HO Oxidation by Fe-OOH Intermediates and Its Effect on Catalytic Efficiency

Overview

Journal ACS Catal

Publisher American Chemical Society

Date 2018 Oct 16

PMID 30319886

Citations 10

Authors

Juan Chen

Apparao Draksharapu

Davide Angelone

Duenpen Unjaroen

Sandeep K Padamati

Ronald Hage

Marcel Swart

Carole Duboc

Wesley R Browne

Affiliations

Soon will be listed here.

Abstract

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

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