Abstract
The substitution reaction of Keggin-type polyoxometalates, [XM 12O 40] n − (X = Si, Ge, P, or As; M = Mo or W), with vanadium(V) ion was investigated with cyclic voltammetry, Raman spectroscopy, and 31P NMR. The effect of organic solvents, such as acetonitrile (ACN), tetrahydrofuran (THF), formamide (FA), N-methylformamide (NMF), and N-methylacetoamide (NMA) on their substitution reactions was examined. In aqueous and aqueous-FA, -NMF, and -NMA solutions, the molybdenum or tungsten unit in the Keggin-anions was substituted with vanadium(V) ion to form V(V)-substituted polyoxometalates, while no substitution reaction occurred in aqueous-ACN and -THF solutions. It is suggested that this results from the relationship between the total anion charge and the permittivity of organic solvents.
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