Electron-Transfer Studies of a Peroxide Dianion

A peroxide dianion (O-2(2-)) can be isolated within the cavity of hexacarboxamide cryptand, [(O-2)CmBDCA-5t-H-6](2-), stabilized by hydrogen bonding but otherwise free of proton or metal-ion association. This feature has allowed the electron-transfer (ET) kinetics of isolated peroxide to be examined chemically and electrochemically. The ET of [(O-2)CmBDCA-5t-H-6](2-) with a series of seven quinones, with reduction potentials spanning 1 V, has been examined by stopped-flow spectroscopy. The kinetics of the homogeneous ET reaction has been correlated to heterogeneous ET kinetics as measured electrochemically to provide a unified description of ET between the Butler-Volmer and Marcus models. The chemical and electrochemical oxidation kinetics together indicate that the oxidative ET of O-2(2-) occurs by an outer-sphere mechanism that exhibits significant nonadiabatic character, suggesting that the highest occupied molecular orbital of O-2(2)- within the cryptand is sterically shielded from the oxidizing species. An understanding of the ET chemistry of a free peroxide dianion will be useful in studies of metal air batteries and the use of [(O-2)CmBDCA-5t-H-6](2-) as a chemical reagent.