Electronic Structure Studies of Molybdenum Oxotransferases

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9316557 Kirk This award is the starter grant increment of Dr. Kirk's Postdoctoral Reseaerch Fellowship in Chemistry. The main thrust of the research is a combined experimental and theoretical study of oxygen transfer by Group VI metals in both biological and inorganic systems. A combined spectroscopic approach utilizing variable-temperature, variable-field magnetic circular dichroism, single crystal polarized absorption, and resonance Raman spectroscopies will probe the Mo(V) state of xanthine oxidase catalytic intermediates. These enzyme studies will be complemented by parallel investigations of relevant model compounds which display structural features believed to be present at the enzyme active site. Excited state spectral studies will be used in order to evaluate the results of detailed bonding calculations including self-consistent field scattered wave calculations, transition-state calculations, and density functional methods incorporating Slater or Gaussian-type basis functions. %%% Group VI metals, specifically molybdenum and tungsten are catalytically active towards oxygen transfer in both enzymatic and inorganic systems. These studies will provide a wealth of information concerning the mode of substrate binding to the metal and will directly probe the initial steps in oxo transfer from metal to substrate. ***