Advances in Organometallic Chemistry (eBook)

Front Cover 1
Advances in Organometallic Chemistry, Volume 31 4
Copyright Page 5
Contents 6
Chapter 1. Highly Reduced Metal Carbonyl Anions: Synthesis, Characterization, and Chemical Properties 8
I. Introduction 8
II. Tetracarbonylmetallates (3–) of Manganese and Rhenium 9
III. Pentacarbonylmetallates (3–) of Vanadium, Niobium, and Tantalum 22
IV. Tricarbonylmetallates (3–) of Cobalt, Rhodium, and Iridium 38
V. Tetracarbonylmetallates (4–) of Chromium, Molybdenum, and Tungsten and Related Materials 46
VI. Concluding Remarks 54
References 55
Chapter 2. The Interplay of Alkylidyne and Carbaborane Ligands in the Synthesis of Electronically Unsaturated Mixed-Metal Complexes 60
I. Introduction 60
II. Synthesis of Salts Containing the Anions [W(=CR)(CO),(.5-C2B9H9R'2]- (R = alkyl or aryl R’ = H or Me), [Mo(=CC6H4Me-4)(CO){P(OMe)3}- (.5-C2B9H9Me2)]-,and[W(=CR)(CO)2(.6-C2B10H10Me2)]- (R = aryl)
III. The Carbaborane Group as a Spectator Ligand 66
IV. Expolyhedral B–H–Metal Bonding in Di- and Trimetal Compounds 70
V. Formation of Exopolyhedral s Bonds between Cage Boron Atoms and Transition Elements 77
VI. Reactions Leading to Transfer of Alkylidyne Groups to the Carbaborane Cage 84
II. Synthesis of Salts Containing the Anions [W(=CR)(CO),(.5-C2B9H9R'2] (R = alkyl or aryl R’ = H or Me)
VIlI. Conclusion 94
References 95
Chapter 3. Transition Metal Complexes Incorporating Atoms of the Heavier Main Group Elements 98
I. Introduction 98
II. Gallium, Indium, and Thallium 99
III. Germanium, Tin, and Lead 115
IV. Antimony and Bismuth 137
V. Tellurium 161
References 183
Note Added in Proof 189
Chapter 4. Organo-Transition Metal Compounds Containing Perfluorinated Ligands 190
I. Introduction 190
II. Fluorocarbons vs . Hydrocarbons 190
III. Organometallic Compounds with Perfluorinated Ligands 191
IV. Octafluorocycloocta- 1,3,5, 7-Tetraene and Its Valence Isomers 209
V. Unsuccessful Attempts to Prepare Transition Metal Complexes of OFCOT 211
VI. Manganese Complexes of OFCOT and Perfluorotricyclo[4.2.0.02.5]Octa-3, 7-Dienee 212
VII. Iron Complexes of OFCOT and Perfluorotricyclo[4.2.0.02.5]Octa-3,7-Diene 218
VIII. Cobalt and Rhodium Complexes Derived from OFCOT and Perfluorobicyclo[4.2.0]Octa-2,4,7-Triene 224
IX. Nickel, Palladium, and Platinum Complexes Derived from OFCOT 247
X. Metallation of OFCOT and Its Valence Isomers 252
XI. Vicinal Defluorination of OFCOT to Give µ-Hexafluorocyclooctatrieneyne Complexes of Cobalt 262
XII. Concluding Remarks 268
References 268
Chapter 5. Alkyl- and Aryl-Substituted Main-Group Metal Amides 276
I. Introduction 276
II. Structural Aspects of Alkyl and Aryl Metal Amides 277
III. Organometallic Derivatives of Special Silazanes 283
IV. Conclusion 305
References 306
Chapter 6. Heteronuclear Clusters Containing Platinum and the Metals of the Iron, Cobalt, and Nickel Triads 308
I. Introduction 308
II. Synthesis 309
III. Bonding and Electron Counting 313
IV. Fluxional Behavior and Isomerization Reactions 319
V. Structural and Reactivity Aspects of Hetero-Pt Clusters 335
VI. Catalysis by Hetero-Pt Clusters 390
VII. Addendum 391
References 391
Index 400
Cumulative List of Contributors 412