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

Qiaofei Xu; Xiaopeng Sun; Feng Hu; Rong Wan; Vikram Singh; Pengtao Ma; Jingyang Niu; Jingping Wang

doi:10.3390/ma10101173

Materials (Oct 2017)

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

Qiaofei Xu,
Xiaopeng Sun,
Feng Hu,
Rong Wan,
Vikram Singh,
Pengtao Ma,
Jingyang Niu,
Jingping Wang

Affiliations

Qiaofei Xu: Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecule and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China
Xiaopeng Sun: Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecule and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China
Feng Hu: Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecule and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China
Rong Wan: Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecule and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China
Vikram Singh: Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecule and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China
Pengtao Ma: Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecule and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China
Jingyang Niu: Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecule and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China
Jingping Wang: Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecule and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China

DOI: https://doi.org/10.3390/ma10101173
Journal volume & issue: Vol. 10, no. 10
p. 1173

Abstract

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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.

Published in Materials

ISSN: 1996-1944 (Online)
Publisher: MDPI AG
Country of publisher: Switzerland
LCC subjects: Technology: Electrical engineering. Electronics. Nuclear engineering; Technology: Engineering (General). Civil engineering (General); Science: Natural history (General): Microscopy; Science: Physics: Descriptive and experimental mechanics
Website: http://www.mdpi.com/journal/materials/

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