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A Crown‐Shaped Ru‐Substituted Arsenotungstate for Selective Oxidation of Sulfides with Hydrogen Peroxide
Author(s) -
Han Mengdan,
Niu Yanjun,
Wan Rong,
Xu Qiaofei,
Lu Jingkun,
Ma Pengtao,
Zhang Chao,
Niu Jingyang,
Wang Jingping
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201800748
Subject(s) - hydrogen peroxide , selectivity , acetonitrile , chemistry , polyoxometalate , catalysis , ruthenium , ligand (biochemistry) , lacunary function , medicinal chemistry , methanol , hydrogen bond , peroxide , inorganic chemistry , photochemistry , organic chemistry , molecule , biochemistry , receptor , mathematics , pure mathematics
An acetate‐bridged Ru‐substituted arsenotungstate [H 2 N(CH 3 ) 2 ] 14 [As 4 W 40 O 140 {Ru 2 (CH 3 COO)} 2 ] ⋅ 22 H 2 O ( 1 ) has been synthesized and structurally characterized. Four Ru atoms occupy the respective lacunary S2 sites of the crown‐shaped polyanion [As 4 W 40 O 140 ] 28− , and each Ru atom is coordinated by one As atom and five μ 2 ‐O atoms, comprising four from the S2 site and one from the acetate ligand. To the best of our knowledge, this coordination of the Ru atom, with an Ru−As bond length of 2.377(3)–2.387(3) Å, is unprecedented in polyoxometalate (POM) chemistry. Notably, 1 exhibits high efficiency, excellent selectivity, and good recyclability for the oxidation of sulfides with hydrogen peroxide (H 2 O 2 ). Catalytic oxidation of various sulfides in the presence of 1 gives superior conversion and selectivity for sulfones in acetonitrile, whereas sulfoxides are obtained in methanol.