Abstract
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.
Highlights
Selective oxidation of sulfides are important transformations in synthetic organic chemistry and active area of research in industries, as the corresponding oxidation products i.e., sulfoxides and sulfones play vital roles in the synthesis of fine chemicals, pharmaceuticals, oxotransfer reagents, biologically active molecules, and ligands of chiral catalysts [1,2,3,4,5,6,7]
Structural analysis reveals that 1 and 2 exhibit similar centrosymmetric structure, which consists of one transition metal (TM) ion sandwiched by two same subunits {Mo2 O5 (O3 PCH3 C(O)PO3 )}
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
Summary
Selective oxidation of sulfides are important transformations in synthetic organic chemistry and active area of research in industries, as the corresponding oxidation products i.e., sulfoxides and sulfones play vital roles in the synthesis of fine chemicals, pharmaceuticals, oxotransfer reagents, biologically active molecules, and ligands of chiral catalysts [1,2,3,4,5,6,7]. UHP (Hydrogen peroxide–Urea adduct) [10], NaClO [11], NaIO4 [12], and oxone [13], etc., have been developed along with the previously explored biological enzymes and transition metal based (TMs) catalysts that are being employed in the process [14,15,16,17,18]. The excellent catalysts should be highly efficient, selective, robust, and have good recyclability [20]
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