(μ-Peroxo)bis[pyridine(phthalocyaninato)iron(III)] as a convenient catalyst for the four-electron reduction of dioxygen

Kenichi Oyaizu, Agus Haryono, Junichiro Natori, Eishun Tsuchida

    Research output: Contribution to journalArticle

    19 Citations (Scopus)

    Abstract

    A remarkable increase in the selectivity of four-electron reduction of O2 at an iron phthalocyanine complex adsorbed on a carbon electrode is accomplished by the use of a peroxo-bridged pyFeIIIPc-O2-PcFeIIIpy (py = pyridine, Pc = phthalocyanine dianion). Electroreduction of the dimer adsorbed on an electrode produced two solid state, cofacially fixed iron(II) phthalocyanine molecules under acidic conditions. Raman studies on the adsorbate revealed the restricted dynamics of the phthalocyanine rings adsorbed on a solid support that was responsible for the facile accommodation of an O2 molecule between the adjacent two iron(II) atoms. The contrast with the catalytic behavior of a mononuclear iron(II) stems from the formation of a μ-peroxo bond upon the reaction with O2, which subsequently cleaves under acidic conditions to produce two molecules of H2O.

    Original languageEnglish
    Pages (from-to)3737-3742
    Number of pages6
    JournalJournal of the Chemical Society - Faraday Transactions
    Volume94
    Issue number24
    Publication statusPublished - 1998

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    pyridines
    Iron
    Oxygen
    iron
    catalysts
    Catalysts
    Molecules
    Electrons
    Electrodes
    electrons
    Adsorbates
    molecules
    Dimers
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    Carbon
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    ASJC Scopus subject areas

    • Physical and Theoretical Chemistry

    Cite this

    (μ-Peroxo)bis[pyridine(phthalocyaninato)iron(III)] as a convenient catalyst for the four-electron reduction of dioxygen. / Oyaizu, Kenichi; Haryono, Agus; Natori, Junichiro; Tsuchida, Eishun.

    In: Journal of the Chemical Society - Faraday Transactions, Vol. 94, No. 24, 1998, p. 3737-3742.

    Research output: Contribution to journalArticle

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    abstract = "A remarkable increase in the selectivity of four-electron reduction of O2 at an iron phthalocyanine complex adsorbed on a carbon electrode is accomplished by the use of a peroxo-bridged pyFeIIIPc-O2-PcFeIIIpy (py = pyridine, Pc = phthalocyanine dianion). Electroreduction of the dimer adsorbed on an electrode produced two solid state, cofacially fixed iron(II) phthalocyanine molecules under acidic conditions. Raman studies on the adsorbate revealed the restricted dynamics of the phthalocyanine rings adsorbed on a solid support that was responsible for the facile accommodation of an O2 molecule between the adjacent two iron(II) atoms. The contrast with the catalytic behavior of a mononuclear iron(II) stems from the formation of a μ-peroxo bond upon the reaction with O2, which subsequently cleaves under acidic conditions to produce two molecules of H2O.",
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    AU - Natori, Junichiro

    AU - Tsuchida, Eishun

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    AB - A remarkable increase in the selectivity of four-electron reduction of O2 at an iron phthalocyanine complex adsorbed on a carbon electrode is accomplished by the use of a peroxo-bridged pyFeIIIPc-O2-PcFeIIIpy (py = pyridine, Pc = phthalocyanine dianion). Electroreduction of the dimer adsorbed on an electrode produced two solid state, cofacially fixed iron(II) phthalocyanine molecules under acidic conditions. Raman studies on the adsorbate revealed the restricted dynamics of the phthalocyanine rings adsorbed on a solid support that was responsible for the facile accommodation of an O2 molecule between the adjacent two iron(II) atoms. The contrast with the catalytic behavior of a mononuclear iron(II) stems from the formation of a μ-peroxo bond upon the reaction with O2, which subsequently cleaves under acidic conditions to produce two molecules of H2O.

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