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details). By irradiation with visible light to I, the intramolecular
oxygen-to-POM(V3d/W5d) charge transfer efficiently occurs,
followed by the single electron transfer from a sulfide to the
excited POM to afford a sulfide cation radical species. The
reduced I is reoxidized by O2, and a superoxide anion radical
species is likely formed.17 Then, the reaction of the cation
radical species and the superoxide species gives the
corresponding sulfoxide.
Chem. Rev., 2016, 116, 9850; (c) H. DYOi,I:G10.-.1T0.3Z9/hCa8nCgC,0H35.-1M9A.
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In conclusion, we have successfully developed an efficient
and selective visible-light-responsive photocatalytic system
(a) K. Suzuki, F. Tang, Y. Kikukawa, K. Yamaguchi and N.
Mizuno, Angew. Chem., Int. Ed., 2014, 53, 5356; (b) K. Suzuki,
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based
on
γ-Keggin-type
divanadium-containing
phosphotungstate TBA4H[γ-PV2W10O40] (I) for the selective
oxygenation of sulfides to sulfoxides utilizing O2 as the sole
oxidant. The introduction of vanadium atoms into the
phosphotungstate skeleton and the structure of the
divanadium-containing γ-Keggin-type POM were both crucial
for its high activity. Various aromatic sulfides with both
electron-donating and electron-withdrawing functional groups,
and alkyl sulfides could be efficiently oxygenated into the
desired sulfoxides using the proposed photocatalytic system.
This work was supported in part by JSPS KAKENHI Grant
Number 17H03037.
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J. M. Cameron, S. Fujimoto, K. Kastner, R.-J. Wei, D. Robinson,
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Conflicts of interest
There are no conflicts to declare.
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those of vanadium-free TBA3H4[γ-PW10O36] (e.g., 4.23 eV;
HOMO–2 (O2p) to LUMO (W5d)). Because the crystal
structure of I has not been determined, the calculations
were performed with a model structure by removing one
proton from [H2PV2W10O40]3–.11 This assumption may cause
some discrepancies between the excitation energies
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