Structure-Reactivity Relationships in Fluorinated and Charged Radical Systems

University Of Florida, Gainesville FL

Investigators

Abstract

With this award the Organic and Macromolecular Chemistry Program renews its support for the work of Dr. William R. Dolbier of the Department of Chemistry at the University of Florida in Gainesville. The major purpose of the work is to build on the discoveries made with earlier NSF funding in the physical organic chemistry of organic molecules containing fluorine, and to develop applications in the areas of organic synthesis, industrial polymers, and biochemistry. Dr. Dolbier will also be investigating the reactions of distonic radical cations, species with an unpaired electron and a positive electrical charge on different atoms in the same molecule. The combination of synthesis, kinetic and mechanistic studies, and theoretical chemistry will provide excellent training for the postdoctoral and graduate students who will work on the project. It should be mentioned that Dr. Dolbier was this year's winner of the ACS Award for Creative Work in Fluorine Chemistry. The work falls into four general radical reaction classes: C-H transfer, cyclizations, cyclopropylcarbinyl ring opening, and reactions of distonic radical cations. Both relative and absolute rate constants are measured after generating the radicals by fast flash photolysis - developing useful correlations between structure and reactivity that can be used to make predictions for molecules where the kinetic data are unavailable.