Metal-Metal Bonds and Clusters in Chemistry and Catalysis

This book contains a series of papers and abstracts from the 7th Industry-University Cooperative Chemistry Program symposium held in the spring of 1989 at Texas A&M University. The symposium was larger than previous IUCCP symposia since it also celebrated the 25 years that had elapsed since the initial discovery by F. A. Cotton and his co-workers of the existence of metal-metal quadruple bonds. Cotton's discovery demonstrated that multiple bonding in inorganic systems is not governed by the same constraints observed in organic chemistry regarding s and p orbital involvement. The d orbitals are involved in the multiple bonding description. The quadruple bond involves considerable d orbital overlap between adjacent metal centers. Part I of this series of papers focuses upon the impact of this discovery and describes further contributions to the development of the field. Multiple metal-metal bonding now is known to permeate broad areas of transition metal chemistry. The understanding of metal-metal bonding that developed as a result of the discovery of multiple metal-metal bonding awakened a new chemistry involving metal clusters. Clusters were defined by Cotton to be species containing metal-metal bonding. Clusters in catalysis therefore seemed a logical grouping of papers in this symposium. Clusters play an every increasing role in the control of chemical reactions. Part II of this book describes some of the interesting new developments in this field. In Part III the papers examine the role clusters play in describing and understanding solid state materials. Front Matter....Pages i-x A Quarter-Century of Metal-Metal Multiple Bonds....Pages 1-6 The Multiple Metal-Metal Bond: Twenty-Five Years of Synthetic Serendipity and Structural Discovery....Pages 7-17 Theoretical Studies of Dinuclear Compounds with Multiple Metal-Metal Bonds....Pages 19-39 Uses of Metal Clusters in Homogeneous and Heterogeneous Catalysis....Pages 41-54 Reactivity of Dinuclear and Tetranuclear Clusters of Molybdenum and Tungsten....Pages 55-74 Clusters and Their Implications for Catalyis....Pages 75-89 Metal Clusters in the Solid State....Pages 91-102 Nature of Bimetallic Clusters....Pages 103-112 Thermochemical Aspects of Organotransition Metal Chemistry. Insights Provided by Metal-Ligand Bond Enthalpies....Pages 113-125 Metal Clusters and Supported Metal Catalysts....Pages 127-140 Mechanistic Features of Carbonyl Cluster Rearrangement....Pages 141-160 Selective Oxidation Chemistry on Soluble Oxides: A Progress Report....Pages 161-170 The Study of Clusters of Polylithium Organic Compounds and Structural Studies of Polylithium Organic Compounds....Pages 171-194 Organometallic Chemical Vapor Deposition of GaAs and Related Semiconductors Using Novel Organometallic Precursors....Pages 195-204 Surface Chemistry of Mixed-Metal Systems....Pages 205-214 Organometallic Chemical Vapor Deposition of Aluminum Nitride and Aluminum Metal....Pages 215-230 Solid State Carbon-13 NMR of Metal Carbonyls....Pages 231-247 Surface Chemistry of Metal and Semiconductor Clusters....Pages 249-264 The Electronic Structure of Metal Dimers and Metal Clusters: The Eighteen-Electron Rule vs . Skeletal Electron-Pair Counting....Pages 265-273 Experimental Measures of Metal-Metal Sigma, Pi, and Delta Bonding from Photoelectron Spectroscopy....Pages 275-298 Formation, Structure and Luminescent Properties of Metal-Metal Bonded Compounds of the Late Transition Metal and Post Transition Metal Ions....Pages 299-309 The Preparation and Characterization of New Heteropolyoxofluorometalate Anion, [FeW 17 O 56 F 6 H 5 ] 8− ....Pages 311-311 Facile Exchange of Terminal, Doubly Bridging, and Quadruply Bridging Carbonyl Ligands in Solution: Crystal Structure and Solution Dynamics of LWM 3 (CO) 12 H, L=C 5 H 5 , C 5 Me 5 and M=Os, Ru....Pages 312-313 Thermal