H₂O₂ Oxidation by FeIII–OOH Intermediates and Its Effect on Catalytic Efficiency

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Abstract

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 FeIV=O species such as [(N4Py)FeIV=O]2+ formed by homolytic cleavage of the O-O bond of an FeIII-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 FeIV=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)FeIV=O]2+ oxidizes stoichiometric H₂O₂ rapidly, the rate of formation of FeIV=O from the FeIII-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 FeIII-OOH intermediate and thereby prevents formation of the FeIV=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 FeIII-OOH intermediate is less than the rate of the O-O bond homolysis and the subsequent reaction of the FeIV=O species with a substrate.

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