Nickel and Oxo-Vanadium Complexes of Adenine on Modified Mesoporous MCM-41 as Chemoselective, Efficient, and Reusable Catalysts in the Oxidation of Sulfides and Oxidative Coupling of Thiols.

Abstract

A highly efficient superior catalyst of Ni (II) and VO (IV) metal complexes supported on MCM-41 has been synthesized and developed for chemoselective oxidation of sulfides to sulfoxides and oxidative coupling of thiols to their corresponding disulfides using H2O2 as a green and efficient procedure. All sulfoxides and disulfides were obtained in short reaction times with excellent yields. The over-oxidation of sulfides or thiols was not observed and all products were synthesized in high purity. These catalysts could be recovered and reused several times without any significant loss in their catalytic activity. Compared to the old catalysts in the literature, these catalysts showed better activity and selectivity for the synthesis of sulfoxide and disulfide derivatives, which shows the novelty of this work. At first, the mesoporous MCM-41 was synthesized, and further, its surface was modified by (3-chloropropyl)-triethoxysilane (CPTES). Then, the modified MCM-41 (nPrCl-MCM- 41) was functionalized by adenine. In the next step, the functionalized MCM-41 (6AP-MCM- 41) was used as support for the immobilization of nickel and oxo-vanadium as final catalysts (Ni-6AP-MCM-41 or VO-6AP-MCM-41). The structure and properties of these catalysts have been identified by XRD, SEM, TGA, FT-IR, and AAS spectral analyses. These catalysts were used in the chemoselective oxidation of sulfides and oxidative coupling of thiols. These complexes catalyzed all reactions well at room temperature. According to the results obtained, the hydroxyl groups of some derivatives, including 2-(methylthio) ethanol or 2,2-(phenylthio) ethanol, remained unchanged during the reaction. The method has been found to possess the advantages of low cost, high efficiency, high yields, recovery, and reusability for several runs without significant loss in the catalytic activity.