The secondary coordination sphere controlled reactivity of a ferric-superoxo heme: unexpected conversion to a ferric hydroperoxo intermediate by reaction with a high-spin ferrous heme.

Abstract

A bio-inspired heme complex involving both a proton donor and an axial imidazole ligand reduces the activation energy for the formation of a ferric hydroperoxo intermediate. A high-spin ferrous heme is shown to be capable of reducing its superoxy species to generate a ferric hydroperoxo intermediate for the first time.