H₂O₂ Oxidation by Fe^III-OOH Intermediates and Its Effect on Catalytic Efficiency

The oxidation of the C-H and C=C bonds of hydrocarbons with H₂O₂ catalyzed by non-heme iron complexes with pentadentate ligands is widely accepted as involving a reactive Fe^IV=O species such as [(N4Py)Fe^IV=O]²⁺ formed by homolytic cleavage of the O-O bond of an Fe^III-OOH intermediate (where N4Py is 1,1-bis(pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)methanamine). We show here that at low H₂O₂ concentrations the Fe^IV=O species formed is detectable in methanol. Furthermore, we show that the decomposition of H₂O₂ to water and O₂ is an important competing pathway that limits efficiency in the terminal oxidant and indeed dominates reactivity except where only sub-/near-stoichiometric amounts of H₂O₂ are present. Although independently prepared [(N4Py)Fe^IV=O]²⁺ oxidizes stoichiometric H₂O₂ rapidly, the rate of formation of Fe^IV=O from the Fe^III-OOH intermediate is too low to account for the rate of H₂O₂ decomposition observed under catalytic conditions. Indeed, with excess H₂O₂, disproportionation to O₂ and H₂O is due to reaction with the Fe^III-OOH intermediate and thereby prevents formation of the Fe^IV=O species. These data rationalize that the activity of these catalysts with respect to hydrocarbon/alkene oxidation is maximized by maintaining sub-/near-stoichiometric steady-state concentrations of H₂O₂, which ensure that the rate of the H₂O₂ oxidation by the Fe^III-OOH intermediate is less than the rate of the O-O bond homolysis and the subsequent reaction of the Fe^IV=O species with a substrate.