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.

Table of Contents:
Twenty-Five Years of Chemistry Since the Discovery of the Quadruple Metal-Metal Bond.- A Quarter-Century of Metal-Metal Multiple Bonds.- The Multiple Metal-Metal Bond: Twenty-Five Years of Synthetic Serendipity and Structural Discovery.- Theoretical Studies of Dinuclear Compounds with Multiple Metal-Metal Bonds.- Uses of Metal Clusters in Homogeneous and Heterogeneous Catalysis.- Reactivity of Dinuclear and Tetranuclear Clusters of Molybdenum and Tungsten.- Clusters and Their Implications for Catalysis.- Metal Clusters in the Solid State.- Clusters in Catalysis.- Nature of Bimetallic Clusters.- Thermochemical Aspects of Organotransition Metal Chemistry. Insights Provided by Metal-Ligand Bond Enthalpies.- Metal Clusters and Supported Metal Catalysts.- Mechanistic Features of Carbonyl Cluster Rearrangement.- Selective Oxidation Chemistry on Soluble Oxides: A Progress Report.- The Study of Clusters of Polylithium Organic Compounds and Structural Studies of Polylithium Organic Compounds.- Clusters in Materials.- Organometallic Chemical Vapor Deposition of GaAs and Related Semiconductors Using Novel Organometallic Precursors.- Surface Chemistry of Mixed-Metal Systems.- Organometallic Chemical Vapor Deposition of Aluminum Nitride and Aluminum Metal.- Solid State Carbon-13 NMR of Metal Carbonyls.- Surface Chemistry of Metal and Semiconductor Clusters.- Bonding and Spectroscopy in Clusters.- The Electronic Structure of Metal Dimers and Metal Clusters: The Eighteen-Electron Rule vs. Skeletal Electron-Pair Counting.- Experimental Measures of Metal-Metal Sigma, Pi, and Delta Bonding from Photoelectron Spectroscopy.- Formation, Structure and Luminescent Properties of Metal-Metal Bonded Compounds of the Late Transition Metal and Post Transition Metal Ions.- Abstracts.- The Preparation and Characterization of New Heteropolyoxofluorometalate Anion, [FeW17O56F6H5]8?.- Facile Exchange of Terminal, Doubly-Bridging, and Quadruply Bridging Carbonyl Ligands in Solution: Crystal Structure and Solution Dynamics of LWM3(CO)12H, L=C5H5, C5Me5 and M=Os,Ru.- Thermal Constants and Structure of Tin Clusters.- Reactivity and Isomerization of Mo2(ALLYL)4.- Surface Coordination/Organometallic Chemistry of Monometal and Bimetallic Electrocatalysts.- Ambient-Temperature Chloroaluminate Molten Salts: Solvents for Chloro Complex Electrochemistry and for Reductive Condensation Syntheses.- The Maximum Strength of the Chemical Bond between Two Metal Atoms.- Reactions of (?7-C7H7)M(?5-C5H5), M = Ti or Zr, with Carboxylic and Dithiocarboxylic Acids.- Model Hydrodesulfurization Systems: Reactions of Sulfur Containing Molecules on Ni(110).- Electrochemical Studies of Triangular Niobium Cluster, Nb3O2(SO4)6.3H2O5?, in Sulfuric Acid.- Reactivity of Dithioethers toward [Re2H8]2?.- Theoretical Investigations of the Metal-Metal Interactions within the Trinuclear Au2Pt(CH2(S)PH2)4 Complex.- Structural and Theoretical Studies on Heteronuclear Transition-Metal Clusters Containing the Alkylidyne Ligand.- Electronic Structure and Nature of Bonding in Transition Metal Dimers.- Theoretical Calculations on the Interaction of Bridging Carbonyls with Transition Metal Dimers.- Bimetallic Hydroformylation Catalysis.- 252CF-Plasma Desorption Mass Spectra of Very Large Clusters.- Systematic Kinetic Studies of Associative and Dissociative Reactions of Substituted Metal Carbonyl Clusters: The Intimate Mechanisms.- Mixed Pd-Au and Pt-Au Cluster Compounds.- Stability of Small Biclusters of Transition Metals with Semi-Conductors.- The Topology of the Total Charge Density in BinuclearTransition-Metal Complexes that Formally Contain Metal-Metal Bonds.- The Effect of Carbonyl Ligands on Osmium and Ruthenium Metal-Metal Bonds.- Contributors.