Kinetics and Mechanisms of Organometallic Reactions

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In this research supported in the Inorganic, Bioinorganic and Organometallic Chemistry Program, Theodore L. Brown of the University of Illinois at Urbana-Champaign, will investigate the kinetics and mechanisms of organometallic reactions. The focus will be mainly on transition-metal carbonyl complexes and specifically on the properties of reaction intermediates formed in the course of organometallic reactions. These studies are important for the fundamental understanding of organo- metallic chemistry and catalytic processes involving organo- metallic compounds. One class of reaction intermediate to be studied is the metal carbonyl radicals, which possess an odd number of electrons (often seventeen or nineteen) in the metal valence orbitals. A second class of intermediate is formed by loss of a ligand, usually carbon monoxide, bound to the metal. The technique of flash photolysis using a dinitrogen laser will be employed to study these intermediates. Another aspect of the research will involve a comprehensive study of the steric and electronic properties of ligands, primarily phosphorus ligands. The approach will involve experimental studies of appropriate series of reactions; compilation of these results and results from a large body of existing literature; and analysis of these data with new statistically valid methods. The end result may be a useful system for effective design of catalysts by using ligands which impart predictable and desirable properties to the catalysts.