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A Specialist Periodical Report
Organometal I ic Chemistry Volume 1
A Review of the Literature Published during 1971
Senior Reporters E. W. Abel, Department of Chemistry, University of Exeter F. G. A. Stone, Department of Inorganic Chemistry, University of Bristol
Reporters D. A. Armitage, Queen Elizabeth College, Uni,versity of London M. A. Bennett, Australian National University, Canberra, Australia M. 1. Bruce, University of Bristol R. F. Bryan, University of Virginia, Charlottesville, Virginia, U.S.A. J. A. Connor, University of Manchester J. D. Cotton, University of Queensland, Brisbane, Australia B. C. Crosse, National Lending Library, Boston Spa M. Green, University of Bristol J. P. Maher, University of Bristol R. J. Mawby, University of York F. J. McQuillin, University of Newcastle upon Tyne T. Onak, California State University, Los Angeles, U S A .
0 Copyright 1972
The Chemical Society Burlington House, London, W l V OBN
ISBN: 0 85186 501 1
Library of Congress Catalog Card No. 72-83459
Printed in Great Britain by Alden & Mowbray Ltd
at the Alden Press, Oxford
Fore word
This first volume of the Specialist Periodical Reports on Organometallic Chemistry further extends the topics covered by this series. It reviews the synthesis, structure, and chemical and physical properties of those com- pounds containing carbon-to-metal bonds. In order to keep the text to a manageable size, the volume does not provide a complete coverage of every aspect of the chemistry of these compounds. Readers are referred to other Reports in the Chemical Society’s series such as: ‘Spectroscopic Properties of Inorganic and Organometallic Compounds’, Senior Reporter N. N. Green- wood; ‘Inorganic Chemistry of the Transition Elements’, Senior Reporter B. F. G. Johnson; and ‘Inorganic Reaction Mechanisms’, Senior Reporter J. Burgess.
The organo-derivatives of the main-group metals have been reviewed by element groups; however, the compounds of the transition metals have been surveyed according to ligand type. In this way it is hoped to maintain a flexibility of emphasis in this rapidly advancing field.
This first volume essentially covers the literature of organometallic chemis- try for 1971, and cites about 2500 references. In a few cases, however, prob- lems such as the United States docks strike prevented authors having access to some of the later 1971 literature. In these cases the Reporters will cover any relevant 1971 papers in the next volume, and will hence preserve continuity.
The Senior Reporters accept responsibility for the space allocated to the various sections. Each chapter is essentially self-contained. Occasionally the reader will fmd that certain results are mentioned in more than one chapter. However, we believe a certain amount of overlap between related subjects is not undesirable.
The Fifth International Conference on Organometallic Chemistry was held in Moscow on 16th-21st August 1971. Almost one thousand people attended the Conference; and two volumes of abstracts which run to a total of 1300 pages reflect current trends in organometallic chemistry. Organo- metallic chemistry was, moreover, one of the main topics at the 23rd Inter- national Congress of Pure and Applied Chemistry held in Boston (U.S.A.), 26th-30th July 1971. The lectures have been published (Volume 6 of the Proceedings, Butterworths, 1971).
E.W.A. F.G.A.S.
Contents
Chapter 1 Group I . The Alkali and Coinage Metals By B. C. Crosse
1 Lithium Structural and Bonding Studies Polylithio-compounds Halogenocarbon Derivatives Some Organic Reactions
2 Sodium and Potassium
3 Copper, Silver, and Gold Copper and Silver 7t-Complexes a-Bonded Organo-copper and -silver Compounds Gold
Chapter 2 Group II. The Alkaline Earths and Zinc and its
By B. C. Crosse
1 Beryllium
2 Magnesium Preparation and Composition Reactions Inversions and Rearrangements Halogenocarbon Derivatives
3 Calcium, Strontium, and Barium
4 Zinc and Cadmium
Congeners
5 Mercury Preparative Reactions Mercuration and Demercuration Reactions
7
10 10 11 14
17
19 19 21 23 25
26
27
29 30 35
vi
Other Reactions Carbene Precursors
Contents
37 38
Chapter 3 Group 111. Boron, Aluminium, Gallium, Indium,
