h o d of o b t a i n i n g M o e s s b a u e r

s p e c t r a of surfaces.

It h a s b e e n s h o w n s a 9 t h a t t h e s u r f a c e s e l e c t i v i t y o f r e s o n a n c e e l e c t r o n M o e s s b a u e r s p e c t r o s c o p y w i t h a p r o p o r t i o n a l c o u n t e r c a n be i m p r o v e d by d e t e c t i n g t h e sum s i g n a l s of K - c o n v e r s i o n electrons.

and K - A u g e r

T h e p r o b i n g d e p t h h a s b e e n e s t i m a t e d f r o m t h e r a n g e of

K - A u g e r e l e c t r o n s t o be

1 2 0 n m in t h e c a s e o f F e - 5 7 M o e s s b a u e r

Furthermore,depth-selective Moessbauer spectroscopy

measurements.

f o r t w o layers h a s b e e n m a d e p o s s i b l e by o b s e r v i n g t h e abovem e n t i o n e d s p e c t r u m and t h e c o n v e n t i o n a l r e s o n a n c e - e l e c t r o n Moessbauer spectrum, nm respectively.

t h e p r o b i n g d e p t h s of w h i c h a r e 1 2 0 n m and 3 0 0

In order to record several Moessbauer spectra

simultaneously, as in t h e c a s e of d e p t h - s e l e c t i v e M o e s s b a u e r spectroscopy, a microcomputer b e e n used.

equipped with interface circuits has

A m e t h o d t o s t u d y t h e c o m p o s i t i o n and depth

d i s t r i b u t i o n of p h a s e s p r e s e n t in s u r f a c e layers of 0-50nm h a s b e e n developedsg0.

The method

is based o n t h e a n a l y s i s of t h e

M o e s s b a u e r s p e c t r a r e c o r d e d by m e a n s of c o n v e r s i o n e l e c t r o n s e m e r g i n g at a p p r o x i m a t e l y

t h e i n i t i a l e n e r g y at d i f f e r e n t angles

r e l a t i v e t o t h e layer s u r f a c e . experimental

A n o t h e r p a p e r r e p o r t s s g 1 an

i n v e s t i g a t i o n of the depth and s u r f a c e s e l e c t i v i t y in

F e - 5 7 DCEMS performed using a high-resolution

electron-energy

analyser combined with a Moessbauer spectrometer.

DCEM S p e c t r a

w e r e r e c o r d e d in u l t r a h i g h v a c u u m at d i f f e r e n t e l e c t r o n e n e r g i e s f r o m 6.5

t o 7.3

k e V ( w i t h 2.7%

E

energy r e s o l u t i o n ) and f o r t h e f i r s t

427

Mossbauer Spectroscopy t i m e at d i f f e r e n t e l e c t r o n - e m i s s i o n

angles,theta,relative

to the

a b s o r b e r s u r f a c e n o r m a l ( f r o m t h e t a = 10’ t o 72O) u s i n g a t e s t a b s o r b e r c o n s i s t i n g of a t h i n a l p h a - F e l a y e r o n a t h i c k s t a i n l e s s s t e e l substrate.

T h e a l p h a - F e and s t a i n l e s s - s t e e l M o e s s b a u e r

s p e c t r a a r e a s w e r e f o u n d t o be in very good a g r e e m e n t w i t h t h e o r e t i c a l c a l c u l a t e d values.

It h a s b e e n c o n f i r m e d t h a t t h e

s u r f a c e s i g n a l is e n h a n c e d by m e a s u r i n g at g l a n c i n g a n g l e s r e l a t i v e t o t h e a b s o r b e r surface.

S u r p r i s i n g l y , t w o p a p e r s h a v e a p p e a r e d in

t h e l i t e r a t u r e o f G u r a c h e v s k i i et al?”’

5 9 3 which describe a

m e t h o d used t o d e t e c t l o w - e n e r g y c o n v e r s i o n and A u g e r e l e c t r o n s which are involved in the transition of the resonance-excited Fe-57 n u c l e u s t o t h e g r o u n d state.

