title: Discrete spherical hexadecavanadates incorporating a bromide with oxidative bromination activity.
abstract: Two discrete hexadecavanadates, (n-Bu4N)4[V16O38(X)] (X = Cl(-) (1) and X = Br(-) (2)), were synthesized by a reaction of [V10O26](4-) with a template anion resulting in the incorporation of chloride or bromide in the {V16} spherical cluster framework. The reaction of [V10O26](4-) with p-toluenesulfonic acid proceeded under an aerobic environment to give 2 in the presence of an excess amount of bromide anion, which acted as both a template anion and a reducing reagent for the formation of the mixed-valence framework. For the synthesis of cluster 1, additional reductive conditions were required due to the weak reducing ability of the chloride anion. The crystal structures of 1 and 2 were determined using single-crystal X-ray diffraction analysis. Both were found to consist of a discrete [V(V)9V(IV)7O38(X)](4-) framework by the linkage of VO5 pyramidal units. Cyclic voltammetric studies of 1 and 2 in acetonitrile showed a series of stepwise reversible redox processes, which were due to the redox of the spherical polyoxovanadate frameworks. The oxidative bromination reactions of aromatic substrates were also investigated using cluster 2 as a catalyst under aerobic conditions.
authors.affiliation: Department of Chemistry, Graduate School of Natural Science and Technology, Kanazawa University, Kakuma, Kanazawa, 920-1192, Japan.
authors.forename: Naohiro
authors.initials: N
authors.lastname: Kato
authors.forename: Yoshihito
authors.initials: Y
authors.lastname: Hayashi
mesh_terms: D001965:Bromides / Q000737:chemistry*; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010084:Oxidation-Reduction; D014638:Vanadates / Q000737:chemistry*
chemical_list: D001965:Bromides; D009942:Organometallic Compounds; D014638:Vanadates