By J. P. Maher and Thallium
1 Introduction
2 Boron General Preparations Radical Reactions
Mechanisms and Kinetics Preparative Reactions involving Radicals
Nucleophilic Displacements at Tetrahedral Boron
Displacement of the Alkyl Groups attached to
Olefin Elimination and Addition
Non-radical Mechanisms and Kinetics
Centres
Boranes
Reactions of R,B Organic Reactions of R3B Hydrido-organoboranes Compounds containing Boron-Nitrogen Bonds Borinic and Boronic Acids and their Derivatives
Synthesis Reactions
Compounds containing Boron-Chalcogen Bonds Compounds containing Boron-Halogen Bonds
Preparations and Reactions Structures, Bonding, and Exchange Reactions Organic Applications
Mechanisms and Kinetics Various Reactions
3 Aluminium
Transition-metal-Organoaluminium Systems
4 Gallium
5 Indium
6 Thallium Trial kyl t halliums-R ST 1 Dialkylthallium and Diarylthallium Compounds-
RzTlX
40
41 41 41 43 43 50 53
53
56 58 59 61 66 68 73 73 74 76 77
79 79 82 86 86 90 91
93
94
96 96
97
Contents vii
Monoalkylthallium and Monoarylthallium Compounds
Organic Reactions Thallium(1) Cyclopentadienides
-RTIXZ
Chapter 4 Group 111. The Carboranes By T. Onak
Chapter 5 Group IV. The Silicon Group By D. A . Armitage
1 Introduction
2 Formation of the Carbon-Metal Bond Synthesis Reactions of M-C Compounds
3 Cleavage of the Carbon-Metal Bond
4 Mechanistic Studies of Carbon-Metal Bond Cleavage Rearrangement Reactions involving the Silicon-
Carbon Bond
5 Thermochemical, Spectroscopic, and Structural Studies
6 Cyclopentadienyl Derivatives of the Group IV Elements
7 Addition Reactions
8 Alkali-metal Derivatives R3MM’
9 Catenation
10 Carbenes and their Silicon Group Congeners
11 Mercury Derivatives
12 Free Radicals
13 Hydrides of Silicon and Germanium
14 Organotin Hydrides
15 Boron Derivatives
16 Nitrogen Derivatives Diazo-compounds Azides Addition Reactions Silazanes Aminosilanes
98 101 103
104
117
118 118 122
122
125
127
128
129
131
132
133
136
140
141
144
149
150
151 151 153 154 157 159
17 Phosphine, Arsine, and Stibine Derivatives 162
Contents viii 18 Silicon-Oxygen Compounds
Alkoxysilanes and Siloxanes Rearrangements involving Compounds containing the
Silyl Esters Organosilicon Peroxides
Si-0 Bond
19 Germanium-Oxygen Compounds
20 Tin-Oxygen Compounds
21 Sulphur Derivatives
22 Lead-Oxygen and Lead-HaIogen Compounds
23 Halogen Exchange Reactions
24 Complexes of Silicon, Germanium, Tin, and Lead
25 Structural Determinations
26 Bonding in Group IV Organometallic Compounds
Chapter 6 Metal Carbonyls By E. W. Abel and F. G. A. Stone
1 Introduction
2 Spectroscopic Studies
3 Preparation of Carbonyl Compounds
4 Hydrido(carbony1)metal Complexes
5 Halogeno- and Azido-(carbony1)metal Complexes
Chapter 7 Organometallic Compounds containing Metal-
By J. D. Cotton
1 Introduction
2 Compounds containing Transition Metal-Transition
Compounds containing Isolated Bonds and Bond
Transition Metal Clusters
Metal Bonds
Metal Bonds
Sequences
3 Compounds containing Bonds between Transition Metals and the Elements of Groups IB-W
Group IB
164 164
1 67 170 170
171
172
174
177
178
179
180
181
184
185
187
191
192
194
194
194 200
207 207
Group IIB 207
Contents ix
210 210 21 1 21 1 21 2 21 2 21 3 21 5 21 5 21 6 217 222 224 225
Group IIIB Boron Aluminium Indium and Thallium
General Preparative Work The Nature of the Metal-Metal Bond Titanium Group Chromium Group Manganese Group Iron Group Cobalt Group Nickel Group
Group IV
Group V
4 Compounds containing Group mB-Group IV Element Bonds
Chapter 8 Substitution Reactions of Metal and Organo- metal Carbonyls with Group V and VI Donor Ligands
By R. J. Mawby
1 Introduction
2 General Papers on Metal Carbonyl Complexes
3 Group V
4 GroupVI Complexes of Cro, Moo and Wo Halogenocarbonyl Complexes of MoII and W" Cyclopentadienyl Carbonyl Complexes of Mo" and WI1
5 GroupVII Complexes of Mno and Reo Cyclopentadienyl Carbonyl Complexes of Mn' Other Complexes of Mn' and Re'
Complexes of the Cluster Carbonyls Mononuclear Complexes of Feo and Ruo Complexes containing the Mz(C0)6 Unit (M = Fe or
Cyclopentadienyl Carbonyl Complexes of Fe" Other Complexes of Fe", Ru", and 0s"
6 Group Vm: Fe, Ru, and 0 s
Ru)
226
228
228
229
229 229 235 236
238 238 238 239
242 242 242
243 245 247
X
