Coordination of BF4 - to oxovanadium(V) complexes, evidenced by the redox potential of oxovanadium(IV/V) couples in CH2Cl2

Kenichi Oyaizu, Eniya Listiani Dewi, Eishun Tsuchida

    Research output: Contribution to journalArticle

    19 Citations (Scopus)

    Abstract

    The oxidation of oxovanadium(IV) complexes [LVIVO] (L = tetradentate Schiff-base ligands such as N,N′-ethylenebis- (salicylideneaminate)(2-) (salen) and N,N′ -2,2-dimethylpropylenebis(salicylideneaminate)(2-) (salpn)) to [LVVO]+, believed to be responsible for the voltammetric response near 0.6 V vs Ag/AgC in CH2Cl2 in the presence of tetrabutylammonium tetrafluoroborate as a supporting electrolyte, is in fact coupled to a homogeneous process where [LVO]+ coordinates BF4 - to form a neutral complex formulated as [LVOBF4]. The formation constants for [VO(salen)BF4] and [VO(salpn)BF4] are evaluated to be Ksalen -1 = 1.1 × 102 M-1 and Ksalpn -1 = 1.4 × 10 M-1, respectively. Crystal structure of [VO(salen)BF4] reveals that one of the fluorine atoms in BF4 - is so close to the vanadium(V) atom as to be practically bound in the solid state.

    Original languageEnglish
    Pages (from-to)1070-1075
    Number of pages6
    JournalInorganic Chemistry
    Volume42
    Issue number4
    DOIs
    Publication statusPublished - 2003 Feb 24

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    vanadium
    imines
    fluorine
    atoms
    Atoms
    Vanadium
    Schiff Bases
    Fluorine
    electrolytes
    solid state
    Electrolytes
    ligands
    oxidation
    crystal structure
    Crystal structure
    Ligands
    Oxidation
    disalicylaldehyde ethylenediamine
    Oxidation-Reduction
    oxovanadium IV

    ASJC Scopus subject areas

    • Inorganic Chemistry

    Cite this

    Coordination of BF4 - to oxovanadium(V) complexes, evidenced by the redox potential of oxovanadium(IV/V) couples in CH2Cl2 . / Oyaizu, Kenichi; Dewi, Eniya Listiani; Tsuchida, Eishun.

    In: Inorganic Chemistry, Vol. 42, No. 4, 24.02.2003, p. 1070-1075.

    Research output: Contribution to journalArticle

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    abstract = "The oxidation of oxovanadium(IV) complexes [LVIVO] (L = tetradentate Schiff-base ligands such as N,N′-ethylenebis- (salicylideneaminate)(2-) (salen) and N,N′ -2,2-dimethylpropylenebis(salicylideneaminate)(2-) (salpn)) to [LVVO]+, believed to be responsible for the voltammetric response near 0.6 V vs Ag/AgC in CH2Cl2 in the presence of tetrabutylammonium tetrafluoroborate as a supporting electrolyte, is in fact coupled to a homogeneous process where [LVO]+ coordinates BF4 - to form a neutral complex formulated as [LVOBF4]. The formation constants for [VO(salen)BF4] and [VO(salpn)BF4] are evaluated to be Ksalen -1 = 1.1 × 102 M-1 and Ksalpn -1 = 1.4 × 10 M-1, respectively. Crystal structure of [VO(salen)BF4] reveals that one of the fluorine atoms in BF4 - is so close to the vanadium(V) atom as to be practically bound in the solid state.",
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    AB - The oxidation of oxovanadium(IV) complexes [LVIVO] (L = tetradentate Schiff-base ligands such as N,N′-ethylenebis- (salicylideneaminate)(2-) (salen) and N,N′ -2,2-dimethylpropylenebis(salicylideneaminate)(2-) (salpn)) to [LVVO]+, believed to be responsible for the voltammetric response near 0.6 V vs Ag/AgC in CH2Cl2 in the presence of tetrabutylammonium tetrafluoroborate as a supporting electrolyte, is in fact coupled to a homogeneous process where [LVO]+ coordinates BF4 - to form a neutral complex formulated as [LVOBF4]. The formation constants for [VO(salen)BF4] and [VO(salpn)BF4] are evaluated to be Ksalen -1 = 1.1 × 102 M-1 and Ksalpn -1 = 1.4 × 10 M-1, respectively. Crystal structure of [VO(salen)BF4] reveals that one of the fluorine atoms in BF4 - is so close to the vanadium(V) atom as to be practically bound in the solid state.

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