Ligand Topology Effect on the Reactivity of a Mononuclear Nonheme Iron(IV)-Oxo Complex in Oxygenation Reactions

Mononuclear nonheme iron(IV)-oxo complexes with two different topologies, cis-??-[FeIV(O)(BQCN)]2+ and cis-??-[FeIV(O)(BQCN)]2+, were synthesized and characterized with various spectroscopic methods. The effect of ligand topology on the reactivities of nonheme iron(IV)-oxo complexes was investigated in C???H bond activation and oxygen atom-transfer reactions; cis-??-[FeIV(O)(BQCN)]2+ was more reactive than cis-??-[FeIV(O)(BQCN)]2+ in the oxidation reactions. The reactivity difference between the cis-?? and cis-?? isomers of [FeIV(O)(BQCN)]2+ was rationalized with the FeIV/III redox potentials of the iron(IV)-oxo complexes: the FeIV/III redox potential of the cis-?? isomer was 0.11 V higher than that of the cis-?? isomer