Spectroscopic Characterization of a Hydroperoxo–Heme Intermediate: Conversion of a Side‐On Peroxo to an End‐On Hydroperoxo Complex

Abstract

Modeling job: Protonation of a closed seven-coordinate side-on heme peroxide can switch its spin state from high- to low-spin and convert the η2 binding fashion into a monodentate configuration to afford the corresponding hydroperoxide (see scheme). The end-on low-spin ferric hydroperoxo–heme species bear a covalently appended axial imidazole ligand and are easily prepared.