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Reactivity of bis(mu-hydroxo) divanadium site in gamma-H2SiV2W10O40(4-) with hydroxo compounds
Yoshinao Nakagawa1, Kazuhiro Uehara, Noritaka Mizuno
1Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
Abstract:
The reactivity of divanadium-substituted silicotungstate, gamma-H2SiV2W10O40(4-) (I), 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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