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, [M^IVO(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^IVO is more reactive than Mn^IVO. The latter is shown to react through excited state reactivity (ESR).