Preparation and electrochemical behaviors of phenoxide-coordinated iron(III) porphyrins.
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概要
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A new series of iron(III) porphyrins having various phenoxide anions as the axial ligand, [Fe<SUP>III</SUP>(porphyrin)(4-X–C<SUB>6</SUB>H<SUB>4</SUB>O<SUP>−</SUP>)] (porphyrin=octaethylporphyrin and tetraphenylporphyrin; X=OCH<SUB>3</SUB>, CH<SUB>3</SUB>, H, C<SUB>6</SUB>H<SUB>5</SUB>, Cl, Br, COCH<SUB>3</SUB>, CN, CHO, and NO<SUB>2</SUB>) were synthesized. All these complexes are five-coordinated high-spin complexes (<I>S</I>=5⁄2). Their electrochemical behaviors were investigated by the cyclic voltammetry and the controlled potential coulometry. The complexes showed significantly negative potentials for the Fe<SUP>II</SUP>/Fe<SUP>III</SUP> redox couple (−0.4–−0.8 V). A good linear relationship was found between the half-wave potentials of the Fe<SUP>II</SUP>/Fe<SUP>III</SUP> redox couple and the Hammett σ-values of the substituent X. A new characteristic feature is the appearance of the redox peaks of the coordinated phenoxide anions near the redox couple of the porphyrin ring oxidoreduction. The role of the tyrosine-67 in the enzymatic mechanism for cytochrome c is discussed.
- 公益社団法人 日本化学会の論文
著者
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Sugimoto Hiroshi
Department Of Aeronautics And Astronautics Graduate School Of Engineering Kyoto University
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Mori Masayasu
Department of Chemistry, Faculty of Science, Osaka City University
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Ueda Nobuhiro
Department of Chemistry, Faculty of Science, Osaka City University
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