Mononuclear nonheme iron(IV)-oxo and manganese(IV)-oxo complexes in oxidation reactions: experimental results prove theoretical prediction

Abstract

Reactivities of mononuclear nonheme iron(IV)-oxo and manganese(IV)-oxo complexes bearing a pentadentate N4Py ligand, [(MO)-O-IV(N4Py)](2+) (M = Fe and Mn), are compared in hydrogen atom transfer (HAT) and oxygen atom transfer (OAT) reactions; theoretical and experimental results show that (FeO)-O-IV is more reactive than (MnO)-O-IV. The latter is shown to react through excited state reactivity (ESR).