Controllable Synthesis of Lindqvist Alkoxopolyoxovanadate Clusters as Heterogeneous Catalysts for Sulfoxidation of Sulfides.

Six alkoxohexavanadate-based Cu- or Co-POVs [Cu(dpa)(acac)(H2 O)]2 [V6 O13 (OMe)6 ] (1), [Cu(phen)(acac)(MeOH)]2 [V6 O13 (OMe)6 ] (2), [Co(dpa)(acac)2 ]2 [V6 O13 (OMe)6 ]·2MeOH (3), [Co(phen)(acac)2 ]2 [V6 O13 (OMe)6 ] (4), [Cu(dpa)(acac)]2 [VIV 2 VV 4 O12 (OMe)7 ] (5), and [Cu(dpa)(acac)(MeOH)]2 [VIV 2 VV 4 O11 (OMe)8 ] (6) (POV = polyoxovanadate; dpa = 2,2'-dipyridine amine; phen = 1,10-phenanthroline; acac = acetylacetone anion) have been synthesized by controlling the reaction conditions and characterized by single-crystal X-ray diffraction and powder X-ray diffraction analyses, FT-IR spectroscopy, element analyses, and X-ray photoelectron spectroscopy. In compounds 1-4 and 6, Cu or Co complexes and alkoxohexavanadate anions are assembled through electrostatic interactions. Differently, in compound 5, seven-methoxo-substituted Lindqvist-type [V6 O12 (OMe)7 ]2- are bridged to Cu complex via terminal O atoms by coordination bonds. All compounds 1-6 exhibit excellent heterogeneous catalytic performance in oxidative desulfurization and CEES ((2-chloroethyl) ethyl sulfide, a sulfur mustard simulant) abatement with H2 O2 as oxidant. Among them, the catalytic activity of 6 [conv. of DBT (dibenzothiophene) up to 100% in 6 h; conv. of CEES reached 100% and selectivity of CEESO ((2-chloroethyl) ethyl sulfoxide) up to 85% after 4 h] outperforms others and can be reused without losing its activity.