A photoelectron multiplier w a s used

as a d e t e c t i o n o f light p u l s e s f r o m m i c r o d i s c h a r g e s

in r a r i f i e d

a i r , c a u s e d by e l e c t r o n s e m i t t e d f r o m t h e s u r f a c e of a s a m p l e u n d e r irradiation. A thin proportional counter for scattering Moeesbauer spectrom e t r y ( C E M S and X - r a y M o e s s b a u e r s p e c t r o m e t r y ) h a s b e e n designed594

and its w o r k i n g c h a r a c t e r i s t i c 6

studied t o find the

o p t i m a l c o n d i t i o n f o r t h e e f f e c t i v e d e t e c t i o n of t h e resonar?t s c a t t e r e d X-ray.

With t h e newly designed proportional counter,

s c a t t e r i n g M o e s s b a u e r s p e c t r a o f s t e e l s w e r e m e a s u r e d and t h e m a g n e t i s m and c h e m i c a l c o m p o s i t i o n of t h e s t e e l s u r f a c e l a y e r s analysed.

T h e c o n s t r u c t i o n of a s i m p l e gas-flow p r o p o r t i o n a l

c o u n t e r s u i t a b l e f o r o p e r a t i o n b e t w e e n 100 and 4 0 0 K w i t h o u t t h e 595 need f o r a n e v a c u a t e d c r y o g e n i c s y s t e m h a s b e e n d e s c r i b e d

.

Different g a s m i x t u r e s w e r e s t u d i e d o v e r t h e t e m p e r a t u r e r a n g e and He/5%CO w a e f o u n d t o be m o s t s u i t a b l e at 100K.

T h e system was

t e s t e d using s t a n d a r d f o i l s t o o b t a i n t h e o p t i m u m o p e r a t i n g conditions.

LQW-concentration Fe-based samples were also studied

t o s h o w t h e i m p o r t a n c e of i n v e s t i g a t i n g s u r f a c e p h e n o m e n a at d i f f e r e n t temperatures.

I n a n o t h e r paper596

the working

p r i n c i p l e , f e a t u r e s , a n d c o n s t r u c t i o n of a b e t a - r e s o n a n c e

detector

ueed for backscattering Moessbauer spectroscopy have been deecribed a l o n g w i t h e x a m p l e s f o r s t a i n l e s s - s t e e l and F e p l a t e samples.

A

conversion-electron Moesebauer spectrometer which allows measurem e n t s t o b e m a d e a t l o w temperature(80K) h a s b e e n f a b r i c a t e d 5 9 7 u s i n g a c e r a m i c e l e c t r o n multiplier. the CEM spectrum of beta-FeOOH = 50K),

(TN =

It w a s ueed t o d i s c r i m i n a t e 2 7 3 K ) from g a m m a - F e O O H

(TN

which were produced o n steel surfaces as corrosion products

428

Spectroscopic Properties of Inorganic and Organometallic Compounds

f o l l o w i n g e x p o s u r e of s t e e l in an a i r - H C l - H 2 0 atmosphere. i n s t r u m e n t a t i o n f o r t h e c o m b i n a t i o n of a M o e s s b a u e r

The

spectrometer

w i t h a h o l l o w - c o r e b e t a s p e c t r o m e t e r has b e e n d e s c r i b e d 5 9 8 detail.

The conversion-electron

in

s p e c t r a o b t a i n e d w e r e f o u n d t o be

u n s a t i s f a c t o r y f o r the m e a s u r e m e n t s o f c h a r g e and s p i n d e n s i t i e s of the 4:-electrons. Iron.-The -

f a v o u r a b l e p r o p e r t i e s of t h e F e - 5 7 M o e s s b a u e r g a m m a -

r a d i a t i o n and its a s s o c i a t e d c o n v e r s i o n e l e c t r o n s r e s u l t in m o s t of t h e a p p l i c a t i o n s of t h e C E M S t e c h n i q u e o v e r t h e past y e a r being c o n c e r n e d w i t h t h e i r o n - 5 7 effect. discussed under the headings 'steels

T h e s e a p p l i c a t i o n s are n o w

'films and i m p l a n t a t i o n studies',

and c o r r o s i o n products', and 'chemical

F i l m s and I m p l a n t a t i o n Studies.

reactions).

Hyperfine interaction parameters

n e a r c l e a n and A g - c o v e r e d Fe(ll0)

s u r f a c e s w e r e measured5"

for

the f i r s t t i m e by m e a n s of in s i t u c o n v e r s i o n - e l e c t r o n M o e s s b a u e r spectroscopy.

