Catalysis of the electroreduction of O2 to H2O by vanadium-salen complexes in acidified dichloromethane

Eishun Tsuchida, Kenichi Oyaizu, Eniya Listiani Dewi, Takahiro Imai, Fred C. Anson

    Research output: Contribution to journalArticle

    48 Citations (Scopus)

    Abstract

    Addition of stoichiometric quantities of trifluoromethanesulfonic (triflic) acid to solutions of VIVO(salen) (H2-salen = N,N′-ethylenebis(salicylideneamine)) in dichloromethane produces the μ-oxo dinuclear vanadium(IV) complex [(salen)VIVOVIV(salen)]2+ ([VIVOVIV]2+). Addition of significant excesses of triflic acid converts the dimer into [VIV(salen)]2+. In dichloromethane solutions containing 0.1 M tetrabutylammonium tetrafluoroborate, the [VIVOVIV]2+ complex undergoes disproportionation and dissociation reactions to produce a solution containing an equimolar mixture of VIVO(salen), [VIII(salen)]+, and [VIVOVV]3+. The oxophilic [VIII(salen)]+ complex reacts with O2 to accomplish a four-electron reduction of O2: 2[VIII(salen)]+ + O2 → 2[VVO(salen)]+. These reactions can be exploited to carry out catalytic electroreductions of O2 to H2O in acidified dichloromethane solutions of VIVO(salen) at unusually positive potentials.

    Original languageEnglish
    Pages (from-to)3704-3708
    Number of pages5
    JournalInorganic Chemistry
    Volume38
    Issue number16
    Publication statusPublished - 1999

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    Vanadium
    Methylene Chloride
    vanadium
    Catalysis
    catalysis
    acids
    dimers
    dissociation
    disalicylaldehyde ethylenediamine
    electrons
    Dimers

    ASJC Scopus subject areas

    • Inorganic Chemistry

    Cite this

    Catalysis of the electroreduction of O2 to H2O by vanadium-salen complexes in acidified dichloromethane. / Tsuchida, Eishun; Oyaizu, Kenichi; Dewi, Eniya Listiani; Imai, Takahiro; Anson, Fred C.

    In: Inorganic Chemistry, Vol. 38, No. 16, 1999, p. 3704-3708.

    Research output: Contribution to journalArticle

    Tsuchida, Eishun ; Oyaizu, Kenichi ; Dewi, Eniya Listiani ; Imai, Takahiro ; Anson, Fred C. / Catalysis of the electroreduction of O2 to H2O by vanadium-salen complexes in acidified dichloromethane. In: Inorganic Chemistry. 1999 ; Vol. 38, No. 16. pp. 3704-3708.
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    AU - Dewi, Eniya Listiani

    AU - Imai, Takahiro

    AU - Anson, Fred C.

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    AB - Addition of stoichiometric quantities of trifluoromethanesulfonic (triflic) acid to solutions of VIVO(salen) (H2-salen = N,N′-ethylenebis(salicylideneamine)) in dichloromethane produces the μ-oxo dinuclear vanadium(IV) complex [(salen)VIVOVIV(salen)]2+ ([VIVOVIV]2+). Addition of significant excesses of triflic acid converts the dimer into [VIV(salen)]2+. In dichloromethane solutions containing 0.1 M tetrabutylammonium tetrafluoroborate, the [VIVOVIV]2+ complex undergoes disproportionation and dissociation reactions to produce a solution containing an equimolar mixture of VIVO(salen), [VIII(salen)]+, and [VIVOVV]3+. The oxophilic [VIII(salen)]+ complex reacts with O2 to accomplish a four-electron reduction of O2: 2[VIII(salen)]+ + O2 → 2[VVO(salen)]+. These reactions can be exploited to carry out catalytic electroreductions of O2 to H2O in acidified dichloromethane solutions of VIVO(salen) at unusually positive potentials.

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