Mononuclear nonheme iron(iv)–oxo and manganese(iv)–oxo complexes in oxidation reactions: experimental results prove theoretical prediction.

Reactivities of mononuclear nonheme iron(iv)–oxo and manganese(iv)–oxo complexes bearing a pentadentate N4Py ligand, [MIVO(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 FeIVO is more reactive than MnIVO. The latter is shown to react through excited state reactivity (ESR). [ABSTRACT FROM AUTHOR]