Journal
INORGANIC CHEMISTRY
Volume 44, Issue 24, Pages 9068-9075Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic051163x
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The reactivity of divanadium-substituted silicotungstate, gamma-H2SiV2W10O404- (1), with hydroxo compounds of alcohols, carboxylic acids, and water is reported. The reaction of the bis(mu-hydroxo) divanadium site in I with primary alcohols and formic acid smoothly proceeds to form corresponding monoesters and monoformate, respectively, and the crystal structures of the monomethyl and monoethyl esters and the monoformate of I are determined. The oxygen exchange between the hydroxo group and water proceeds easily. On the other hand, bulky compounds of 2-propanol, tert-butyl alcohol, and acetic acid hardly react with the bis(mu-hydroxo) divanadium site (equilibrium constant < 0.01) because of the steric crowding between the methyl groups and the polyoxometalate framework.
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