This project involves the computational study of the mechanism of hydroxylation of saturated hydrocarbons by a variety of oxidants including those that model monooxygenases such as P-450. Further development of previous work will bring computational chemistry to bear on the energetics of O-O bond cleavage during oxidation reactions. The relationships between different reaction pathways will be examined in a comparative manner that will hopefully provide an all encompassing mechanism for such reactions as dioxirane, peroxynitrous acid, and iron (III) hydroperoxides. Monooxygenase models utilize porphyrin iron(III) hydroxides and hydrogen peroxide complexes, using multireference methods.
With this Award, the Organic and Macromolecular Chemistry Program continues support for the research of Professor Robert D. Bach of the University of Delaware. Professor Bach uses computers to model chemical reactions in an attempt to learn the precise chain of events that occur. An important reaction and one that Professor Bach focuses on is the oxygenation of saturated hydrocarbon molecules -- those that are inert to most chemical reactions due to almost exclusive presence of strong C-H and C-C single bonds. This kind of reaction is one way in which petrochemical feedstocks are converted into useful oxygen-containing materials such as alcohols. It also is carried out in living organisms by the P-450 enzyme.
