Electrochemical investigations of the complexes resulting from the acid-promoted deoxygenation and dimerization of (N,N′-ethylenebis(salicylideneaminato))oxovanadium(IV)

Eishun Tsuchida, Kimihisa Yamamoto, Kenichi Oyaizu, Naoki Iwasaki, Fred C. Anson

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    Abstract

    Electrochemical confirmation that (N,N′-ethylenebis(salicylideneaminato))oxovanadium(IV), VO(salen), reacts with trifluoromethanesulfonic acid (CF3SO3H) or triphenylmethyl tetrafluoroborate (Ph3C(BF4)) to form a deoxygenated complex, VIV(salen)2+, and a μ-oxodinuclear complex, [(salen)VOV(salen)]X2, (X = CF3SO3 - or BF4 -) is presented. Cyclic voltammograms of VO(salen) in the presence of CF3SO3H or Ph3C(BF4) exhibit reversible waves with formal potentials near 0.5 and 0.8 V (vs Ag/AgCl). The cathodic wave at 0.5 V is argued to arise from the combined reduction of V(salen)2+ and the μ-oxo dimeric complex and the wave at 0.8 V from the oxidation of the V(salen)2+ complex. The diffusion coefficients of these three complexes in acetonitrile were determined. The dimerization of VO(salen) is initiated by deoxygenation of the V=O center by H+ or Ph3C+ to produce V(salen)2+ which enters into an equilibrium with a second VO(salen) complex to produce the μ-oxo dimer. The kinetics of the second order dimerization reaction were monitored, and the equilibrium contant for the formation of the μ-oxo dimer in acetonitrile was evaluated as 0.7 mM-1.

    Original languageEnglish
    Pages (from-to)1056-1063
    Number of pages8
    JournalInorganic Chemistry
    Volume33
    Issue number6
    Publication statusPublished - 1994

    Fingerprint

    deoxygenation
    Dimerization
    dimerization
    acids
    Acids
    acetonitrile
    dimers
    diffusion coefficient
    oxidation
    Dimers
    kinetics
    disalicylaldehyde ethylenediamine
    oxovanadium IV

    ASJC Scopus subject areas

    • Inorganic Chemistry

    Cite this

    Electrochemical investigations of the complexes resulting from the acid-promoted deoxygenation and dimerization of (N,N′-ethylenebis(salicylideneaminato))oxovanadium(IV). / Tsuchida, Eishun; Yamamoto, Kimihisa; Oyaizu, Kenichi; Iwasaki, Naoki; Anson, Fred C.

    In: Inorganic Chemistry, Vol. 33, No. 6, 1994, p. 1056-1063.

    Research output: Contribution to journalArticle

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    abstract = "Electrochemical confirmation that (N,N′-ethylenebis(salicylideneaminato))oxovanadium(IV), VO(salen), reacts with trifluoromethanesulfonic acid (CF3SO3H) or triphenylmethyl tetrafluoroborate (Ph3C(BF4)) to form a deoxygenated complex, VIV(salen)2+, and a μ-oxodinuclear complex, [(salen)VOV(salen)]X2, (X = CF3SO3 - or BF4 -) is presented. Cyclic voltammograms of VO(salen) in the presence of CF3SO3H or Ph3C(BF4) exhibit reversible waves with formal potentials near 0.5 and 0.8 V (vs Ag/AgCl). The cathodic wave at 0.5 V is argued to arise from the combined reduction of V(salen)2+ and the μ-oxo dimeric complex and the wave at 0.8 V from the oxidation of the V(salen)2+ complex. The diffusion coefficients of these three complexes in acetonitrile were determined. The dimerization of VO(salen) is initiated by deoxygenation of the V=O center by H+ or Ph3C+ to produce V(salen)2+ which enters into an equilibrium with a second VO(salen) complex to produce the μ-oxo dimer. The kinetics of the second order dimerization reaction were monitored, and the equilibrium contant for the formation of the μ-oxo dimer in acetonitrile was evaluated as 0.7 mM-1.",
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    AU - Yamamoto, Kimihisa

    AU - Oyaizu, Kenichi

    AU - Iwasaki, Naoki

    AU - Anson, Fred C.

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