Cleavage and Formation of C-S and C-N Bonds in Heterocyclic Compounds by Homogeneous Transition Metal Complexes

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This award in the Inorganic, Bioinorganic and Organometallic Chemistry Program supports research by Professor William D. Jones at the University of Rochester to develop new hydrodesulfurization techniques and synthetic applications for the cleavage and formation of C-S and C-N bonds in thiophenes and heterocyclic nitrogen containing compounds with transition metal fragments. The objectives are to: (1) provide basic information about the requirements for the cleavage of these strong and/or hindered C-X bonds (X = S, N), (2) provide information about the mechanism(s) for C-X bond cleavage, (3) examine structural motifs for the binding of sulfur- and nitrogen-containing organic compounds to metals, (4) understand the chemistry of metal sulfhydryl and sulfido compounds, their interconversion, and their lability, and (5) develop catalytic systems for manipulation of C-S and C-N bonds. New concepts to be explored include the determination of electronic effects on bond cleavage and the use of supported systems for catalysis. Both undergraduate and graduate students will be trained at an advanced level to use the concepts of inorganic, organic, analytical, and physical. The University of Rochester has a joint program with Hampton University to attract students from underrepresented groups from the Hampton M.S. program directly into the Rochester Ph.D. program. The scientific work is aimed at a better understanding of how to desulfurize the most resistant polyalkylated dibenzothiophenes still found in hydrocarbon fuels. This knowledge will help in meeting the new EPA standards for low sulfur emissions from fuels. Another impact of the work is in developing new synthetic routes to nitrogen-containing heterocycles, a fundamental building block in many biologically important compounds.