In Situ Ligand-Transformation-Involved Synthesis of Inorganic-Organic Hybrid Polyoxovanadates as Efficient Heterogeneous Catalysts for the Selective Oxidation of Sulfides.

By intentionally involving in situ ligand transformation in the reaction system, two inorganic-organic hybrid polyoxovanadates (POVs), [Co(HDTBA)VO] () and [Ni(HO)(DTBA)VO(OH)]·4HO (), have been synthesized by using a hydrothermal method, where the 3,5-di[1,2,4]triazol-1-ylbenzoic acid (HDTBA) ligand originated from in situ hydrolysis of 3,5-di[1,2,4]triazol-1-ylbenzonitrile in the self-assembly process. The inorganic layers [Co(VO)] containing [VO] circle clusters were linked by HDTBA ligands to yield a 3D framework structure of compound . There existed a kind of binuclear [(DTBA)VO(OH)] vanadium cluster grafted directly by two DTBA ligands through the sharing of carboxyl oxygen atoms in compound , further extended into a 2D layer by nickel centers. The investigations on the catalytic properties indicated that compounds and as heterogeneous catalysts, especially , owned satisfying catalytic performances for catalyzing the selective oxidation of sulfides to sulfoxides in the presence of -butyl hydroperoxide as an oxidant, accompanied by excellent conversion of 100% and selectivity of above 99%, providing a promising way for developing inorganic-organic hybrid POVs as effective heterogeneous catalysts for catalyzing the selective oxidation of sulfides.