Heterogeneously Catalyzed Aerobic Oxidation of Sulfides with a BaRuO₃ Nanoperovskite

A rhombohedral BaRuO₃ nanoperovskite, which was synthesized by the sol-gel method using malic acid, could act as an efficient heterogeneous catalyst for the selective oxidation of various aromatic and aliphatic sulfides with molecular oxygen as the sole oxidant. BaRuO₃ showed much higher catalytic activities than other catalysts, including ruthenium-based perovskite oxides, under mild reaction conditions. The catalyst could be recovered by simple filtration and reused several times without obvious loss of its high catalytic performance. The catalyst effect, ¹⁸O-labeling experiments, and kinetic and mechanistic studies showed that substrate oxidation proceeds with oxygen species caused by the solid. The crystal structure of ruthenium-based oxides is crucial to control the nature of the oxygen atoms and significantly affects their oxygen transfer reactivity. Density functional theory calculations revealed that the face-sharing octahedra in BaRuO₃ likely are possible active sites in the present oxidation in sharp contrast to the corner-sharing octahedra in SrRuO₃, CaRuO₃, and RuO₂. The superior oxygen transfer ability of BaRuO₃ is also applicable to the quantitative conversion of dibenzothiophene into the corresponding sulfone and gram-scale oxidation of 4-methoxy thioanisole, in which 1.20 g (71% yield) of the analytically pure sulfoxide could be isolated.