T h e i n c r e a s e in t h e q u a d r u p o l e s p l i t t i n g r e f l e c t e d

the r e d u c t i o n in s y m m e t r y in the t o p m o s t monolayer,and

the magnetic

hyperfine fields provided information o n magnetic order near the s u r f a c e w i t h m o n o l a y e r resolution.

An additive hyperfine field

p e r t u r b a t i o n m o d e l h a s b e e n used6'' composition-modulated

t o a n a l y s e t h e C E M S of

F e - V films.

T h e t h e o r e t i c a l p r e d i c t i o n of a

r e d u c e d m o m e n t at t h e i n t e r f a c e w a s v e r i f i e d and t h e a n t i f e r r o m a g n e t i c m o m e n t o n the V a t o m s n e a r t h e i n t e r f a c e s u p p o r t e d , but t h e p r e d i c t e d o s c i l l a t o r y m o m e n t of t h e inner F e l a y e r s w a s discounted.

M a g n e t i s a t i o n p r o c e s s e s n e a r t h e s u r f a c e of p o l y -

c r y s t a l l i n e and s i n g l e - c r y s t a l F e p l a t e s w e r e s t u d i e d by M o e s s b a u e r e m i s s i o n and CEM s p e c t r o s c o p y and by the m a g n e t o - o p t i c a l effect601. 5 n m - 2 0 m.

Kerr

T h e M o e s s b a u e r m e t h o d s w e r e used t o p r o b e d e p t h s of T h e v a l u e s of H o b t a i n e d w e r e found t o be c o n s i s t e n t

w i t h t h e b r e a k in t h e b u l k m a g n e t i s a t i o n curve.

C E M S and EXAFS

w e r e u s e d 6 0 2 t o s t u d y e m e r s e d e l e c t r o d e i n v e s t i g a t i o n s of p a s s i v a t e d iron films.

C E M S h a s a l s o b e e n u s e d t o s t u d y c a r b o n d e p o s i t i o n o n iron

603

.

C a r b o n d e p o s i t s w e r e f o r m e d o n F e f o i l s by t h e c a t a l y t i c d e c o m p o s i t i o n of a M e 2 C O - C 0 2 m i x t u r e conversion-electron Moessbauer

and t h e n s t u d i e d by

spectroscopy.

T h e r e s u l t s indicated

that w u s t i t e ( F e O ) c a t a l y s e d t h e C d e p o s i t i o n p r o c e s s and c e m e n t i t e

Mossbauer Spectroscopy

429

(Fe C) played a role in forming carbon filaments by disseminating 3 the wustite. The surface technique has been used by Tomashevskii et alpo4 for the determination of the carburised layer structure in Fe.

Tests were made o n Armco F e saturated with C-14, and the

distribution of C-14 in F e was determined by layer-by-layer removal. The C diffusion coefficient value ( 2 = 2 . 2 x 2 cm 1 s ) was calculated for the tested carburisation conditions, and information about the structural state of the diffusion zone was obtained from analysis of the Moessbauer spectra. A number of papers have appeared reporting the use of conversionelectron Moessbauer spectroscopy to study ion-beam-induced atomic mixing at iron-metal interfaces6 0 5 - 6 0 8 . Fe-A1 interfaces 6 0 5 y 6 0 6 .

Two papers deal with

In the first paper605 the authors

used both CEM and transmission Moessbauer spectroecopies so that the structural state of nearly equiatomic FeAl multilayers before and after Xe3+ ion-beam mixing could be studied.

The as-ion-

beam-mixed material gave rise to a Moessbauer spectrum exhibiting a doublet.

From the CEMS-TEM study of annealing (300-750K) after ion

beam mixing the well known B 2 superstructure could be detected at temperatures as low as 470K.

In the second paper606 both ion-

beam-induced atomic mixing and the effect of thermally activated transformations at the Fe-A1 interface were studied.

The CEMS

spectra of the as-deposited sample showed that not all the Fe-57 atoms in the interface region see the environment as in alpha-Fe but have one or more A1 neighbours.

T h e interface layers were

transformed o n bombardment with 100 keV Ar+ ions at a dose of

1 0 l 6 ionslcm’ into a random metastable alloy having an average composition of Fe55A145.

