Advances in Organometallic Chemistry (eBook)

Front Cover 1
Advances in Organometallic Chemistry, Volume 25 4
Copyright Page 5
Contents 6
Chapter 1. Silenes 10
I. Introduction and History 10
II. Synthesis of Silenes 16
III. Physical Properties of Silenes 19
IV. Calculations Concerning the Properties of Silenes 28
V. Dimerization of Silenes 32
VI. Reactions of Silenes: Additions to the Double Bond 35
VII. Molecular Rearrangements of Silenes 44
VIII. Summary 47
References 47
Chapter 2. Metalla-Derivatives of ß-Diketones 54
I. Introduction 54
II. General Classes of Compounds 56
III. Metalla-ß-ketoimines 65
IV. Interligand Carbon–Carbon Coupling Reactions 69
References 79
Chapter 3. Organometallic Sonochemistry 82
I. Introduction and Intent 82
II. Mechanisms of the Chemical Effects of Ultrasound 83
III. Experimental Influences on Sonochemistry 93
IV. Overview of the Chemical Effects of Ultrasound 101
V. Organometallic Sonochemistry 104
VI. Concluding Remarks 120
References 121
Chapter 4. Carbene and Carbyne Complexes of Ruthenium, Osmium, and Iridium 130
I. Introduction 130
II. Bonding Models and Reactivity Patterns for Transition Metal Carbene and Carbyne Complexes 131
III. N-, O-, S-, and Se-Substituted Carbene Complexes 143
IV. Nonheteroatom-Substituted Carbene (Alkylidene) Complexes 164
V. Dihalo- and Monohalocarbene Complexes 178
VI. Carbyne Complexes of Ruthenium and Osmium 190
VII. Conclusion 202
References 203
Chapter 5. Borabenzene Metal Complexes 208
I. Introduction 208
II. Nomenclature 209
III. Historical Perspective 209
IV. Structure and Bonding 211
V. Synthetic Methods 219
VI. Reactions at the Metal Center 232
VII. Reactions at the Coordinated Ligand 236
VIII. Applications 241
IX. Concluding Comments 241
X. Addendum 242
References 243
Chapter 6. The Synthesis of Organometallics by Decarboxylation Reactions 246
I. Introduction 246
II. Mechanism 247
III. Thermal Decarboxylation 252
IV. Radical Initiated Decarboxylation 277
References 280
Chapter 7. Detection of Transient Organometallic Species by Fast Time-Resolved IR Spectroscopy 286
I. Introduction 286
II. Time-Resolved IR Measurements: Technical Considerations 296
III. IR Kinetic Spectroscopy of Organometallic Transients 308
IV. Concluding Remarks 320
References 322
Chapter 8. Carbonyl Derivatives of Titanium, Zirconium, and Hafnium 326
I. Introduction 327
II. Binary Carbonyl Complexes 328
Ill. Carbonyl Complexes Not Containing p-Bonded Hydrocarbon Ligands 328
IV. Formation of the Group 4B Metallocene Dicarbonyls 331
V. Physical, Spectroscopic, and Structural Properties of the Various Group 4B Metallocene Dicarbonyls 356
VI. Monocarbonyl Derivatives of Titanocene 360
VII. Monocarbonyl Derivatives of Zirconocene 374
VIII. Monocarbonyl Derivatives of Hafnocene 380
IX. Group 4B Carbonyl Complexes Containing n-Bonded Acyclic Hydrocarbon Ligands 381
X. Group 4B Carbonyl Complexes Containing One .5-C5H5 Ring 383
XI. Group 4B Carbonyl Complexes Containing .-Arene Rings 384
References 385
Index 390
Cumulative List of Contributors 406
X. Group 4B Carbonyl Complexes Containing One .5-C5H5 Ring 384