title: Highly reduced, polyoxo(alkoxo)vanadium(III/IV) clusters.
abstract: 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]infinity (2), [V13(O)13(EtO)15(EtOH)(RCO2)3] in which R=adamantyl (3) or Ph3C (4), and [V11(O)12(EtO)13(EtOH)(Ph3CCO2)2(MePO3)] (5) are reported, revealing these to be {VIII 16VIV 2} (1), {VIII 9VIV 3VV} (3 and 4) and {VIII 3VIV 8} (5) clusters, while 2 consists of isolated {VIII 8VIV 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.
authors.affiliation: School of Chemistry, The University of Manchester, Manchester M13 9PL, UK.
authors.forename: Ian S
authors.initials: IS
authors.lastname: Tidmarsh
authors.forename: Rebecca H
authors.initials: RH
authors.lastname: Laye
authors.forename: Paul R
authors.initials: PR
authors.lastname: Brearley
authors.forename: Maheswaran
authors.initials: M
authors.lastname: Shanmugam
authors.forename: E Carolina
authors.initials: EC
authors.lastname: Sañudo
authors.forename: Lorenzo
authors.initials: L
authors.lastname: Sorace
authors.forename: Andrea
authors.initials: A
authors.lastname: Caneschi
authors.forename: Eric J L
authors.initials: EJ
authors.lastname: McInnes