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Two New Sandwich-Type Polyoxomolybdates Functionalized with Diphosphonates: Efficient and Selective Oxidation of Sulfides to Sulfones

Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecule and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China
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Materials 2017, 10(10), 1173; https://doi.org/10.3390/ma10101173
Received: 5 September 2017 / Revised: 30 September 2017 / Accepted: 7 October 2017 / Published: 13 October 2017
Two sandwich-type polyoxomolybdates Na8[MO2{Mo2O5(O3PCH3C(O)PO3)}2] (M = Ni2+ (1); Co2+ (2)) were synthesized by one-pot reaction of Na2HPMo12O40·14H2O, 1-hydroxy ethidene diphosphonic acid (HEDP=HOC(CH3)(PO3H2)2), and (1) NiCl2/CoCl2 (2). Compounds 1 and 2 were characterized by single crystal X-ray analysis, X-ray powder diffraction (XRPD), IR spectroscopy, 31P NMR spectra, UV-vis spectroscopy, and thermogravimetric analyses (TGA). Structural analysis reveals that 1 and 2 exhibit similar centrosymmetric structure, which consists of one transition metal (TM) ion sandwiched by two same subunits {Mo2O5(O3PCH3C(O)PO3)}. The clusters 1 and 2 show efficient catalytic activities for oxidation of thioanisole. Moreover, they are catalytically selective for oxidizing thioanisole. Both resuable polyoxomolybdates 1 and 2 catalysts show good thermo- and hydrolytic stability. It is noted that compound 1 shows outstanding catalytic activity for oxidation of various sulfides to corresponding sulfones with 93–100% selectivity at 97–100% conversion in one hour under mild conditions, which is potentially valuable to the removal of organic sulfides. View Full-Text
Keywords: polyoxomolybdates; catalyst; oxidation of sulfides polyoxomolybdates; catalyst; oxidation of sulfides
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MDPI and ACS Style

Xu, Q.; Sun, X.; Hu, F.; Wan, R.; Singh, V.; Ma, P.; Niu, J.; Wang, J. Two New Sandwich-Type Polyoxomolybdates Functionalized with Diphosphonates: Efficient and Selective Oxidation of Sulfides to Sulfones. Materials 2017, 10, 1173.

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