Catalytic behavior of a μ-oxo dimanganese(III) octaethylporphyrin in O2 reduction

Kenichi Oyaizu, Agus Haryono, Hiroyuki Yonemaru, Eishun Tsuchida

    Research output: Contribution to journalArticle

    20 Citations (Scopus)

    Abstract

    The electrochemistry of a μ-oxo dimanganese(III) octaethylporphyrin (II) and those of the corresponding mononuclear complexes MnIII(OEP)Cl (I), MnIII(OEP)ClO4 (III) and MnIII(OEP)OH (IV) (where OEP represents octaethylporphyrin) were studied. When complex II was adsorbed on an electrode and placed in aqueous acidic electrolyte solutions, efficient catalysis of the four-electron reduction of O2 to H2O was accomplished. A control experiment using an electrode modified with the mononuclear manganese(III) complex I resulted in a significant decrease in the selectivity for the four-electron reduction. The hydroxomanganese(III) complex IV was produced in the course of the oxidation of MnII(OEP) to MnIII(OEP)+ with O2 under acidic conditions. Complex I was isolated as single crystals and characterized by X-ray crystallography. Although complex II was not isolated as single crystals, the long manganese-axial ligand distance (2.385 Å) in I provided an estimate that a similar geometry would be true for II, allowing accommodation of an O2 molecule between the two manganese atoms in the adsorbed cofacial porphyrins.

    Original languageEnglish
    Pages (from-to)3393-3399
    Number of pages7
    JournalJournal of the Chemical Society - Faraday Transactions
    Volume94
    Issue number22
    Publication statusPublished - 1998 Nov 21

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    Manganese
    manganese
    Single crystals
    Electrodes
    electrodes
    Electrons
    X ray crystallography
    single crystals
    Porphyrins
    accommodation
    Electrochemistry
    electrochemistry
    porphyrins
    Electrolytes
    Catalysis
    crystallography
    catalysis
    electrons
    selectivity
    electrolytes

    ASJC Scopus subject areas

    • Physical and Theoretical Chemistry

    Cite this

    Catalytic behavior of a μ-oxo dimanganese(III) octaethylporphyrin in O2 reduction. / Oyaizu, Kenichi; Haryono, Agus; Yonemaru, Hiroyuki; Tsuchida, Eishun.

    In: Journal of the Chemical Society - Faraday Transactions, Vol. 94, No. 22, 21.11.1998, p. 3393-3399.

    Research output: Contribution to journalArticle

    Oyaizu, Kenichi ; Haryono, Agus ; Yonemaru, Hiroyuki ; Tsuchida, Eishun. / Catalytic behavior of a μ-oxo dimanganese(III) octaethylporphyrin in O2 reduction. In: Journal of the Chemical Society - Faraday Transactions. 1998 ; Vol. 94, No. 22. pp. 3393-3399.
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    abstract = "The electrochemistry of a μ-oxo dimanganese(III) octaethylporphyrin (II) and those of the corresponding mononuclear complexes MnIII(OEP)Cl (I), MnIII(OEP)ClO4 (III) and MnIII(OEP)OH (IV) (where OEP represents octaethylporphyrin) were studied. When complex II was adsorbed on an electrode and placed in aqueous acidic electrolyte solutions, efficient catalysis of the four-electron reduction of O2 to H2O was accomplished. A control experiment using an electrode modified with the mononuclear manganese(III) complex I resulted in a significant decrease in the selectivity for the four-electron reduction. The hydroxomanganese(III) complex IV was produced in the course of the oxidation of MnII(OEP) to MnIII(OEP)+ with O2 under acidic conditions. Complex I was isolated as single crystals and characterized by X-ray crystallography. Although complex II was not isolated as single crystals, the long manganese-axial ligand distance (2.385 {\AA}) in I provided an estimate that a similar geometry would be true for II, allowing accommodation of an O2 molecule between the two manganese atoms in the adsorbed cofacial porphyrins.",
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    AU - Oyaizu, Kenichi

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    AU - Yonemaru, Hiroyuki

    AU - Tsuchida, Eishun

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    N2 - The electrochemistry of a μ-oxo dimanganese(III) octaethylporphyrin (II) and those of the corresponding mononuclear complexes MnIII(OEP)Cl (I), MnIII(OEP)ClO4 (III) and MnIII(OEP)OH (IV) (where OEP represents octaethylporphyrin) were studied. When complex II was adsorbed on an electrode and placed in aqueous acidic electrolyte solutions, efficient catalysis of the four-electron reduction of O2 to H2O was accomplished. A control experiment using an electrode modified with the mononuclear manganese(III) complex I resulted in a significant decrease in the selectivity for the four-electron reduction. The hydroxomanganese(III) complex IV was produced in the course of the oxidation of MnII(OEP) to MnIII(OEP)+ with O2 under acidic conditions. Complex I was isolated as single crystals and characterized by X-ray crystallography. Although complex II was not isolated as single crystals, the long manganese-axial ligand distance (2.385 Å) in I provided an estimate that a similar geometry would be true for II, allowing accommodation of an O2 molecule between the two manganese atoms in the adsorbed cofacial porphyrins.

    AB - The electrochemistry of a μ-oxo dimanganese(III) octaethylporphyrin (II) and those of the corresponding mononuclear complexes MnIII(OEP)Cl (I), MnIII(OEP)ClO4 (III) and MnIII(OEP)OH (IV) (where OEP represents octaethylporphyrin) were studied. When complex II was adsorbed on an electrode and placed in aqueous acidic electrolyte solutions, efficient catalysis of the four-electron reduction of O2 to H2O was accomplished. A control experiment using an electrode modified with the mononuclear manganese(III) complex I resulted in a significant decrease in the selectivity for the four-electron reduction. The hydroxomanganese(III) complex IV was produced in the course of the oxidation of MnII(OEP) to MnIII(OEP)+ with O2 under acidic conditions. Complex I was isolated as single crystals and characterized by X-ray crystallography. Although complex II was not isolated as single crystals, the long manganese-axial ligand distance (2.385 Å) in I provided an estimate that a similar geometry would be true for II, allowing accommodation of an O2 molecule between the two manganese atoms in the adsorbed cofacial porphyrins.

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