Synthetic and Electrochemical Studies of Porphyrin Derivatives and Developement of Artificial Metalloenzymes

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meso-Diphenyletioporphyrin II (DPEP) was prepared and its redox behaviors were studied by cyclic voltammetryin comparison with meso- tetraphenylporphine (TPP), octaethylporphyrin (OEP), and protoporphyrin IX dimethylester (PPIXDME). the redox potentials and basicity data of DPEP were found to be similar to those of OEP and PPIXDME.Redox behavior of high-spin meso-diaryletioporphyrin II (DAEP) iron(III) complexes were investigated through both of equatorial and axial ligand effects. The redox potentials due to porphyrin ring were affected only by the equatorial ligands, whereas the axial ligands affected remarkably the metal redox reactions of high-spin ferric porphyrins, whether the redox potentials due to porphyrin ring or metal could be learned by examining the dependence of the redox potentials on substituents.Redox behaviors of high-spin phenoxy and phenylthio Fe(III) porphyrins were investigated by cyclic voltammetry. The hetero-anion-ligated Fe(III) porphyrins showed a new anodic peak not observed for corresponding Fe(III) porphyrin chloride. High-spin Fe(III) porhpyrins were oxidized by controlled potential electrolysis to give the single-electron oxidation products, which were characterized by spectrophotometric (UV,V,IR) and electron spin rsonance (ESR) measurements. The single-electron oxidation products of phenoxide-ligated Fe(III) porphyrins were not Fe(III) prphyrin -cation radical of Fe(IV) prphyrin but a high-spin Fe(III) porphyrin ligated a single-electron oxidized phenoxide at an axial position.