Results of the annealing studies o n

this system have also been described.

In addition to these studies

Ogale et el.6 0 7 y 6 0 8 have investigated the ion-beam-induced and subsequent thermal transformations at the Fe-Si and Fe-Ge interfaces.

In the former607, the ion-beam-mixed sample showed

significant changes in the values of hyperfine interaction parameters subsequent to vacuum annealing treatment at 450K for one hour while precipitation of alpha-Fe and Fe3Si were obtained o n annealing at 700K.

I n the paper dealing with the iron-germanium

interface, the ion-beam-mixed

samples exhibited the presence of

the magnetic FeGe phase along with F e atoms situated in interstitial positions having a tetrahedral environment about Ge.

Spectroscopic Properties of Inorganic and Organometallic Compounds

430

T h e as-deposited as well as ion-beam-mixed composites showed s i g n i f i c a n t s t r u c t u r a l r e l a x a t i o n s o n a n n e a l i n g a t 350K. S i m i l a r i t i e s and d i f f e r e n c e s b e t w e e n t h i s i n t e r f a c e and t h o s e of F e - A 1 and F e - S i w e r e t h e n considered. converdion-electron Moessbauer

B o t h F e - 5 7 and Sn-119

spectrometry were applied to the

i n v e s t i g a t i o n o f t h e c o m p o s i t i o n a l v a r i a t i o n s of t h e F e - S n i n t e r m e t a l l i c a l l o y p r o d u c e d at t h e s u r f a c e of 9 0 n m t h i c k Sne l e c t r o - d e p o s i t e d s t e e l by t h e r m a l treatment609. alloyed layer of F e S n 2 ,

+

FeSn

FeSn2,

FeSn,

The fully

+

FeSn

Fe3SnC,

and F e S n C w a s f o r m e d by t h e t h e r m a l t r e a t m e n t f o r 30 m i n u t e s at 3 3 0 0 , 4 0 0 , 5 0 0 , 600,and 700K r e s p e c t i v e l y , a n d the t h i c k n e s s of t h e F e - S n layer w a s o b s e r v e d t o increase w i t h i n c r e a s i n g temperature. T h e C E M s p e c t r a h a v e b e e n r e c o r d e d 6 1 0 f o r Fe-40%at. implanted w i t h A 1 2 + o r F e 2 + ions and f o r Fe-50%at. w i t h A r 3 + ions. meter

A1

A 1 implanted

T h e v a r i a t i o n of t h e l o n g - d i s t a n c e o r d e r p a r a -

as a f u n c t i o n of the m a g n e t i c h y p e r f i n e s p l i t t i n g w a s g i v e n

f o r A 1 2 + - i m p l a n t e d Fe-40%at.

A l , and n o m a g n e t i c h y p e r f ine

s p l i t t i n g w a s o b s e r v e d f o r i m p l a n t a t i o n in Fe-SO%at. S t e e l s and C o r r o s i o n Products.

Al.

I n a r e v i e w 6 1 1 of r e c e n t d e v e l o p -

m e n t s in c o n v e r s i o n - e l e c t r o n M o e s s b a u e r s p e c t r o s c o p y f o r s u r f a c e a n a l y e i s U j i h i r a h a s d e s c r i b e d t h e a p p l i c a t i o n o f t h e t e c h n i q u e to the following:

t h e c h a r a c t e r i s a t i o n of c o r r o s i o n p r o d u c t s o r

phosphated coatings produced o n steel, of t h e h a r d e n e d s t e e l s u r f a c e ,

the layer-by-layer analysis

the e s t i m a t i o n of i n t e r m e t a l l i c

c o m p o u n d s f o r m e d b e t w e e n F e - Z n and F e - S n i n t e r f a c e s ,

and s t u d i e s

of s u r f a c e d e p o s i t i o n of F e c o m p o u n d s by the c r y s t a l l i s a t i o n of a m o r p h o u s Fe. R e s u l t s h a v e b e e n p r e s e n t e d 6 1 2 o n t h e a n i s o t r o p y of t h e M o e s s b a u e r e f f e c t on t h e s u r f a c e of t h e s t e e l 4 5 s a m p l e w i t h c r y s t a l l o g r a p h i c t e x t u r e of t h e s u r f a c e r e s u l t i n g f r o m grinding. T w o M o e s s b a u e r s p e c t r o s c o p i c m e t h o d s 6 1 3 w e r e d e v e l o p e d f o r the study of t h e m a g n e t i c t e x t u r e of s t e e l s h e e t s , w h i c h w e r e based o n r e c o r d i n g t h e c o n v e r s i o n e l e c t r o n s or t h e c h a r a c t e r i s t i c e m i s s i o n a c c o m p a n y i n g i n t e r n a l c o n v e r s i o n of gamma-quanta.

