Alkyl- and Aryl-Substituted Corroles. 4. Solvent Effects on the Electrochemical and Spectral Properties of Cobalt Corroles

Solvent effects on the electrochemistry and spectroscopic properties of alkyl- and aryl-substituted corroles in nonaqueous media are reported. The oxidation and reduction of six compounds containing zero to seven phenyl or substituted phenyl groups on the macrocycle were studied in four different nonaqueous solvents (CH2Cl2, PhCN, THF, and pyridine) containing 0.1 M tetra-n-butylammonium perchlorate. Dimers were formed upon oxidation of all corroles in CH2Cl2, but this was not the case in the other three solvents, where either monomers or dimers were formed upon oxidation depending upon the solvent Gutmann donor number and the number or location of aryl substituents on the macrocycle. The half-wave potentials were analyzed as a function of the number of aryl substituents on the macrocycle as well as the concentration of added pyridine to PhCN solutions of the compound, and these data were combined with data from the spectroelectrochemistry experiments to determine the stoichiometry of the species actually in solution after the first oxidation or first reduction of each compound. The results of these experiments indicate that reduction of the bispyridine adduct (Cor)CoIII(py)2 proceeds via the monopyridine complex (Cor)CoIII(py) to give in each case the unligated cobalt(II) corrole [(Cor)CoII]-. In contrast, pyridine remains coordinated after electrooxidation, and the final product was characterized as [(Cor)CoIII(py)2]+.