(600cb) A DFT Study for the Catalytic Oxidation of Terminal Alkenes

Kanika Mittal* and Linda J. Broadbelt

Department of Chemical and Biological Engineering, Northwestern University, Evanston, IL 60208

e-mail: kanikamittal2013@u.northwestern.edu

Abstract

The conversion of olefins to oxides is an important step in the production of a large number of chemicals for a variety of applications, especially in polymer blending, in the production of a large number of bulk, fine, and pharmaceutical-grade chemicals, and intermediates for synthesizing other organic compounds. Despite the high demand and need, technological improvements can still be made in order to achieve adequate yields and selectivities for the desired oxide. This work was aimed at developing a mechanistic understanding of oxidation processes over Mn-tmtacn complexes using hydrogen peroxide as the oxidant for a series of alkenes, with a focus on cyclooctene.  Quantum chemical calculations on different reactants, intermediates and transition states were carried out with the goal of developing structure/reactivity correlations to estimate rate coefficients for key elementary steps on other catalysts and for other substrates of interest.