Biomimetic Chemistry of Chromium. Intramolecular Conversion of Hydroperoxochromium(III) to Oxochromium(V)

Abstract

Transition metal hydroperoxo complexes, LMOOH (L = ligand system, M = transition metal), are important intermediates in many catalytic oxidations by molecular oxygen and hydrogen peroxide. These complexes typically react as electrophiles and one-electron oxidants and show no tendency to form oxenes, presumably because the nonparticipating ligands do not stabilize the metal in the 4+ or 5+ oxidation state. We now report that a synthetic hydroperoxochromium(III) complex of a non-porphyrin, saturated macrocycle undergoes intramolecular conversion to Cr(V). 30 refs., 1 fig.