Highly reduced, polyoxo(alkoxo)vanadium(IIII/IV) clusters

Ian S. Tidmarsh, Rebecca H. Laye, Paul R. Brearley, Maheswaran Shanmugam, E. Carolina Sañudo, Lorenzo Sorace, Andrea Caneschi, Eric J L McInnes

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    A family of high nuclearity oxo(alkoxo)vanadium clusters in unprecedentedly low oxidation states is reported, synthesised from simple vanadium diketonate precursors in alcohols under solvothermal conditions. Crystal structures of [V18(O)12(OH)2-(H2O) 4(EtO)22(O2CPh)6(acac)2] (1), [V16Na2(O)18(EtO)16(EtOH) 2(O2CPh)6-(HO2CPh)2] ∞ (2), [V13(O)13(EtO)15-(EtOH) (RCO2)3] in which R = adamantyl (3) or Ph3C (4), and [V11(O)12-(EtO)13(EtOH)(Ph 3CCO2)2(MePO3)] (5) are reported, revealing these to be (VIII16VIV2} (1), {VIII9V1V3VV) (3 and 4) and {VIII3VIV8} (5) clusters, while 2 consists of isolated {VIII8VIV 8} clusters bridged into polymeric chains by (Na2-(OEt) 2) fragments. Solvothermal conditions are essential to the formation of these species, and the level of oxidation of the isolated clusters is in part controlled by the crystallisation time, with the lowest mean-oxidation-state species being isolated by direct crystallisation on controlled cooling of the reaction solutions. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.
    Original languageEnglish
    Pages (from-to)6329-6338
    Number of pages9
    JournalChemistry - A European Journal
    Issue number22
    Publication statusPublished - 2007


    • Cluster compounds
    • Polyoxometalates
    • Solvothermal synthesis
    • Vanadium


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