The Organometallic Chemistry of the Transition Metals

522 Pages·2014·7.2 MB·English

by  Robert H. Crabtree

THE
ORGANOMETALLIC
CHEMISTRY OF THE
TRANSITION METALS

THE
ORGANOMETALLIC
CHEMISTRY OF THE
TRANSITION METALS
Sixth Edition
ROBERT H. CRABTREE
Yale University, New Haven, Connecticut
Copyright © 2014 by John Wiley & Sons, Inc. All rights reserved.
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Library of Congress Cataloging-in-Publication Data:
Crabtree, Robert H., 1948–
The organometallic chemistry of the transition metals / by Robert H. Crabtree.—
Sixth edition.
pages cm
Includes bibliographical references and index.
ISBN 978-1-118-13807-6 (cloth)
1. Organometallic chemistry. 2. Organotransition metal compounds. I. Title.
QD411.8.T73C73 2014
547′.056–dc23
2013046043
Printed in the United States of America
ISBN: 9781118138076
10 9 8 7 6 5 4 3 2 1
CONTENTS
Preface xi
List of Abbreviations xiii
1 Introduction 1
1.1 Why Study Organometallic Chemistry?, 1
1.2 Coordination Chemistry, 3
1.3 Werner Complexes, 4
1.4 The Trans Effect, 9
1.5 Soft versus Hard Ligands, 10
1.6 The Crystal Field, 11
1.7 The Ligand Field, 19
1.8 The sdn Model and Hypervalency, 21
1.9 Back Bonding, 23
1.10 Electroneutrality, 27
1.11 Types of Ligand, 29
References, 37
Problems, 38
2 Making Sense of Organometallic Complexes 40
2.1 The 18-Electron Rule, 40
2.2 Limitations of the 18-Electron Rule, 48
2.3 Electron Counting in Reactions, 50
2.4 Oxidation State, 51
v
vi COnTEnTS
2.5 Coordination number and Geometry, 57
2.6 Effects of Complexation, 60
2.7 Differences between Metals, 63
References, 66
Problems, 67
3 Alkyls and Hydrides 69
3.1 Alkyls and Aryls, 69
3.2 Other σ-Bonded Ligands, 84
3.3 Metal Hydrides, 86
3.4 Sigma Complexes, 89
3.5 Bond Strengths, 92
References, 95
Problems, 96
4 Carbonyls, Phosphines, and Substitution 98
4.1 Metal Carbonyls, 98
4.2 Phosphines, 109
4.3 n-Heterocyclic Carbenes (nHCs), 113
4.4 Dissociative Substitution, 115
4.5 Associative Substitution, 120
4.6 Redox Effects and Interchange Substitution, 122
4.7 Photochemical Substitution, 124
4.8 Counterions and Solvents in Substitution, 127
References, 129
Problems, 131
5 Pi-Complexes 134
5.1 Alkene and Alkyne Complexes, 134
5.2 Allyls, 140
5.3 Diene Complexes, 144
5.4 Cyclopentadienyl Complexes, 147
5.5 Arenes and Other Alicyclic Ligands, 154
5.6 Isolobal Replacement and Metalacycles, 158
5.7 Stability of Polyene and Polyenyl Complexes, 159
References, 160
Problems, 161
6 Oxidative Addition and Reductive Elimination 163
6.1 Introduction, 163
6.2 Concerted Additions, 166
COnTEnTS vii
6.3 S 2 Pathways, 168
n
6.4 Radical Mechanisms, 170
6.5 Ionic Mechanisms, 172
6.6 Reductive Elimination, 173
6.7 σ-Bond Metathesis, 179
6.8 Oxidative Coupling and Reductive Fragmentation, 180
References, 182
Problems, 182
7 Insertion and Elimination 185
7.1 Introduction, 185
7.2 CO Insertion, 187
7.3 Alkene Insertion, 192
7.4 Outer Sphere Insertions, 197
7.5 α, β, γ, and δ Elimination, 198
References, 201
Problems, 201
8 Addition and Abstraction 204
8.1 Introduction, 204
8.2 nucleophilic Addition to CO, 207
8.3 nucleophilic Addition to Polyenes and Polyenyls, 208
8.4 nucleophilic Abstraction in Hydrides, Alkyls, and
Acyls, 215
8.5 Electrophilic Addition and Abstraction, 216
8.6 Single-Electron Transfer and Radical Reactions, 219
References, 221
Problems, 222
9 Homogeneous Catalysis 224
9.1 Catalytic Cycles, 224
9.2 Alkene Isomerization, 231
9.3 Hydrogenation, 233
9.4 Alkene Hydroformylation, 242
9.5 Alkene Hydrocyanation, 245
9.6 Alkene Hydrosilylation and Hydroboration, 246
9.7 Coupling Reactions, 248
9.8 Organometallic Oxidation Catalysis, 250
9.9 Surface, Supported, and Cooperative Catalysis, 251
References, 253
Problems, 256
viii COnTEnTS
10 Physical Methods 259
10.1 Isolation, 259
10.2 1H nMR Spectroscopy, 260
10.3 13C nMR Spectroscopy, 264
10.4 31P nMR Spectroscopy, 266
10.5 Dynamic nMR, 268
10.6 Spin Saturation Transfer, 271
10.7 T and the nuclear Overhauser Effect, 272
1
10.8 IR Spectroscopy, 276
10.9 Crystallography, 279
10.10 Electrochemistry and EPR, 281
10.11 Computation, 283
10.12 Other Methods, 285
References, 287
Problems, 288
11 M–L Multiple Bonds 290
11.1 Carbenes, 290
11.2 Carbynes, 302
11.3 Bridging Carbenes and Carbynes, 305
11.4 N-Heterocyclic Carbenes, 306
11.5 Multiple Bonds to Heteroatoms, 310
References, 313
Problems, 315
12 Applications 317
12.1 Alkene Metathesis, 317
12.2 Dimerization, Oligomerization, and Polymerization of
Alkenes, 324
12.3 Activation of CO and CO , 332
2
12.4 C–H Activation, 336
12.5 Green Chemistry, 343
12.6 Energy Chemistry, 344
References, 347
Problems, 349
13 Clusters, Nanoparticles, Materials, and Surfaces 353
13.1 Cluster Structures, 354
13.2 The Isolobal Analogy, 364
13.3 nanoparticles, 368