Advances in Organometallic Chemistry (eBook)

Cover 1
Copyright Page 5
Contents 6
Contributors 10
Chapter 1. Decamethylsilicocene: Synthesis, Structure, Bonding and Chemistry 12
I. Introduction 12
II. Synthesis and Structure of Decamethylsilicocene 14
III. Bonding in Decamethylsilicocene 18
IV. Chemistry of Decamethylsilicocene (1) 20
V. Conclusions and Perspectives 42
References 43
Chapter 2. Organometallic Phosphorous and Arsenic Betaines 46
I. Introduction 47
II. Synthesis of Betaines (+)E15–C–E14–X(–) (I) and (+)E15–C–E14(–) (II) (E15 = P, As E14 = Si, Ge, Sn
III. Structure of Betaines (+)E15–C–E14–X(–) I and (+)E15–C–E14(–) II According to X-ray Data 60
IV. NMR Parameters of Betaines (+)E15–C–E14–X(–) I and (+)P–C–E14(–) II 63
V. Reactivity of Betaines (+)E15–C–E14–X(–) I and (+)E15–C–E14(–) II (E15 = P, As E14 Si, Ge, Sn
VI. Quantum-Chemical Investigation of Potential Energy Surfaces of Betaines (+)E15–C–E14–X(–) I and (+)E15–C–E14(–) II 81
VII. Conclusion 99
References 100
Chapter 3. Coordination Compounds with Organoantimony and Sbn Ligands 106
I. Introduction 106
II. Complexes with R3Sb, R2SbX, AND RSbX2 (R = alkyl, aryl, SiMe3 X = halogen, OR, SR) Ligands
III. Complexes with R2Sb–SbR2 AND R2Sb (R = alkyl, aryl) Ligands 110
IV. Complexes with R2Sb–Y–SbR2 (R = alkyl, aryl Y = CH2, O, S) Ligands
V. Complexes with R2Sb–Yn–SbR2 (R = alkyl, aryl Yn = (SbR)2, 0-C6H4, (CH2)3, S(MeSb)S) Ligands
VI. Complexes with (RSb)n (R = alkyl, aryl) and Sbn Ligands 133
VII. Concluding Remarks 138
References 138
Chapter 4. Ladder Polysilanes 144
I. Introduction 144
II. Synthesis 148
III. Structure 150
IV. Electronic Properties 154
V. Reactions 156
VI. Conclusion 174
References 174
Chapter 5. Structure–Reactivity Relationships in the Cyclo-Oligomerization of 1,3-Butadiene Catalyzed by Zerovalent Nickel Complexes 178
I. Introduction 179
II. Catalytic Reaction Cycles for the Nickel-Catalyzed Cyclo-Oligomerization of 1,3-Butadiene 181
III. Computational Models and Methods 186
IV. Theoretical Exploration of Critical Elementary Reaction Steps 190
V. Influence of Electronic and Steric Factors on Individual Elementary Steps of the C8-Cyclo-Oligomer Generating Reaction Channel 208
VI. Theoretically Re.ned Catalytic Cycles for the Nickel-Catalyzed Cyclo-Oligomerization Reactions of 1,3-Butadiene 216
VII. Regulation of the Cyclo-Oligomer Product Selectivity 222
VIII. Regulation of the C8:C12-Cyclo-Oligomer Product Distribution 226
IX. Conclusion 230
References 232
Chapter 6. Group 13/15 Organometallic Compounds„Synthesis, Structure, Reactivity and Potential Applications 236
I. Introduction 236
II. Lewis Acid–Base Adducts 240
III. Compounds of the Type [R2MER'2]x 268
IV. Monomers, Heterocycles and Cages of the Type [RMER']x 302
V. Potential Applications of Group 13/15 Organoelement Compounds in Material Sciences 308
VI. Conclusions and Outlook 317
References 318
Index 330
Cumulative List of Contributors for Volumes 1–36 338
Cumulative Index for Volumes 37–49 342