PUB - Publikationen an der Universität Bielefeld

Peroxo complexes are key intermediates in water oxidation catalysis (WOC). Cobalt plays an important role in WOC, either as oxides CoOx or as {CoIII(mu-1,2-peroxo)CoIII} complexes, which are the oldest peroxo complexes known. The oxidation of {CoIII(mu-1,2-peroxo)CoIII} complexes had usually been described to form {CoIII(mu-1,2-superoxo)CoIII} complexes; however, recently the formation of {CoIV(mu-1,2-peroxo)CoIII} species were suggested. Using a bis(tetradentate) dinucleating ligand, we present here the synthesis and characterization of {CoIII(mu-1,2-peroxo)(mu-OH)CoIII} and {CoIII(mu-OH)2CoIII} complexes. Oxidation of {CoIII(mu-1,2-peroxo)(mu-OH)CoIII} at -40 °C in CH3CN provides the stable {CoIII(mu-1,2-superoxo)(mu-OH)CoIII} species and activates electrophilic reactivity. Moreover, {CoIII(mu-1,2-peroxo)(mu-OH)CoIII} catalyzes water oxidation, not molecularly but rather via CoOx films. While {CoIII(mu-1,2-peroxo)(mu-OH)CoIII} can be reversibly deprotonated with DBU at -40 °C in CH3CN, {CoIII(mu-1,2-superoxo)(mu-OH)CoIII} undergoes irreversible conversions upon reaction with bases to a new intermediate that is also the decay product of {CoIII(mu-1,2-superoxo)(mu-OH)CoIII} in aqueous solution at pH > 2. Based on a combination of experimental methods, the new intermediate is proposed to have a {CoII(mu-OH)CoIII} core formed by the release of O2 from {CoIII(mu-1,2-superoxo)(mu-OH)CoIII} confirmed by a 100% yield of O2 upon photocatalytic oxidation of {CoIII(mu-1,2-peroxo)(mu-OH)CoIII}. This release of O2 by oxidation of a peroxo intermediate corresponds to the last step in molecular WOC.