Effect of External Electric Fields on the Oxidation Reaction of Olefins by Fe(IV)OCl–Porphyrin Complexes

Abstract

Abstract Insights of environmental perturbation (an external electric field, EEF) are complicated but important in terms of experiments. In this paper, we report theoretical results of the effect of an EEF on olefin epoxidation by an Fe(IV)OCl–porphyrin complex using density functional theory. The EEF along the electron flow greatly affects the potential energy profile, and thereby affects the reaction mechanism and stabilization of the species. The results show that a negative EEF catalyzes ethylene epoxidation, whereas a positive EEF inhibits the reaction. Moreover, an EEF can exchange the ground state with the low-lying excited states. Therefore, the potential energy profile along the epoxidation reaction is mainly modified by the electron transfer from ethylene to the Fe(IV)OCl–porphyrin complex.