Theoretical Suggestion of a Methane Hydroxylation Catalyst

Abstract

Motivated by a recent study on light-induced solar cell that Iridium-oxo complex over WO₃ electrode catalyze water oxidation reaction, we investigated the methane hydroxylation reaction by the same complex. Herein we focused on the closed-shell singlet state reaction due to the no-radical intermediate mechanism although this reaction is energetically unfavored reaction. Using intrinsic bond orbital analysis, we found that the C–H bond cleavage reaction proceed via the hydride transfer mechanism. From the view point of orbital interaction between σ orbital (C–H bond in methane) and π* orbital (Ir=O bond in Ir complex), we demonstrated that the reactivity of the methane hydroxylation reaction in the closed shell singlet state depends on the energy level of π* orbital.