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

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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