The Mechanism of Oxygen Atom Transfer

University Of Delaware, Newark DE

Investigators

Abstract

With the support of the Organic Dynamics Program in the Chemistry Division, Professor Robert D. Bach, of the Department of Chemistry at the University of Delaware, will continue theoretical studies of oxygen transfer processes in both small molecules and in biomolecules. These are systems that are difficult to characterize and among the most challenging both theoretically and computationally. While the mechanism of oxygen transfer from such classical oxygen donors as peracids, dioxiranes and oxaziridines to a variety of nucleophiles such as alkenes, amines, sulfides and phosphines in two-electron processes are now reasonably well understood, much is yet to be learned about the oxidation of saturated hydrocarbons by one-electron oxidative reactions. Aided by a highly accurate systematic study of O-O bond dissociation energies, Professor Bach has placed his conclusions about the energetics of oxygen transfer on a sound thermodynamic basis. The proposed work will lead to a better understanding of oxidation reactions using high level theoretical and computational methods to explicitly examine the potential role of the excited singlet electronic structure of peroxynitrous acid in hydrogen atom abstraction processes. Professor Robert D. Bach, of the Department of Chemistry at the University of Delaware, with the support of the Organic Dynamics Program, studies the mechanism of oxygen atom transfer, which is important in understanding the metabolism of drugs in the body. This work is especially important to understanding how the family of enzymes known as cytochrome P-450 metabolizes drugs in animals.