Use of 2-methyl-1-phenylpropan-2-yl hydroperoxide (MPPH) as a mechanistic probe for the heterolytic versus homolytic O-O bond cleavage of tert-alkyl hydroperoxide by iron(III) porphyrin complex

Abstract

The mechanism of the O-O bond cleavage of tert-alkyl hydroperoxide by iron(III) porphyrin complexes has been studied using 2-methyl-1-phenylpropan-2-yl hydroperoxide (MPPH) as a mechanistic probe; the hydroperoxide O-O bond is cleaved both heterolytically and homolytically and partitioning between the two pathways significantly depends on the reaction conditions such as the pH of the reaction solutions and the nature of porphyrin and axial ligands.