Inorganic Chemistry, Vol.37, No.5, 1037-1043, 1998
(5,10,15,20-tetramethylporphyrinato)cobalt(II) : A remarkably active catalyst for the electroreduction of O-2 to H2O
Unlike most simple, monomeric cobalt porphyrins, the cobalt tetramethylporphyrin identified in the title catalyzes the electroreduction of O-2 to H2O instead of H2O2. On graphite electrodes, coatings of the porphyrin prepared by irreversible adsorption from chloroform solutions catalyze the electroreduction of O-2 in aqueous HClO4 at unusually positive potentials. Both the title porphyrin and the corresponding unsubstituted cobalt porphine are argued to derive their activity as four-electron reduction catalysts from their propensity to form dimers (or higher aggregates) in solution and, presumptively, on the surface of graphite electrodes.