Mechanistic Investigations of Group 14 Cation Radical Reactions

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With this Prior award, the Organic and Macromolecular Chemistry Program supports the continuing research of Dr. Joseph Dinnocenzo in the Department of Chemistry of the University of Rochester. The research focuses on the mechanisms of fragmentation of organometallic radical cations containing Group 14 elements (Si, Ge, Sn, and Pb) in solutions containing nucleophiles. A combination of kinetic and stereochemical experiments will be used to distinguish between concerted and stepwise addition/elimination mechanisms.The proposed research involves fundamental studies of fragmentation reactions of positively charged, odd-electron species containing C-M bonds, where M is silicon, germanium, tin or lead. The results will provide insights into the structures, reactivities, and reaction mechanisms of these Group 14 cation radical intermediates, and are likely to be of broad interest to organic and physical chemists. Intermediates of this type are likely to be useful for organic synthesis, and may be involved in the formation of solid state materials such as silicon photoresists. The work will provide excellent training for the personnel involved, two of whom are women.