A chameleon catalyst for nonheme iron-promoted olefin oxidation

Abstract

We report the chameleonic reactivity of two nonheme iron catalysts for olefin oxidation with H₂O₂ that switch from nearly exclusive cis-dihydroxylation of electron-poor olefins to the exclusive epoxidation of electron-rich olefins upon addition of acetic acid. This switching suggests a common precursor to the nucleophilic oxidant proposed to Fe^III-η²-OOH and electrophilic oxidant proposed to Fe^V(O)(OAc), and reversible coordination of acetic acid as a switching pathway.