Abstract
The monovanadium-substituted polyoxometalate anion [VMo(7)O(26)](5-), exhibiting a β-octamolybdate archetype structure, was selectively prepared as pentapotassium [hexaikosaoxido(heptamolybdenumvanadium)]ate hexahydrate, K(5)[VMo(7)O(26)]·6H(2)O (VMo(7)), by oxidation of a reduced vanadomolybdate solution with hydrogen peroxide in a fast one-pot approach. X-ray structure analysis revealed that the V atom occupies a single position in the cluster that differs from the other positions by the presence of one doubly-bonded O atom instead of two terminal oxide ligands in all other positions. The composition and structure of VMo(7) was also confirmed by elemental analyses and IR spectroscopy. The selectivity of the synthesis was inspected by a (51)V NMR investigation which showed that this species bound about 95% of V(V) in the crystallization solution. Upon dissolution of VMo(7) in aqueous solution, the [VMo(7)O(26)](5-) anion is substantially decomposed, mostly into [VMo(5)O(19)](3-), α-[VMo(7)O(26)](4-) and [V(2)Mo(4)O(19)](4-), depending on the pH.