F o r electrical-

technology steel the former method showed a nearly isotropic m a g n e t i c t e x t u r e w h e r e a s t h e latter o n e indicated t h e m a g n e t i s a t i o n of d o m a i n s p r e d o m i n a n t l y along t h e s h e e t r o l l i n g direction.

The

Mossbauer Spectroscopy

431

p h a s e s t r u c t u r e of laser-modif ied s u r f a c e l a y e r s of alloys614

has

a l s o b e e n studied by CEMS. T h e c o r r o s i o n p r o d u c t s 6 1 5 of m i l d s t e e l in a n acid m e d i u m h a v e b e e n i d e n t i f i e d u s i n g CEMS.

I n a n o t h e r p a p e r by R a o et

the

r e s u l t s of C E M S c h a r a c t e r i s a t i o n of b o r i d e p h a s e s b e f o r e and a f t e r p u l s e d l a s e r t r e a t m e n t at 3 J / c m 2 h a v e b e e n presented. c e m e n t a t i o n w a s used t o p r o d u c e 1 0 - 4 5

A pack

t h i c k b o r i d e d layers.

The

CEMS spectrum showed different boride phases present on the steel, s u c h a s F e 2 B and F e B , a n d , a s t h e t h i c k n e s s o f t h e b o r i d e layer i n c r e a s e d , t h e F e B w a s i n c r e a s i n g l y f o r m e d o v e r an u n d e r l y i n g F e 2 B layer of laser. C h e m i c a l Reactions.

In situ conversion-electron Moessbauer studies

h a v e b e e n c a r r i e d o u t a n a l p h a - and g a m m a - F e 2 0 3 g a s - s e n s o r materials617.

I n f o r m a t i o n o n t h e s u r f a c e s t a t e s of t h e o x i d e s

w a s o b t a i n e d at 4OO0C T h e gas-sensing

( a l p h a p h a s e ) and at 250°C

( g a m m a phase).

a c t i v i t y d e p e n d e d o n a n u m b e r of f a c t o r s i n c l u d i n g

t h e amount of r e m a i n i n g s u l p h a t e ion + t h e m i c r o s t r u c t u r e , a n d

a

s p e c i e s g e n e r a t e d t h r o u g h t h e r e d u c t i o n of

s m a l l a m o u n t of Fe(I1)

alpha-Fe203 gas sensor w a s confirmed to be due to t h e reduction

of gamma-Fe203

t o Fe3,x04.

-

T h i n f i l m s of F e 2 0 3

d e p o s i t e d o n t o t r a n s p a r e n t c o n d u c t i n g g l a s s e s by a s p r a y p y r o l y s i s t e c h n i q u e w e r e c h a r a c t e r i e e d by CEMS618.

T h e g r o w t h of t h i n

Fe203 films w a s found to be dependent upon the substrate m a t e r i a l used,* glasses.

tin(1V)

o x i d e , indium o x i d e , a n d z i n c o x i d e coated

T h e C E M S s p e c t r a of C o F e

0.6, 0.8, and 1.0) w e r e

A l x 0 4 ( 5 = 0.1, 0.3, r o o m t e m p e r a t u r e and t h e

c a t i o n d i s t r i b u t i o n s f o r all s a m p l e s d e r i v e d and c o m p a r e d w i t h those distributions for powdered samples from normal transmission measurements.

T h e f r a c t i o n of C o 2 + ions at t h e t e t r a h e d r a l

l a t t i c e s i t e s w a s f o u n d t o i n c r e a s e linearly w i t h t h e A 1 content. I n a n o t h e r paper620 in C o 2 + F e 2 , x C ~ 3 + 0 4

the CEMS results on the cation distribution (0