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Volume 7
Mechanisms of Inorganic and Organometallic Reactions
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Volume 7
Mechanisms o/Inorganic and Organometallic Reactions
Edited by
M. V. Twigg Imperial Chemieal Industries P.L. C. Billingham, Cleveland, United Kingdom
SPRINGER SCIENCE+BUSINESS MEDIA, LLC
The Library of Congress has cataloged this serial title as folIows:
Mechanisms of inorganic and organometallic reactions. - Vol. I--New York: Plenum Press, cl983-
v.: ill.; 24 cm. Editor: M. V. Twigg. ISSN 0740-8900 = Mechanisms of inorganic and organometallic reactions.
1. Chemical reactions - Collected works. 2. Chemistry, Inorganic - Collected works. 3. Organometallic chemistry-Collected works. 4. Organometallic compounds-Collected works. I. Twigg, M. V. QD50l.M425 541.3'9'.05-dc19 87-648073
Library of Congress [87061
ISBN 978-1-4613-6650-8 ISBN 978-1-4615-3710-6 (eBook) DOI 10.1007/978-1-4615-3710-6
© 1991 Springer Science+Business Media New York Originally published by Plenum Press, New York in 1991 Softcover reprint of the hardcover I st edition 1991
All rights reserved
AACR 2 MARC-S
No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher
Contributors
M. Bochmann School of Chemical Sciences, University of East Anglia, Univer-sity Plain, Norwich NR47TJ, U.K.
1. Burgess Chemistry Department, The University, Leicester LEI 7RH, U.K.
E. C. Constable University Chemical Laboratory, Lensfield Road, Cambridge CB2 lEW, U.K.
R. 1. Cross Chemistry Department, University of Glasgow, Glasgow, Scotland G128QQ, U.K.
R. van Eldik Institut fUr Anorganische Chemie, Universitat Witten/Herdecke, Stockumer Strasse 10, 5810 Witten-Annen, Germany
1. F. Endicott Chemistry Department, Wayne State University, Detroit, Michigan, 48202
R. W. Hay Chemistry Department, University of St. Andrews, St. Andrews, Scotland KY169ST, U.K.
D. A. House Chemistry Department, University of Canterbury, Christchurch 1, New Zealand
v
vi Contributors
L. A. P. Kane-Maguire Chemistry Department, Wollongong University, Wol-longong, NSW 2500, Australia
S. F. Lincoln Department of Inorganic and Organic Chemistry, University of Adelaide, Adelaide, South Australia 5001, Australia
D. H. Macartney Department of Chemistry, Queen's University, Kingston, Ontario K7L 3N6, Canada
A. McAuley Chemistry Department, University of Victoria, Victoria, British Columbia V8W 3P6, Canada
K. G. Orrell Chemistry Department, University of Exeter, Stocker Road, Exeter, Devon EX44QD, U.K.
R. D. Pike Chemistry Department, Brown University, Providence, Rhode Island, 02912
A. J. Poe Chemistry Department, University of Toronto, Toronto, Ontario M5S 1A1, Canada
K. Schneider Institut fUr Anorganische Chemie, Universitiit Witten/Herdecke, Stockumer Strasse 10,5810 Witten-Annen, Germany
G. Steadman Chemistry Department, University of Swansea, Singleton Park, Swansea, Wales SA2 8PP, U.K.
T. Whitcombe Chemistry Department, University of Victoria, Victoria, British Columbia V8W 3P6, Canada
Preface
The objective of Mechanisms of Inorganic and Organometallic Reactions is to provide an ongoing critical review of the literature concerned with the mechanisms of reactions of inorganic and organometallic compounds. The main focus is on reactions in solution, although solid state and gas phase studies are included where they provide relevant mechanistic insight.
Each volume covers an eighteen month literature period, and this, the seventh volume in the series, deals with papers published during July 1988 through December 1989. Where appropriate, there are references to earlier work, and also to specific sections in previous volumes. Coverage continues to span the whole area as comprehensively as possible in each volume, and although it is impossible for it to be absolutely complete, every effort is made to include all the important published work that is relevant to the elucidation of reaction mechanisms.
Numerical data are reported in the units used by the original authors, and they are only converted to common units when making comparisons. The basic format of earlier volumes is retained to facilitate tracing progress over several years in a particular topic; this can now be done for more than a decade worth of research.
