Mechanistic Studies of Oxygen Evolution and Hydrogen Atom Transfer in Enzymes and Biomimatic Models

Purdue University, West Lafayette IN

Investigators

Abstract

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor Mahdi Abu-Omar at Purdue University to investigate metal mediated hydrogen atom transfer (HAT) and to study the reactions involved with chlorite dismutase. The objectives of the HAT chemistry are to: (1) study the kinetics and mechanism(s) of hydrogen atom transfer (HAT) in a series of tosylimido complexes of corrole (Mn, Cr, and V) and their oxo analogs, and (2) expand the utility of HAT with these novel imido complexes to achieve catalytic amination of C-H bonds. A second project is concerned with the reaction chemistry (dismutation/destruction) of the chlorite ion (ClO2 -), which is formed by perchlorate respiring bacteria. The mechanism of chlorite dismutation in the enzyme chlorite dismuatse (Cld) will be studied and compared with water soluble prophyrinoid models. Understanding reaction rates and mechanisms of metal mediated HAT reactions relates to harnessing these reactions for benign functionalization of C-H bonds. The study of chlorite dismutation in enzyme and models has ramifications for the chemistry of chloride oxyanions in the environment. Postdoctoral, graduate, and undergraduate researchers will learn to make molecules, measure kinetics, perform state-of-the art spectroscopic experiments, and analyze data to gain molecular (mechanistic) insight, and present their research findings.