We have used dioxygen, not artificial oxidants such as peracids, iodosylarenes, and hydroperoxides, in the generation of a mononuclear nonheme oxoiron(IV) complex, [Fe(IV)(TMC)(O)]2+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), from its corresponding Fe(II) complex, [Fe(TMC)(CF3SO3)2]. The formation of oxoiron(IV) species by activating dioxygen was markedly dependent on iron(...