In the last volume, ligand reactivity of both coordination and organometallic compounds were brought together in Chapter 12, and, in response to numerous positive comments from readers, this arrangement has been maintained. There have been some similar suggestions about oscillating reactions, and this topic may have a separate section in the next volume.
As always, thanks are due to all of the contributors for the tremendous effort that goes into collecting references and producing the chapters, and to the publishers for help and support during the production and distribution of the series.
vii
viii Preface
The support and encouragement of many readers who send reprints or preprints of their publications are also very much appreciated. General comments and suggestions from readers are always most welcome.
M. V. Twigg
Contents
Part L Electron Transfer Reactions
Chapter 1. Electron Transfer: General and Theoretical
J. F. Endicott
1.1. Overview and General Aspects of Reactions in Fluid Media 3 1.2. Electronic Coupling (Kel) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2.1. The Distance Dependence of Electron Transfer Rates. . . . . 5 1.2.2. Electric and Magnetic Field Effects on Electronic Coupling
and Related Problems of Photoinduced Electron Transfer 8 1.3. The Free-Energy Dependence of Electron Transfer Reactions: The
"Inverted Region" Problem .................................. 10 1.4. The Effects of Solvent Dynamics .............................. 12 1.5. Metal-to-Metal and Ligand-to-Ligand Charge Transfer ("Inter-
valence" Transfer) .......................................... 14
Chapter 2. Redox Reactions between Two Metal Complexes
D. H. Macartney
2.1. Introduction................................................ 15 2.2. Reactions of Metal Aqua and Oxo Ions........................ 15
2.2.1. Titanium............................................. 15 2.2.2. Vanadium and Chromium. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
ix
x Contents
2.2.3. Iron................................................. 17 2.2.4. Molybdenum and Tungsten . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.3. Reactions of Metal Ion Complexes ............................ 18 2.3.1. Chromium........................................... 18 2.3.2. Manganese........................................... 18 2.3.3. Iron, Ruthenium, and Osmium ......................... 19 2.3.4. Cobalt and Rhodium. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 2.3.5. Nickel, Palladium, and Platinum. . . . . . . . . . . . . . . . . . . . . . . . 21 2.3.6. Copper and Silver .................................... 22 2.3.7. Technetium and Rhenium. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 2.3.8. ytterbium............................................ 36
2.4. Reactions with Metalloproteins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36 2.4.1. Introduction......................................... 36 2.4.2. Copper Proteins ........... . . . . . . . . . . . . . . . . . . . . . . . . . . . 36 2.4.3. Hemoglobin and Myoglobin. . . . . . . . . . . . . . . . . . . . . . . . . . . . 39 2.4.4. Cytochromes......................................... 39 2.4.5. Iron-Sulfur Proteins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
Chapter 3. Metal-Ligand Redox Reactions
A. McAuley and T. W. Whitcombe
3.1. Introduction................................................ 47 3.2. Oxygen, Peroxide, and Other Oxygen Compounds. . . . . . . . . . . . . . . 48
3.2.1. Dioxygen............................................ 48 3.2.2. Hydrogen Peroxide ................................... 50 3.2.3. Alkyl Hydroperoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
3.3. Nitrogen Compounds and Oxyanions . . . . . . . . . . . . . . . . . . . . . . . . . . 55 3.3.1. Hydrazine, Azides, Hydroxylamines, and Derivatives. . . . . . 55 3.3.2. Oxynitrogen Compounds .............................. 55 3.3.3. Amines and Nitriles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3.4. Sulfur Compounds and Oxyanions ............................ 57 3.4.1. Peroxodisulfate and Peroxomonosulfate ................. 57 3.4.2. Sulfur Dioxide and Sulfite Ions. . . . . . . . . . . . . . . . . . . . . . . . . 58 3.4.3. Sulfoxides........................................... 59 3.4.4. Alkyl Sulfur Compounds .............................. 60 3.4.5. Selenium, Tellurium, and Elemental Sulfur. . . . . . . . . . . . . . . 62
3.5. Halogen, Halides, and Halogen Oxyanions ..................... 62 3.5.1. Halogens............................................ 62 3.5.2. Halides.............................................. 63 3.5.3. Oxyhalogen Compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
3.6. Phosphorus, Arsenic, and Oxycompounds ...................... 65 3.6.1. Phosphorus Oxyanions ................................ 65 3.6.2. Phosphines and Arsines ............................... 65
3.7. Inorganic Radicals........................................... 66
