Advances in Organometallic Chemistry (eBook)

Cover 1
Contents 6
Contributors 10
Chapter 1. The Chemical and Catalytic Reactions of Hydrido-chloro-carbonylbis (triisopropylphosphine)osmium(II) and Its Major Derivatives 12
I. Introduction 13
II. Spectroscopic Features and Coordination Polyhedron of OsHCl(CO)(Pi Pr3)2 14
III. Addition Reactions to OsHCl(CO)(Pi Pr3)2: Formation of Six-Coordinate Hydrido-Chloro-Carbonyl Derivatives 16
IV. Addition of the Os––H Bond of OsHCl(CO)(Pi Pr3)2 to Carbon–Carbon Triple Bonds: Formation of Alkenyl Derivatives 18
V. Formation of Hydride-Vinylidene Complexes by Addition of Terminal Alkynes to OsHCl(CO)(Pi Pr3)2 22
VI. Formation of Dienyl Complexes by Reaction of OsHCl(CO)(Pi Pr3)2 with Enynes 25
VII. Reactions of OsHCl(CO)(Pi Pr3)2 with Alkynols: Formation of a,ß-Unsaturated Carbene Complexes 28
VIII. Reactions of OsHCl(CO)(Pi Pr3)2 with HX Molecules: Formation of Dihydrogen Derivatives 30
IX. The Complex OsCl2( n2-H2)(CO)(Pi Pr3)2 as Precursor of Carbene, Alkenyl-Carbene,and u -Bis-Carbene Derivatives 32
IX. The Complex OsCl2(.2-H2)(CO)(Pi Pr3)2 as Precursor of Carbene, Alkenyl-Carbene,and µ-Bis-Carbene Derivatives 32
X. Reaction of OsHCl(CO)(Pi Pr3)2 with n-BuLi. The Chemistry of the Dihydride OsH2(CO)( 2-CH2==CHEt)(Pi Pr3)2 35
XI. Reactions of OsH2(.2-H2)(CO)(Pi Pr3)2 with Alkynes: Alkynyl and Related Compounds 43
XII. Reaction of OsHCl(CO)(Pi Pr3)2 with NaBH4: The Chemistry of OsH(.2-H2BH2)(CO)(Pi Pr3)2 49
XIII. Decomposition of OsH(.2-H2BH2)(CO)(Pi Pr3)2 in the Presence of Alcohols: Synthesis and Reactions of Hydride-Alkyl Compounds 51
XIV. Reactions of OsHCl(CO)(Pi Pr3)2 with C5H6 and Na[HBpz3]: Cyclopentadienyl and Tris(pyrazolyl)borate Compounds 55
XV. Reactions of OsHCl(CO)(Pi Pr3)2 with NaXR (X=O, S) 57
XVI. Other Metathetical Reactions on the Chloride Ligand of OsHCl(CO)(Pi Pr3)2 61
XVII. OsHCl(CO)(Pi Pr3)2 as a Homogeneous Catalyst 62
XVIII. Final Remarks 66
References 67
Chapter 2. Chemistry of o-Carboranyl Derivatives 72
I. Introduction 72
II. Group IV-B Derivatives (Si, Ge, Sn) of o-Carborane 74
III. Metal Compounds Containing an X,Y-Carboranyl Chelating Ligand 88
IV. Metal Compounds Containing a Dithiolato-o-Carborane 94
V. Reactivity of o-Carborane 99
VI. Ligand Design Derived from o-Carborane 104
VII. Concluding Remarks 106
References 108
Chapter 3. The Chemistry of Borabenzenes (1986–2000) 112
I. Introduction 112
II. Synthesis of Neutral Borabenzene–Ligand Adducts 113
III. Synthesis of Anionic Boratabenzenes 116
IV. Boratabenzenes: Structure and Bonding 119
V. Reactivity of Transition Metal Complexes of Boratabenzenes 124
VI. Conclusion 128
References 128
Chapter 4. Recent Advances in the Chemistry of Group 14–Group 16 Double Bond Compounds 132
I. Introduction 132
II. Theoretical Aspects 134
III. Synthetic Methods 138
IV. Structures and Physical Properties 167
V. Reactivities 171
VI. Concluding Remarks 173
References 174
Chapter 5. The M–C Bond Functionalities Bonded to an Oxo-Surface Modeled by Calix[4]arenes 178
I. Introductory Remarks: Scope and Limits 178
II. Introduction 179
III. Metalation of Calix[4]arenes and O-Alkylated Calix[4]arenes Using Transition Metals 181
IV. Low-Valent Metalla-Calix[4]arenes 183
V. The Organometallic Functionalization of the Metalla-Calix[4]arenes 197
References 238
Chapter 6. From AIX/GaX Monohalide Molecules to Metalloid Aluminum and Gallium Clusters 246
I. Introduction 246
II. Cocondensation Technique and Synthesis of Metastable AlX or GaX Solutions 248
III. Metalloid Al Clusters 252
IV. Metalloid Ga Clusters 266
V. Conclusions and Outlook 288
References 290
Chapter 7. Multiple Bonds Involving Aluminum and Gallium Atoms 294
I. Introduction 294
II. Organoaluminum Compounds Containing Multiple Bonds 294
III. Organogallium Compounds Containing Multiple Bonds 297
IV. Conclusion 304
References 304
Index 306
Cumulative List of Contributors for Volumes 1–36 314
Cumulative Index for Volumes 37–47 318