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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    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
    Issue number6
    Publication statusPublished - 1994


    ASJC Scopus subject areas

    • Inorganic Chemistry

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