Structure-Reactivity Relations of Transition Metal ElectrodeReactions Characterized by Large Structural Change

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This project, supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program, involves studies of structure-reactivity relationships in heterogeneous electron transfer reactions of transition metal complexes with particular emphasis on complexes that undergo large inner sphere structural changes concommitant with the electron transfer. The primary objective of the work is to provide quantitative tests of current theories of structural and environmental effects on hetereogeneous electron transfer rates. This will involve the measurement of accurate rates of heterogeneous electron transfer rates and the use of computational methods (molecular mechanics and both semiempirical and ab initio quantum mechanistic) to model the inner sphere barrier to the electron transfer. A secondary objective is to develop methods that provide accurate heterogeneous rate constants. %%% Electron transfer is one of the most fundamental of chemical processes about which much is known but where many issues are unresolved. This project, which is a collaborative effort between an experimental electrochemist and a theoretical physical chemist, is designed to improve our understanding of how changes in the structures of certain metal complexes that accompany an electron transfer affect the rate of the overall process.