Structure and redox properties of a novel decavanadium cluster [(V=O)102-O)93-O)3(C5 H7O2)6] in dichloromethane

Kenichi Oyaizu, E. L. Dewi, E. Tsuchida

    Research output: Contribution to journalArticle

    18 Citations (Scopus)

    Abstract

    A novel decavanadium cluster [(V=O)102-O)93-O)3(C5H7 O2)6] bearing ten oxovanadium(V) centers linked with bridging oxygen atoms was prepared. In contrast to the well known decavanadate ion V10O28/6-, the molecule was soluble in organic solvents such as dichloromethane and 1,1,2,2-tetrachloroethane due to the peripheral acetylacetone ligands. X-ray crystallographic analysis revealed a molecular framework formed by nine square-pyramidal VO5 polyhedra surrounding one VO4 tetrahedron linked through the corners. The molecule consists of approximate three-fold rotational symmetry, allowing the classification of ten vanadium atoms into four chemically equivalent categories. The unique metal core geometry persists in solution, which was demonstrated by the four peaks in the 51V-NMR spectrum. However, the four types of vanadium atom could not be distinguished by electrochemical measurements; consequently, the molecule was a multielectron reservoir which showed a broad cathodic wave near 0.6 V vs. Ag

    Original languageEnglish
    Pages (from-to)136-141
    Number of pages6
    JournalJournal of Electroanalytical Chemistry
    Volume498
    Issue number1-2
    DOIs
    Publication statusPublished - 2001 Feb 16

    Fingerprint

    Methylene Chloride
    Dichloromethane
    Vanadium
    Atoms
    Molecules
    Bearings (structural)
    Vanadates
    Organic solvents
    Metals
    Ligands
    Nuclear magnetic resonance
    Ions
    Oxygen
    X rays
    Geometry
    Oxidation-Reduction

    Keywords

    • Crystal structure
    • Electron transfer
    • Vanadium cluster

    ASJC Scopus subject areas

    • Chemical Engineering(all)
    • Analytical Chemistry
    • Electrochemistry

    Cite this

    Structure and redox properties of a novel decavanadium cluster [(V=O)102-O)93-O)3(C5 H7O2)6] in dichloromethane. / Oyaizu, Kenichi; Dewi, E. L.; Tsuchida, E.

    In: Journal of Electroanalytical Chemistry, Vol. 498, No. 1-2, 16.02.2001, p. 136-141.

    Research output: Contribution to journalArticle

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    abstract = "A novel decavanadium cluster [(V=O)10(μ2-O)9 (μ3-O)3(C5H7 O2)6] bearing ten oxovanadium(V) centers linked with bridging oxygen atoms was prepared. In contrast to the well known decavanadate ion V10O28/6-, the molecule was soluble in organic solvents such as dichloromethane and 1,1,2,2-tetrachloroethane due to the peripheral acetylacetone ligands. X-ray crystallographic analysis revealed a molecular framework formed by nine square-pyramidal VO5 polyhedra surrounding one VO4 tetrahedron linked through the corners. The molecule consists of approximate three-fold rotational symmetry, allowing the classification of ten vanadium atoms into four chemically equivalent categories. The unique metal core geometry persists in solution, which was demonstrated by the four peaks in the 51V-NMR spectrum. However, the four types of vanadium atom could not be distinguished by electrochemical measurements; consequently, the molecule was a multielectron reservoir which showed a broad cathodic wave near 0.6 V vs. Ag",
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