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Title
Japanese:Sulfoxidation with hydrogen peroxide catalyzed by [SeO4{WO(O2)2}2]2-. 
English:Sulfoxidation with hydrogen peroxide catalyzed by [SeO4{WO(O2)2}2]2-. 
Author
Japanese: Keigo Kamata, Tomohisa Hirano, Ryo Ishimoto, Noritaka. Mizuno.  
English: Keigo Kamata, Tomohisa Hirano, Ryo Ishimoto, Noritaka. Mizuno.  
Language English 
Journal/Book name
Japanese:Dalton Transactions 
English:Dalton Transactions 
Volume, Number, Page Vol. 39    No. 23    pp. 5509-5518
Published date 2010 
Publisher
Japanese:Royal Society of Chemistry 
English:Royal Society of Chemistry 
Conference name
Japanese: 
English: 
Conference site
Japanese: 
English: 
DOI https://doi.org/10.1039/c002318c
Abstract The selenium-contg. dinuclear peroxotungstate, [(n-C4H9)4N]2[SeO4{WO(O2)2}2] (I), acts as a homogeneous catalyst for the selective oxidn. of various kinds of cyclic mono- and disulfides with 30% aq. H2O2. The cyclic disulfides were selectively oxidized to the corresponding monosulfoxides with one equiv. of H2O2 with respect to the sulfides. In the presence of two equiv. of H2O2, the oxidn. of dibenzothiophene gave the corresponding sulfone in 98% yield under the mild conditions. The neg. Hammett ﾏ�value (-0.62) for the competitive oxidn. of p-substituted thioanisoles and the low XSO (XSO = (nucleophilic oxidn.)/(total oxidn.)) value of 0.14 for the I-catalyzed oxidn. of thianthrene 5-oxide (SSO) revealed that I is a strong electrophilic oxidant. The reactivities of the di- and tetranuclear peroxotungstates with XO4n- ligands (X = Se(vi), As(v), P(v), S(vi), and Si(iv)) were strongly dependent on the kinds of hetero atoms. The reaction rates for the sulfoxidn. decreased with an increase in the XSO values and a peroxotungstate with a stronger electrophilicity was more active for the sulfoxidn. The kinetic and mechanistic investigations showed that the electrophilic attack of the peroxo oxygen at the sulfur atom is a key step in the sulfoxidn. The computational investigation supported the high chemoselectivitiy for the sulfoxidn. of diallyl sulfide. [on SciFinder(R)]

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