Activation/Driving Force Relationships for the Unimolecular Rearrangement of Radical Ions

Virginia Polytechnic Institute And State University, Blacksburg VA

Investigators

Abstract

With this award, the Organic and Macromolecular Chemistry Program supports the work of Professor James M. Tanko, of the Chemistry Department at Virginia Polytechnic Institute and State University, Blacksburg, VA, for a research project involving investigations of the unimolecular rearrangements of radical ions. In particular, the research will examine the nature of the relationship between the rate and thermodynamic driving force for the ring opening of radical ions containing strained rings. The rates of the rearrangement will be measured using electrochemical techniques and laser flash photolysis. A combination of experiment and theory, including voltametry, molecular orbital calculations, and the theory of dissociative electron transfer will be applied to analyze these systems and to determine the relationship between reaction rate and free energy of reaction. The results of these studies will advance our understanding of organic reaction mechanisms as they apply to biological processes. The research is of particular importance for its expected impact in the area of mechanism-based drug design. The project will contribute to science education and human resource development by training individuals at the undergraduate, graduate and postdoctoral levels. Participants will be educated in the theory and practice of modern organic, bioorganic, and physical chemistry. They will receive practical training in the handling and synthesis of organic compounds, modern analytical techniques, laser flash photolysis, electrochemistry, and proper procedures for the safe handling and disposal of chemical waste.