Advances in Organometallic Chemistry (eBook)

Front Cover 1
Advances in Organometallic Chemistry, Volume 18 4
Copyright Page 5
Contents 6
List of Contributors 10
Chapter 1. Four Decades of Metal Carbonyl Chemistry in Liquid Ammonia: Aspects and Prospects 12
I. Introduction 13
II. Reduction of Metal Carbonyls with Alkali Metals and Sodium Tetrahydridoborate in Liquid Ammonia 15
III. Reactions of the Pentacarbonyl Metalates(–II) and the Decacarbonyl Dimetalates(–I) of Chromium, Molybdenum, and Tungsten 21
IV. Reactions of Metal Carbonyls and Metal Carbonyl Derivatives with Liquid Ammonia 30
V. Reactions of Metal Carbonyls and Metal Carbonyl Derivatives with the Multidentate Nitrogen Ligands bipy, phen, and terpy 53
VI. High-Pressure Syntheses 57
VII. Conclusions 58
References 59
Chapter 2. Organolithium Catalysis of Olefin and Diene Polymerization 66
I. Introduction 66
II. Mechanism of Olefin Polymerization with Polar Ligands 72
III. Mechanism of Diene Polymerization with Polar Ligands 76
IV. Mechanism of Diene Polymerization in Nonpolar Media 82
V. Copolymerization of Dienes and Olefins 89
VI. Use of RLi to Prepare Terminally Functional Diene (Olefin) Polymers 100
VII. Unsolved Problems/Future Trends 104
References 104
Chapter 3. Ziegler–Natta Catalysis 110
I. Scope of Ziegler Catalysis 110
II. Process Operation 116
III. Stereoselectivity, Kinetics, and Mechanism 119
IV. Tailoring Heterogeneous Catalysts 129
V. Homogeneous Ziegler–Natta Catalysts 134
VI. Side Reactions in Homogeneous Catalysts 142
VII. Influence of Water on Homogeneous Catalysts 148
References 154
Chapter 4. Chiral Metal Atoms in Optically Active Organo-Transition-Metal Compounds 162
I. Introduction 163
II. Optical Resolution–Enantiomers 164
III. Optical Resolution–Diastereoisomers 171
IV. Methods of Diastereoisomer Separation 176
V. Scope of the Concept of Chiral Metal Atoms in Optically Active Organo-Transition-Metal Compounds 177
VI. Optical Purity 177
VII. Configurational Stability 179
VIII. Ligand Transformations 180
IX. Stereochemical Aspects of the Racemization and Ligand Exchange of (+)- and (–)-C.5H5Mn(NO)(COR)PAr3 183
X. Metal-Centered Rearrangement in Optically Active Square- Pyramidal Compounds 188
XI. The Stereochemistry of Reactions at Fe — C and Fe-Hal Bonds 191
XII. Miscellaneous Reactions 196
XIII. Optical Induction 197
XIV. Diastereoisomerically Related Pairs of Enantiomers 200
XV. Chiroptical Properties 203
XVI. Absolute Configuration 204
XVII. Table of Optically Active Compounds 206
References 212
Chapter 5. Mixed-Metal Clusters 218
I. Introduction 218
II. Synthesis 220
Ill. Methods of Characterization 253
IV. Reactivity 260
V. Dynamic NMR Studies 268
VI. Almost Mixed-Metal Clusters 276
References 280
Chapter 6. Trends in Organosilicon Biological Research 286
I. Introduction 286
II. Silicon Derivatives of Known Active Compounds 287
III. Silicon Biological Agents without Carbon Analogy 299
IV. Detoxification and Elimination of Silicon Compounds 305
V. Summary 306
References 307
Chapter 7. Boron Heterocycles as Ligands in Transition-Metal Chemistry 312
I. Introduction 312
II. Mononuclear Complexes 318
III. Dinuclear Complexes 335
IV. Trinuclear Complexes 344
V. Conclusion 348
References 348
Subject Index 352
Cumulative List of Contributors 361
Cumulative List of Titles 363