Theoretical Studies of Main Group Organometallic Chemistry

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The Theoretical and Computational Chemistry Program is supporting Prof. Mark Gordon of Iowa State University. The research to be performed will be a combination of theory and code development in quantum chemistry and related areas and applications of modern quantum chemistry to problems in main group organometallic chemistry. The new developments in theory will focus on two areas: (1) an extension of the effective fragment method for solvation to any solvent, to excited states, and to include higher-order intermolecular interactions, and (2) to extend the interface between quantum chemistry and dynamics to facilitate the study of dynamics of liquids and solvation dynamics. One of the key applications areas interfaces with these new theory developments, namely the study of the influence of solvation on mechanisms in organometallic chemistry. Among the many mechanisms of interest are the nature of the ring opening in cyclic organosilicon compounds, the effect of catalysts on reactions such as the hydrosilation and bis-silylation reactions, and the nature of the organometallic coupling reaction. Other applications include a broad-based study of the chemistry of titanium and other Group IVB elements, and quantitative studies of the thermochemistry of main group- transition metal bonding. Although most chemical reactions occur in the presence of a solvent, until very recently, the vast majority of theoretical studies have been carried out on isolated molecules. Even now, most current models that include the effects of solvents do not explicitly treat the individual solvent molecules and therefore cannot determine the nature of the interactions between the chemical system of interest and the solvent. The Gordon group has developed a new solvent model, the effective fragment potential model, that is designed to treat the solvent molecules explicitly. Currently, this model is limited to the most ubiquitous solvent, water. This model will now be extended so that any solvent of interest in organometallic chemistry will be accessible. The new method will be applied to study the effects of solvation on several important chemical reactions. It is anticipated that these studies will provide some fundamental understanding of how these reactions occur and ultimately provide some guidance on the design of new products.