Synthetic Studies in Homogeneous Catalysis and Organometallic Chemistry

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James Collman of Stanford University is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program for research on redox reactions (involving both electron- and atom-transfer mechanisms) of transition-metal poryphrin complexes. Interest will be centered on redox reactions involving more than one electron. Investigations of reductions of dioxygen by dinuclear porphrin complexes involving two dissimilar metals will be continued. Four-electron oxidations of organic complexes by chlorite ion, catalyzed by porphrin complexes will be studied, as well as related electrochemical reactions. Hetrometallic dinuclear porphrin (and related) complexes of second and third row transition elements will be prepared and characterized by several methods in order to ellucidate novel types of metal-metal multiple bond.Oxidation-reduction reactions involving the transfer of several electrons from reductant to oxidant are not rare in nature or in technological applications, but such reactions have been studied relatively infrequently. Building on achievements of the prior period of NSF support, the PI has identified several diverse types of multi-equivalent redox reactions, all of which involve transition metal porphrin complexes as catalysts or reactants. There is a strong probability that increased understanding of such multi-electron redox reactions will have important technological and scientific applications. Four-electron oxidations by chlorite ion, to be studied in this program, are regarded as especially promising.