Advances in Organometallic Chemistry (eBook)

Front Cover 1
Molecular Rearrangements 4
Copyright Page 5
Contents 6
List of Contributors 10
Preface 12
Introduction 14
Chapter 1. 1,2-Anionic Rearrangements of Organosilicon and Germanium Compounds 18
I. Introduction 18
II. The Hydrazine (N.N) Rearrangement 20
III. The Hydroxylamine (O.N) Rearrangement 31
IV. The Wittig (0.C) Rearrangement 35
V. The S.C Rearrangement 41
VI. The N.C Rearrangement 42
VII. Other Anionic Rearrangements, Known and Unknown 44
References 47
Chapter 2. Dyotropic Rearrangements and Related s–s Exchange Processes 50
I. Introduction 50
II. Thermal Rearrangement of 1,2-Bis(Silyl) Derivatives 52
III. Thermal Rearrangement of Allyl Silylmethyl Ethers 64
IV. Thermal Rearrangement of Benzyl Silylmethyl Ethers: A Case for Anchimerically Accelerated Unimolecular Bond Homolysis 69
V. Thermal Rearrangement of N,N-Bis(Trimethylsilyl)-0-Allylhydroxylami~ 72
VI. Thermal Rearrangement of Bis- and Tris(Silyl)hydroxylamines 72
VII. Thermal Rearrangement of Squaric Acid Bis(Trimethylsilyl) Ester . 75
VIII. Miscellaneous s–s Exchange Reactions 77
IX . Outlook 80
References 80
Chapter 3. Rearrangements of Unsaturated Organoboron and Organoaluminum Compounds 84
I. Introduction 84
II. Sigmatropic Rearrangements of Organoboranes 89
III. Migrations in Tetracoordinate Organoboranes 99
IV. Allylic Isomerizing or Derivatizing Reactions of Organoalanes 108
V. Carbalumination via Intermediate Complexes 115
VI. Prospects for Future Developments 123
References 124
Chapter 4. Rearrangements of Organoaluminum Compounds and Their Group III Analogs 128
I. Introduction 128
II. Structures and Bonding in Group III Derivatives 129
III. Monomer–Dimer Equilibria 132
IV. Exchange Processes Involving Dissociated Species 133
V. Exchange Reactions of Group III Alkyl Addition Compounds 135
VI. Intramolecular Exchange Processes 137
VII. Intermolecular Exchange Involving Partial Dissociation 142
VIII. Processes Involving Metal–Multiple Bond Interactions 143
References 146
Chapter 5. Organomagnesium Rearrangements 148
I. lntroduction 148
II. Intramolecular Addition and Ring-Cleavage Rearrangements 149
III. Rearrangement of Allylic Organomagnesium Compounds 177
IV.1,2-Shifts 179
References 180
Chapter 6. Aryl Migrations in Organometallic Compounds of the Alkali Metals 184
I. Introduction 184
II. Migrations of Aryl Groups in Anions 187
III. Migrations of Aryl in Intermediate Radicals 210
IV. Migrations of Aryl in Radical Anions of Aromatic Hydrocarbons and Related Reactions 213
V. Migration of Phenyl in Competition with Cleavage of Benzyl 219
VI. Conclusions 223
References 224
Chapter 7. Fluxional and Nonrigid Behavior of Transition Metal Organometallicp-Complexes 228
I. Introduction 228
II. Developments in Instrumentation and Technique 229
III. Ring Whizzers 239
IV. Rotation of p-Complexes 242
V. Coupling of p-Ligand Rotation with Carbonyl Rearrangement 248
References 253
Chapter 8. s–p Rearrangements of Organotransition Metal Compounds 258
I. Scope and Limitation 258
II. Factors Influencing the Static Modes 259
III. Initiation of the s–p Rearrangement 261
IV. Mechanistic Aspects of the Rearrangement 267
V. The Role of the s-p Rearrangement in Catalysis 269
VI. End-On and Side-On Coordination 288
VII. Vitamin B12 Coenzyme-Catalyzed Rearrangements 292
VIII. Conclusion 295
References 296
Chapter 9. The Olefin Metathesis Reaction 300
I. Introduction 300
II. The Mechanism of the Olefin Metathesis Reaction 302
III. Selectivity in Olefin Metathesis of Unsymmetrically Substituted Ethylenes 316
IV. Metatheses Induced by Metal-Carbenes 322
V. The Stereochemistries of Olefin Metatheses 326
References 330
Chapter 10. Molecular Rearrangements in Polynuclear Transition Metal Complexes 336
I. Introduction 336
II. Dinuclear Metal Carbonyls and Their Derivatives 340
III. Metal Carbonyl and Isonitrile Clusters 343
IV. Hydrido Carbonyl Clusters 349
V. Dinuclear Olefin Complexes 353
VI. Olefin and Acetylene Cluster Complexes 355
VII. Skeletal Atom Migration 358
References 360
Postscript 364
Subject Index 366
Comulative List of Contributors 375
Comulative List of Titles 377