Development of metal complex/electron-transfer composite system realizing enzyme-like function

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In the aim of development of new types homogeneous catalysis by metal complexes which works in the similar fashion to metalloenzymes, the effective combination between metal complexes and electron-transfer systems has been studied. As electron-transfer and electron-donor systems, organic and inorganic reductants, electrochemical and photochemical systems have been used in the various catalytic systems involving oxygenations, oxygen generation from water, etc.in both enzymatic and model systems.1)Selective oxygenations by metal complexesOxygenations by heme and nonheme iron complexes have been extensively studied, and developed new types of oxygenations, e.g., ortho-hydroxylation of phenols in the similar way to tyrosine hydroxylases, aromatic ring cleavage of chlorocatechols as the first model reaction for chlorocatechol dioxygenase, and oxygenation of ortho-aminophenols.2)Biocatalytic reactions other than oxygenationsVarious types of catalytic reactions were performed, e.g.functional catalytic antibody, biological NO generation, oxo-transfer reaction by molybdenum enzymes and model conplexes, modeling of the active center of cytochrome C oxidase and oxygen generation by model complexes.3)Development of model systems for bioinorganicelectron-transfer processModeling of the skillful biological electron-transfer mechanisms has been developed, e.g.photo-excited intramolecular electron-transfer bybiologen-bound porphirins, electron-transfer process by artificial mioglobin, selective oxidation by electrochemical processes.