Structure and Reactivity of a Mononuclear Nonheme Manganese(III)–Iodosylarene Complex

Transition metal–iodosylarene complexes have been proposed to be key intermediates in the catalytic cycles of metal catalysts with iodosylarene. We report the first X-ray crystal structure and spectroscopic characterization of a mononuclear nonheme manganese­(III)–iodosylarene complex with a tetradentate macrocyclic ligand, [MnIII(TBDAP)­(OIPh)­(OH)]2+ (2). The manganese­(III)–iodosylarene complex is capable of conducting various oxidation reactions with organic substrates, such as C–H bond activation, sulfoxidation and epoxidation. Kinetic studies including isotope labeling experiments and Hammett correlation demonstrate the electrophilic character on the Mn–iodosylarene adduct. This novel intermediate would be prominently valuable for expanding the chemistry of transition metal catalysts.