Constants and Structure of Tin Clusters....Pages 314-314 Reactivity and Isomerization of Mo 2 (Allyl) 4 ....Pages 315-315 Surface Coordination/Organometallic Chemistry of Monometal and Bimetallic Electrocatalysts....Pages 316-317 Ambient-Temperature Chloroaluminate Molten Salts: Solvents for Chloro Complex Electrochemistry and for Reductive Condensation Syntheses....Pages 318-318 The Maximum Strength of the Chemical Bond between Two Metal Atoms....Pages 319-319 Reactions of ( η 7 -C 7 H 7 )M( η 5 -C 5 H 5 ), M = Ti or Zr, with Carboxylic and Dithiocarboxylic Acids....Pages 320-320 Model Hydrodesulfurization Systems: Reactions of Sulfur Containing Molecules on Ni(110)....Pages 321-321 Electrochemical Studies of Triangular Niobium Cluster, Nb 3 O 2 (SO 4 ) 6 · 3H 2 O 5− , in Sulfuric Acid....Pages 322-322 Reactivity of Dithioethers Toward [Re 2 X 8 ] 2− ....Pages 323-323 Theoretical Investigations of the Metal-Metal Interactions within the Trinuclear Au 2 Pt(CH 2 (S)PH 2 ) 4 Complex....Pages 324-324 Structural and Theoretical Studies on Heteronuclear Transition-Metal Clusters Containing the Alkylidyne Ligand....Pages 325-325 Electronic Structure and Nature of Bonding in Transition Metal Dimers....Pages 326-326 Theoretical Calculations on the Interaction of Bridging Carbonyls with Transition Metal Dimers....Pages 327-327 Bimetallic Hydroformylation Catalysis....Pages 328-328 252 CF-Plasma Desorption Mass Spectra of Very Large Clusters....Pages 329-329 Systematic Kinetic Studies of Associative and Dissociative Reactions of Substituted Metal Carbonyl Clusters: The Intimate Mechanisms....Pages 330-331 Mixed Pd-Au and Pt-Au Cluster Compounds....Pages 332-332 Stability of Small Biclusters of Transition Metals with Semi-Conductors....Pages 333-333 The Topology of the Total Charge Density in Binuclear Transition-Metal Complexes That Formally Contain Metal-Metal Bonds....Pages 334-334 The Effect of Carbonyl Ligands on Osmium and Ruthenium Metal-Metal Bonds....Pages 335-335 Back Matter....Pages 337-341 This book contains a series of papers and abstracts from the 7th Industry-University Cooperative Chemistry Program symposium held in the spring of 1989 at Texas A & M University. The symposium was larger than previous IUCCP symposia since it also celebrated the 25 years that had elapsed since the initial discovery by F.A. Cotton and his co-workers of the existence of metal-metal quadruple bonds. Cotton's discovery demonstrated that multiple bonding in inorganic systems is not governed by the same constraints observed in organic chemistry regarding s and p orbital involvement. The d orbitals are involved in the multiple bonding description. The quadruple bond involves considerable d orbital overlap between adjacent metal centers. Part I of this series of papers focuses upon the impact of this discovery and describes further contributions to the development of the field. Multiple metal-metal bonding now is known to permeate broad areas of transition metal chemistry. The understanding of metal-metal bonding that developed as a result of the discovery of multiple metal-metal bonding awakened a new chemistry involving metal clusters. Clusters were defined by Cotton to be species containing metal-metal bonding. Clusters in catalysis therefore seemed a logical grouping of papers in this symposium. Clusters play an every increasing role in the control of chemical reactions. Part II of this book describes some of the interesting new developments in this field. In Part III the papers examine the role clusters play in describing and understanding solid state materials Proceedings of the Seventh Industry-University Cooperative Chemistry Program held at Texas A&M University, College Station, Texas, March 20-23, 1989. Proceedings of the Seventh Industry-University Cooperative Chemistry Program held at Texas A & M University, College Station, Texas, March 20-23, 1989