7 Group Vm: Co, Rh, and Ir Complexes of Coo, Rho, and IrO Complexes of CoI, RhI , and Ir'
8 Group VIII: Ni, Pd, and Pt
9 Copper
Chapter 9 Carbene, Nitrene, and Related Complexes By J. A . Connor
1 Synthesis of Carbene Complexes
2 Structure and Bonding in Carbene Complexes
3 Reactions of Carbene Complexes
4 Nitrene Complexes
Chapter 10 Complexes containing Metal-Carbon a-Bonds By M. I. Bruce
1 a-Bonded Complexes Group IV Group V Group VI Group VII Group VIII Group I
2 Compounds Derived from Carbonylmetal Anions
3 Insertion Reactions Carbon Monoxide (and Decarbonylation Reactions) Sulphur Dioxide Olefins and Acetylenes Tetracyanoet hylene Isocyanides
Nitrogen Donors Phosphorus Donors Carbon Donors Sulphur Ligands
4 ortho-Metallation and Related Reactions
Con tents
248 248 250
252
253
254
257
259
260
261 262 263 264 265 266 270
270
274 274 276 277 280 281
282 282 285 288 288
5 Formation of M-C D-Bonds from Olefin or Diene
6 Cobaloximes, Cobalamins, and Related Compounds
7 Organic Derivatives of Schiff-base Complexes
Complexes 288
292
296
Con tents
Chapter 11 Hydrocarbon-Metal r-Complexes By M. A. Bennett
xi
1 Bonding in Mono-olefin and Acetylene Complexes 298
2 Mono-olefin Complexes 298
3 Mono-olefin Chelate Complexes 304
4 Acetylene Complexes 308
5 Acyclic Conjugated Diolefin Complexes 312
6 Cyclic Conjugated Diolefin Complexes 317 Cyclobutadiene Complexes 317 Cyclopentadiene Complexes 319 Complexes of Six- and Seven-membered Rings 321 Complexes of Eight-membered Rings 325
7 Complexes of Chelating Unconjugated Diolefins 330
8 Cationic Metal-Oleh and -Acetylene Complexes 334
9 Complexes Derived from Allenes and from Trimethyl- enemethane 338
10 Complexes of Polycyclic Hydrocarbons 341
Chapter 12 r-Allylic Complexes By M. Green
1 General Developments
2 Tantalum
3 Iron, Ruthenium, and Osmium
4 Cobalt, Rhodium, and Iridium
5 Nickel, Palladium, and Platinum
Chapter 13 r-Cyclopentadienyl, Arene, and Related Com- pounds
By R. J. Mawby
1 Introduction
2 z-Cyclopentadienyl Complexes Features of General Interest Group IV
Preparation of Complexes Other Studies
344
345
345
350
353
366
366 366 367 367 369
xii
Group V Group VI
Preparation of Complexes 0 t her Studies
Group VII Group VIII : Fe, Ru, and 0 s
Preparation of Complexes Other Studies
Group VIII: Co, Rh, and Ir Group VIII: Ni, Pd, and Pt
Preparation of Complexes 0 t her Studies
Other Metals
3 n-Arene Complexes Group VI
Preparation of Complexes 0 t her Studies
Group VII Group VIII: Fe, Ru, and 0 s Group VIII: Co, Rh, and Ir Group VIII: Ni Uranium
4 Carborane Complexes The [B9CzH1 1]2- Ligand and Related Systems Other Carborane Ligands Theory of Bonding in Carborane Complexes
5 Complexes with Other Related Ligands Tris(pyrazoly1)borate Complexes Borabenzene Complexes Borazole Complexes Pyrrole and Pyrrolyl Complexes Thiophen Complexes
Contents
370 371 371 373 373 374 374 376 377 378 378 380 380
381 381 381 382 382 382 383 384 384
384 384 385 385
386 386 387 387 387 387
Chapter 14 Substitution Reactions of Hydrocarbon-Metal
By M. I . Bruce
1 Introduction
2 Results of General Interest
3 Individual Systems
V-Com plexes
(n-C6H6)Cr(CO), (Benchrotrene)
388
388
390 390
Contents xiii
393 393 395 397 408
[(Tr~pylium)Cr(CO)~ J + and Related Complexes ( n-C5H5)Mn(CO), (Cymantrene) ( n-C4H4)Fe(C0), (n-Diex~e)Fe(CO)~ Complexes [( n-CSH5)Fe( n-C6Hs)] + Complexes ( n-C5H&Co and Derived ( n-CsHs)Co( n-diene)
Cobalt-Carbon Cluster Compounds Complexes
4 Chemistry of the Iron-group Metallocenes (Ferrocene, Ruthenocene, and Osmocene)
General General Chemistry Proton N.M.R. Studies Stereochemistry of Ferrocenes Biferrocenyls and Bridged Ferrocenes (Ferro-
Polymeric Ferrocene Derivatives Ferrocene Derivatives containing Heteroatoms
cenophanes)
Boron Silicon and Germanium Phosphorus and Arsenic Sulphur Transition Metals
Ferricinium Salts
Chapter 15 Oxidative-addition and Related Reactions By M. Green
1 Niobium and TanMum
2 Chromium, Molybdenum, and Tungsten
3 Iron, Ruthenium, and Osmium
4 Cobalt, Rhodium, and Iridium
5 Nickel, Palladium, and Platinum
Chapter 16 Homogeneous Catalysis By F. J. McQuilIin
1 General
409 41 1
412 412 413 420 420
422 425 426 426 426 427 428 428 428
431
432
434
436
446
2 Hydrogenation
3 Isomerhation
455
455
458
