Discrete spherical hexadecavanadates incorporating a bromide with oxidative bromination activity?

Dalton Transactions Pub Date: 2013-07-16 DOI: 10.1039/C3DT50521A

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 [VV9VIV7O38(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.

Graphical abstract: Discrete spherical hexadecavanadates incorporating a bromide with oxidative bromination activity
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