Advances in Organometallic Chemistry (eBook)

Front Cover 1
Advances in Organometallic Chemistry, Volume 30 4
Copyright Page 5
Contents 6
Chapter 1. Chemistry of the Cyclopentadienyl Bisphosphine Ruthenium Auxiliary 8
I. Introduction 8
II. Preparation of Cyclopentadienyl Bisphosphine Ruthenium Complexes 9
III. Geometry of (.5-C5H5)(PR3)2RuCl 11
IV. Exchange Reactions of PPh3 in (.5-C5H5)(PPh3)2RuX 15
V. Exchange Reactions of X in (.5-C5H5)(PR3)2RuX 23
VI. Ruthenium Acetylide, Vinylidene, and Carbene Complexes 37
VII. Decomplexation Reactions 71
VIII. Preparation of Ruthenium Complexes Containing .2-Unsaturated Ligands 73
IX. Oligomerization Reactions 75
X. Orthometallation Reactions 77
References 80
Chapter 2. Thermochromic Distibines and Dibismuthines 84
I. Introduction 84
II. Historical Perspective 84
III. Synthesis and Chemical Properties 87
IV. Ultraviolet (UV) and Diffuse Reflectance Spectra 89
V. Structure 91
VI. Theory and Bonding 95
VII. Raman Spectra, Electron Diffraction, and Mössbauer Spectra 97
VIII. Comparison with Similar Compounds 99
IX. Concluding Remarks 102
References 102
Chapter 3. Syntheses, Structures, Bonding, and Reactivity of Main Group Heterocarboranes 106
I. Introduction 106
II. General View of Bonding and Structural Relationships 107
III. Stability 110
IV. Structural Nomeneclature 110
V. Heterocarboranes of Group 2 Elements 111
VI. Heterocarboranes of Group 13 Elements 112
VII. Heterocarboranes of Group 14 Elements 123
VIII. Heterocarboranes of Group 15 Elements 147
IX. Heterocarboranes of Group 16 Elements 154
X. Summary 154
References 154
Chapter 4. .2 Coordination of Si—H s Bonds to Transition Metals 158
I. Introduction 158
II. The (.-C5R'5)L2Mn(H)SiR3 System 161
III. Dinuclear Metal Complexes with Bridging M—H—Si Interactions 181
IV. Other Complexes Possibly Containing M—H—Si Three-Center Bonds 187
V. .2-SiH and .2-CH Complexes: A Comparison 189
References 192
Chapter 5. Isoelectronic Organometallic Molecules 196
I. Introduction 196
II. Isoelectronic Definitions 197
III. Simple Ligands 199
IV. Polyhapto Ligands 215
V. Clusters 225
VI. Conclusions 242
References 243
Chapter 6. Dissociative Pathways in Substitution at Silicon in Solution: Silicon Cations R3Si+, R3SI+ . Nu, and Silene-Type Species R2Si=X as Intermediates 250
I. Introduction 250
II. Silylenium Ion Intermediates 251
III. Silene–Type Species in Elimination–Addition Reactions 272
IV. Borderline SN1–SN2 Mechanisms 279
V. Tetracoordinate Silicon Cations as Intermediates in Nucleophile-Assisted Substitution at Silicon 280
VI. Final Remarks 305
References 305
Index 316
Cumulative List of Contributors 324