Selective Oxidation of Sulfides to Sulfones by H2O2 Catalyzed by Fe-Substituted Sandwich Type Polyoxometalate

Abstract

Catalytic activity of the sandwich-type heteropolytungstates ([(XW 9 O 39 )M 4 ] (n-m)-, where X = P, Si, As and M = Mn, Fe, Co, Ni, Cu and Zn) in the selective oxidation of sulfides to corresponding sulfone with aqueous H 2 O 2 have been studied in acetonitrile. In comparison, different sandwich type polyoxometalates with various transition metals substituted and heteroatoms, TBAPWFe was found to be more active to each other's. This catalyst with 2.5 equivalent of hydrogen peroxide, converted various sulfides to the corresponding sulfone with 96.8-99 % selectivity at 94-97 % conversion. Furthermore, for oxidizing various sulfides to the corresponding sulfone, the sulfide function is highly reactive and other functional groups such as the double bond and hydroxyl group are tolerable. This catalyst indicated very good reusability in the oxidation reaction.

Sandwich type polyoxometalates encapsulated into the mesoporous material: synthesis, characterization and catalytic application in the selective oxidation of sulfides

“…Recently, the use of polyoxometalates was promising not only due to bifunctional redox acid catalysts properties but also due to their unusual properties such as high charges, low cost and low environmental impact. 51–53 …”

“…Recently, the use of polyoxometalates was promising not only due to bifunctional redox acid catalysts properties but also due to their unusual properties such as high charges, low cost and low environmental impact. [51][52][53] The reaction initially performed in the presence of 5.85 mmol of H 2 O 2 as an oxidant, employing 1 mmol (0.17 mL) diphenyl sulde and 50 mg of catalyst in CH 3 CN (2.5 mL) at room temperature. In order to nd the optimum reaction conditions, the effect of different reaction parameters such as the amount of catalyst, the stoichiometry of H 2 O 2 respect to the catalyst and substrate, solvent, reaction time, different dosages of POM into MIL-101 and the catalytic activities of the different catalysts on the selectivity and conversion of the oxidation reaction were studied.…”

Co(NO3)2/covalent organic framework nanoparticles for high-efficiency photocatalytic oxidation of thioanisole

“…17 However, the photocatalytic activities of these photocatalysts for the oxidation reaction of sulfides remain limited even when an additional oxidant (like O 2 ), sacrificial reagent or redox medium was used. [18][19][20] It is still a challenging task to prepare a catalyst that can achieve highefficiency oxidation of sulfide under mild conditions without using a special oxidant or sacrificial reagent.…”

“…Moreover, the photocatalytic performance of Co(NO 3 ) 2 /COF can reach or surpass those reported that were carried out under severe conditions (using O 2 , H 2 O 2 or at 50 1C). 19,20 A detailed comparison is listed in Table S3 (ESI †).…”