Chemical and Electrochemical Generation of Novel Anions and Dianions of Arene and Olefincarbonylmetal Complexes. New Organic Synthetic Methodologies

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This grant in the Organic and Macromolecular Chemistry Program supports research of Prof. Reuben Rieke, University of Nebraska, which is concerned with new chemical reactions of mono- and biscarbonylmetal complexes of arenes and arene-substituted olefins. Of particular interest will be analysis of the reactions of the complex dianions with a variety of electrophiles, because these hold the potential for evolving into useful new synthetic methodologies for complex organic synthesis. The studies on bis-complexes will concentrate on biphenyl and other conjugated diarene systems. The conjugated bis-complexes show the unusual reduction characteristics of one electron per chromium tricarbonyl unit, to give stable dianions. Reaction with primary halides gives high yields to only the ortho product. The mechanistic origins of this regioselectivity will be determined and its utility in new synthetic methodologies will be explored. New mixed metal bis-complex systems of arene-substituted olefins will also be prepared, which should lead to stable dianions upon reduction. The reactions of these dianions with electrophiles offer opportunities for control of regioselectivity between the arene and olefin portions of the molecule. A variety of electrochemical and stereochemical techniques will be used to probe the reaction mechanisms of these reactions.