Mononuclear nonheme iron(<scp>iv</scp>)–oxo and manganese(<scp>iv</scp>)–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, [M(IV)O(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 Fe(IV)O is more reactive than Mn(IV)O. The latter is shown to react through excited state reactivity (ESR).