Contents xi
3.8. Ascorbic Acid, Quinols, Catechols, and Diols . . . . . . . . . . . . . . . . . . . 67 3.8.1. Ascorbic Acid. . . . . .. .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67 3.8.2. Aromatic Diols and Diones ............................ 68 3.8.3. Aromatic and Aliphatic Alcohols ....................... 69
3.9. Carboxylic Acids, Carboxylates, Carbon Dioxide, and Carbon Monoxide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70 3.9.1. Carboxylic Acids and Carboxylates ..................... 70 3.9.2. Carbon Dioxide and Carbon Monoxide................. 71
3.10. Alkyl Halides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71 3.11. Organic Radicals............................................ 72
Part IL Substitution and Related Reactions
Chapter 4. Reactions of Compounds of the Nonmetallic Elements
G. Steadman
4.1. Boron.................................... . . . . . . . . . . . . . . . . . . 77 4.2. Carbon................................... . . . . . . . . . . . . . . . . . . 78 4.3. Silicon..................................................... ·78 4.4. Germanium............................... . . . . . . . . . . . . . . . . . . 82 4.5. Nitrogen................................. . . . . . . . . . . . . . . . . . . 83 4.6. Phosphorus................................ . . . . . . . . . . . . . . . . . 86 4.7. Arsenic.................................................... 91 4.8. Oxygen.................................................... 91 4.9. Sulfur..................................... . . . . . . . . . . . . . . . . . 92 4.10. Selenium and Tellurium. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93 4.11. Halogens, Krypton, and Xenon............................... 94
4.11.1. Fluorine............................................ 94 4.11.2. Chlorine........................... . . . . . . . . . . . . . . . . . 94 4.11.3. Bromine........................... . . . . . . . . . . . . . . . . . 95 4.11.4. Iodine.............................................. 95 4.11.5. Krypton and Xenon.................................. 96
4.12. Oscillating Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
Chapter 5. Substitution Reactions of Inert-Metal ComplexesCoordination Numbers 4 and 5
R. J. Cross
5.1. Introduction................................................ 101 5.2. Associative Ligand Exchange at Square-Planar Platinum(II) ...... 103 5.3. Associative Ligand Exchange at Square-Planar Palladium(II) ..... 105 5.4. Ligand Exchange at Platinum(I1} by Dissociative Processes. . . . . . . 108
xii Contents
5.5. Ligand Exchange at Nickel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110 5.6. Reactions of Planar Ir(I), Rh(I), Au(III), and Cu(lI) Complexes 112 5.7. Five-Coordinate Species. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116 5.8. Trans Effect. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121 5.9. Isomerizations.............................................. 122
Chapter 6. Substitution Reactions of Inert-Metal ComplexesCoordination Numbers 6 and Above: Chromium
D. A. House
6.1. Introduction................................................ 125 6.2. Aquation and Solvolysis of Chromium (III) Complexes. . . . . . . . . . . 128
6.2.1. [Cr(III)(Ls)X]n+ Systems (L = OH2 , NH3 ) • • • • • • • • • • • • • • • 128 6.2.2. Cr(III)-C Bond Rupture. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128 6.2.3. Amine and Other Complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . 129 6.2.4. Dechelation/Chelation Processes ....................... 129 6.2.5. Metal-Ion-Assisted Aquation . . . . . . . . . . . . . . . . . . . . . . . . . . . 129 6.2.6. Porphyrins........................................... 132
6.3. Formation of Chromium(lIl) Complexes . . . . . . . . . . . . . . . . . . . . . . . 132 6.3.1. The Nature of the C2+ Cation in Aqueous Solution. . . . . . . 132 6.3.2. Anation Reactions .................................... 135
6.4. Base Hydrolysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137 6.5. Oxidation and Reduction of Cr(IlI) Complexes . . . . . . . . . . . . . . . . . 139 6.6. Isomerization and Racemization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140 6.7. Photochemistry and Photophysics of Chromium(lIl) Complexes. 141 6.8. The Solid State. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
6.8.1. Single-Crystal X-Ray Structures ........................ 146 6.8.2. Synthesis and Solid-State Decomposition ................ 148
6.9. Other Oxidation States. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149 6.9.1. Chromium(II)........................................ 149 6.9.2. Chromium (IV) ....................................... 149 6.9.3. Chromium(V)........................................ 150 6.9.4. Chromium(VI)....................................... 153
6.10. Catalysis ................................................... 156 6.11. Miscellaneous............................................... 156
