Metal-Oxo and Metal-Peroxo Intermediates in Oxidative Catalysis

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This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor Jay Groves of Princeton University to discover the basic principles of oxidative catalysis and to use these insights for the invention of the next generation of catalysts. The proposal has four focus areas: 1) structure-reactivity correlations among oxo- and peroxo-metal complexes; 2) kinetics and mechanism of aliphatic hydroxylation by oxometalloporphyrins, 3) oxygen transfer to halide ions and the oxidation of water, and 4) anti-Markovnikov hydrofunctionalization of olefins mediated by rhodium porphyrins.The unusual reactivity of oxomanganese(V) porphyrin systems will be investigated in order to: 1) Elucidate the electronic effects in reactivity by looking at periodic relationships, 2) Determine the strength of the forming M=O---H bond, or, equivalently, the bond dissociation energy of M(IV)O-H, 3) Determine why manganese behaves so much differently from iron with the same ligand system in the same catalytic regime, 4) Determine quantitative free energy relationships and deduce relationships between structure and reactivity, and 5) Determine whether these complexes can oxidize halide ions and water.Chemical catalysis is central to the economic health of the nation and the world with about 30% of the GNP of the United States and at least 80% of the chemical industry dependent oncatalytic processes. This research aims to discover the fundamental basis of a number of types of oxidative catalysis and to train the personnel that are necessary for the nation to achieve the technological advances offered by these discoveries and to train the teachers of science for the future.