Abstract
A previously unknown inorganic–organic hybrid polyoxidometalate constructed from oxalate‐functionalized tetra‐ZrIV‐substituted dimeric silicotungstate, (NH4)3Na5K6[Zr4(µ3‐O)2(µ‐OH)2(ox)2(SiW10O37)2]·23H2O (1, ox = oxalate) has been synthesized under mild hydrothermal conditions and characterized by FTIR spectroscopy, elemental analysis, thermogravimetric analysis, single‐crystal and powder X‐ray diffraction. Compound 1 contains a centrosymmetric polyoxidoanion structure with two [SiW10O37]10– units sandwiching a [Zr4(µ3‐O)2(µ‐OH)2(ox)2]6+ cluster. The catalytic performances of 1 involving oxygenation reactions of thioethers by H2O2 were evaluated, showing that 1 is an excellent catalyst for the catalytic oxidation of thioethers to sulfoxides/sulfones.
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