Chapter 7. Substitution Reactions of Inert-Metal ComplexesCoordination Numbers 6 and Above: Cobalt
R. W. Hay
7.1. Aquation................................................... 157 7.2. Catalyzed Aquation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159 7.3. Base Hydrolysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160 7.4. Anation.................................................... 162
Contents xiii
7.5. Solvolysis.................................................. 163 7.6. Isomerization............................................... 164 7.7. Carbonato Complexes........................................ 165 7.8. Vitamin B12 and Cobaloximes ................................. 165
Chapter 8. Substitution Reactions of Inert-Metal ComplexesCoordination Numbers 6 and Above: Other Inert Centers
J. Burgess
8.1. Introduction................................................ 169 8.2. Groups 5 to 7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
8.2.1. Vanadium............................................ 173 8.2.2. Molybdenum......................................... 173 8.2.3. Tungsten............................................ 174 8.2.4. Manganese........................................... 174 8.2.5. Technetium.......................................... 174 8.2.6. Rhenium............................................ 177
8.3. Iron....................................................... 177 8.3.1. Penta- and Tetracyanoferrates .......................... 177 8.3.2. Iron(II)-Diimine Complexes. . . . . . . . .. . . . . . . . . . . . . . . . . . 179 8.3.3. Other Iron(II) Complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181 8.3.4. Iron(III) Complexes .................................. 182
8.4. Ruthenium................................................. 183 8.4.1. Ruthenium(II)........................................ 183 8.4.2. Ruthenium(III)....................................... 186 8.4.3. Ruthenium(IV), Ruthenium(V), and Ruthenium(VI) . . . . . . . 187
8.5. Osmium.................................................... 187 8.6. Rhodium................................................... 188 8.7. Iridium.................................................... 189 8.8. Platinum(IV)............................................... 190
Chapter 9. Substitution Reactions of Labile Metal Complexes
S. F. Lincoln
9.1. General.................................................... 191 9.2. Ligand Substitution on Complexes of Uni- and Bivalent Metal Ions 192
9.2.1. Ligand Substitution on Complexes of Alkali and Alkaline Earth Metal Ions ..................................... 192
9.2.2. Ligand Substitution on Complexes of Gold(I) and Copper(I) 196 9.2.3. Ligand Substitution on Complexes of Uni- and Bivalent First-
Row Transition Metal Ions .;.......................... 197 9.2.4. Ligand Substitution on Complexes of Platinum(II) and Pal-
ladium(II) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
xiv Contents
9.2.5. Ligand Substitution on Complexes of Mercury(II) ........ 208 9.3. Ligand Substitution on Complexes of Trivalent Metal Ions and Metal
Ions of Higher Valency...................................... 209 9.3.1. Ligand Substitution on Complexes of the Trivalent Main
Group Metal Ions.................................... 209 9.3.2. Ligand Substitution on Complexes of the Trivalent Transition
Metal Ions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210 9.3.3. Ligand Substitution on Complexes of the Trivalent Lan-
thanide Ions ......................................... 213 9.3.4. Ligand Substitution on Complexes of Oxo Metal Ions. . . . . 215
9.4. Ligand Substitution Processes in Dimeric and Higher Oligomeric Metal Complexes ........................................... 216
Part III. Reactions of Organometallic Compounds
Chapter 10. Substitution and Insertion Reactions
A. J. Poe
10.1. Substitution Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221 10.1.1. Introduction....................................... 221 10.1.2. Mononuclear Complexes............................ 223 10.1.3. Dinuclear Complexes ............................... 243 10.1.4. Trinuclear and Larger Clusters ....................... 246
10.2. Insertion Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252 10.2.1. Carbon Monoxide Insertion.......................... 252 10.2.2. Other Insertions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
Chapter 11. Metal-Alkyl and Metal-Hydnde Bond Formation and Fission; Oxidative Addition and Reductive Elimination
R. D. Pike
11.1. Introduction............................................... 257 11.2. Dihydrogen Complexes ..................................... 258 11.3. Metal-Hydride Complexes.................................. 260 11.4. C-H Bond Activation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
11.4.1. Unactivated C-H Bonds............................ 263 11.4.2. Activated C-H Bonds.............................. 265 11.4.3. Intramolecular C-H Bonds. . . . . . . . . . . . . . . . . . . . . . . . . . 268
