Late transition metal complexes of oxypyriporphyrin and the platinum(II) complex of oxybenziporphyrin

Abstract

Even though oxypyriporphyrin, a pyridone-containing porphyrinoid system, has the equivalent coordination core to true porphyrins, its coordination chemistry has been little explored. In this study, the first examples of palladium(II), platinum(II) and silver(II) oxypyriporphyrins have been synthesized. Conventional conditions failed to result in the formation of a platinum(II) complex, but moderate yields were obtained when oxypyriporphyrin was reacted with platinum(II) chloride in refluxing mixtures of DMF and acetic acid containing potassium acetate. The palladium(II) and platinum(II) derivatives were characterized by X-ray crystallography. The structurally analogous carbaporphyrinoid system oxybenziporphyrin was also shown to react with platinum(II) chloride under the same conditions to give a platinum(II) hydroxybenziporphyrin complex. Unlike oxybenziporphyrin, this complex is only weakly diatropic. In the presence of base, the diatropic character was reasserted to afford an aromatic anionic species.