ELECTROCHEMISTRY AND SPECTROELECTROCHEMISTRY OF CHLORO(PHTHALOCYANINATO)RHODIUM(III) SPECIES IN SOLUTION-PHASE

The electrochemistry and spectroelectrochemistry of mononuclear chloro (phthalocyaninato)rhodium(III), ClRhIII-Pc, has been studied in the so lution phase, at ambient and low temperature. Reduction leads to a rho dium(II) species, ClRh(II)Pc which is stable at low temperature, with reversible electrochemistry, but at ambient temperature dimerizes gene rating a rhodium-rhodium-bonded dinuclear species. This dinuclear spec ies is oxidized at a much more positive potential than the mononuclear species. The complex electrochemical behavior of these species is sho wn to be due to the presence of three different dinuclear Rh-II specie s with zero, one, or two axially bound chloride ions whose detailed el ectrochemical properties are explored. Reduction of the dinuclear Rh(I I)Pc species leads to a reversibly generated anion radical species.