11.5. Reductive Elimination Forming Carbon-Carbon Bonds......... 271 11.6. Oxidative Addition and Reductive Elimination of Alkyl Halides 274 11.7. Oxidative Addition and Reductive Elimination Involving Two Metal
Centers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
Contents xv
Chapter 12. Reactivity of Coordinated Ligands
R. W. Hay, E. C. Constable, and L. A. P. Kane-Maguire
12.1. Introduction............................................... 279 12.2. Cobalt Complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
12.2.1. Amino Acids and Peptides . . . . . . . . . . . . . . . . . . . . . . . . . . . 279 12.2.2. Carboxylic and Phosphate Esters ..................... 282 12.2.3. Ligand Synthesis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
12.3. Other Metal Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285 12.3.1. Introduction....................................... 285 12.3.2. Reactions of Coordinated Nitriles and Related Ligands 286 12.3.3. Nucleophilic Addition to Coordinated Carbonyls ....... 287 12.3.4. Electrophilic Attack at Coordinated Nitrogen and Oxygen 289 12.3.5. Reactions of Coordinated Phosphorus Compounds. . . . . . 290 12.3.6. Reactions of Coordinated Sulfur Ligands .............. 292 12.3.7. Reactions of Coordinated Heterocyclic Ligands. . . . . . . . . 293 12.3.8. Reactions Involving Cyclometalated Ligands ........... 294
12.4. Organometallic Compounds ................................. 295 12.4.1. Reactions with Nucleophiles ......................... 295 12.4.2. Reactions with Electrophiles ......................... 303
Chapter 13. Rearrangements, Intramolecular Exchanges, and Isomerizations of Organometallic Compounds
K. G. Orrell
13.1. Introduction............................................... 309 13.2. Mononuclear Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
13.2.1. Isomerizations and Ligand Site Exchange. . . . . . . . . . . . . . 309 13.2.2. Ligand Rotations about the Metal-Ligand Bond. . . . . . . . 313 13.2.3. Migration of Metal Atoms between Different Ligand Sites 316 13.2.4. Agostic Bonding and Hydrogen Atom Migrations. . . . . . . 320 13.2.5. Internal Ligand Rearrangements. . . . . . . . . . . . . . . . . . . . . . 321
13.3. Dinuclear Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327 13.3.1. Restricted Rotations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327 13.3.2. Carbonyl Ligand Migrations ......................... 328 13.3.3. Migration of Other Ligands between Metal Atoms ...... 328 13.3.4. Other Exchange Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
13.4. Cluster Compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 333 13.4.1. Rearrangements Involving the Relative Motion of Metal
Atoms in a Cluster ...................... . . . . . . . . . . . 333 13.4.2. Carbonyl Ligand Exchanges. . . . . . . . . . . . . . . . . . . . . . . . . . 335 13.4.3. Other Exchange Processes ........................... 336
xvi Contents
Chapter 14. Homogeneous Catalysis of Organic Reactions by Transition Metal Complexes
M. Bochmann
14.1. General................................................... 339 14.2. Hydrogenations............................................ 340 14.3. Hydrogen Transfer and Dehydrogenations. . . . . . . . . . . . . . . . . . . . . 344 14.4. C-H Activation........... .. ........ .... . ................. 345 14.5. Hydrosilylation............................................ 347 14.6. Nucleophilic Additions to C=C and C=C . . . . . . . . . . . . . . . . . . . . 348 14.7. Olefin Dimerization and Oligomerization. . . . . . . . . . . . . . . . . . . . . . 350 14.8. Alkyne Oligomerization ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352 14.9. Metathesis................................................. 354 14.10. Olefin Polymerization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355 14.11. Alkyne Polymerizations..... . .. .. ..... . . .... ................ 356 14.12. Carbonylations............. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
14.12.1. Carbonylations of C=C and C_C. ........... . .... . . 358 14.12.2. Carbonylation of Organic Halides. . . . . . . . . . . . . . . . . . . . 359 14.12.3. Hydroformylation.................................. 360 14.12.4. Water-Gas Shift Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . 361 14.12.5. CO Reduction and Alcohol Carbonylation . . . . . . . . . . . . 362
14.13. Cross-Coupling Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
Part IV. Compilations of Numerical Data
Chapter 15. Volumes of Activation for Inorganic and Organometallic Reactions: A Tabulated Compilation
R. van Eldik and K. Schneider
15.1. Introduction............................................... 371 15.2. Data in Tabular Form. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 372
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
Index .............................. , . . . . . . . . . . . . . . . . . . . . . . . . . . . . 447