Advances in Organometallic Chemistry (eBook)

Front Cover 1
Advances in Organometallic Chemistry, Volume 20 4
Copyright Page 5
Contents 6
List of Contributors 10
Chapter 1. Transition Metal Formyl Complexes 12
I. Introduction 12
II. Synthesis of Transition Metal Formyl Complexes 14
III. Physical Properties of Transition Metal Formyl Complexes 24
IV. Reactions of Transition Metal Formyl Complexes 26
V. Topics Relating to the Stability and Decompostion of Transition Metal Formyl Complexes 37
VI. Conclusion 44
Addendum 45
References 46
Chapter 2. The Organic Chemistry of Gold 50
I. Introduction 51
II. Organogold(I) Complexes: Prepartion and Characterization 52
III. Reactions of Organogold(I) Complexes 74
IV. Organogold (III) Complexes: Prepartion and Characterization 83
V. Reactions of Organogold (III) Complexes 100
VI Comparisons of Bonding, Soectra, and Reactivity of Organogold (I) and Organogold (III) Complexes 105
VII. Comparisons of Organogold Complexes with Those of Other Metals 112
References 116
Chapter 3. Arsonium Ylides 126
I. Introduction 126
II. Methods of Preparation 127
III. Structure and Physical Properties 136
IV. Chemical Reactions and Synthetic Applications 145
V. Conclusion 164
References 166
Chapter 4. The Methylene Bridge 170
I. Introduction 171
II. Nomenclature 172
III. Historical Background 173
IV. Synthesis of µ-Methylene Transition Metal Complexes 176
V. Theory and Bonding in Simple Dimetallacyclopropane Complexes 208
VI. Structural Features of µ-Methylene Complexes 211
VII. Spectroscopic Characterization of µ-Methylene Metal Complexes 220
VIII. Reactivity of Methylene-Bridged Transition Metal Complexes 227
IX. Catalytic Implications of the Methylene Bridge 239
X. The Group IV µ-Methylene Congeners 242
XI. One Step Beyond the Methylene Bridge: µ(.,.')-Alkanediyl Complexes 248
XII. Challenging Problems and Future Trends 253
Addendum 254
References 263
Chapter 5. Nucleophilic Displacement at Silicon: Recent Developments and Mechanistic Implications 276
I. Introduction 276
II. Nucleophilic Displacement at Silicon:Controlling Factors of the Stereochemistry 277
III. Nucleophilic Displacements at Silicon:A Rationalization of the Stereochemistry by a Frontier-Orbital Approximation 298
IV. Conclding Comments 319
References 320
Chapter 6.The Biological Methylation of Metals and Metalloids 324
I. Introduction 325
II. Methylcobalamin: Chemical Rate Studies 327
III. Other Aqueous Transmethylations: Chemical Rate Studies 333
IV. Biological Transmethylation: Rate Studies 335
V. Mechanisms of Transmethylation 343
VI. Other Aspects of Biological Transmethylation 351
VII. Conclusions 356
Addendum 357
References 359
Index 368
Cumulative List of Contributors 376
Cumulative List of Titles 378