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Proton and Hydride Transfer Reactions involving Organic Ions and Ion Radicals

$415,500FY2000MPSNSF

Utah State University, Logan UT

Investigators

Abstract

With this renewal award the Organic and Macromolecular Chemistry Program supports the work of Dr. Vernon D. Parker at Utah State University in Logan, Utah. The work will extend earlier studies looking into the details of the mechanism of hydrogen transfer reactions from radical cations, positively charged organic compounds with an unpaired electron spin. Intermediates of this type are involved in a number of important biological oxidations by enzymes and industrial oxidation and polymerization reactions. The kinetics of C-H bond cleavage in various radical cations - by either proton or hydride transfer - will be studied by electrochemical and spectrophotometric methods (including stopped-flow) to determine how kinetic isotope effects depend on structure and extent of reaction. The hypothesis that many of these apparently simple bimolecular hydrogen transfer reactions actually take place by two steps with kinetically significant intermediates will be tested by experiments. The work is expected to provide valuable experience to graduate and postdoctoral students, as well as providing fundamental information of use to the organic chemical community.

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