Electron transfer-oxygen transfer oxygenation of sulfides catalyzed by the H5PV2Mo10O40 polyoxometalate

Alexander M. Khenkin, Gregory Leitus, Ronny Neumann

Research output: Contribution to journalArticle

72 Citations (Scopus)

Abstract

The oxygenation of sulfides to the corresponding sulfoxides catalyzed by H5PV2Mo10O40 and other acidic vanadomolybdates has been shown to proceed by a low-temperature electron transfer-oxygen transfer (ET-OT) mechanism. First, a sulfide reacts with H 5PV2Mo10O40 to yield a cation radical-reduced polyoxometalate ion pair, R2 , H5PVIVVVMo10O40, that was identified by UV-vis spectroscopy (absorptions at 650 and 887 nm for PhSMe and H5PVIVVVMo 10O40) and EPR spectroscopy (quintet at g = 2.0079, A = 1.34 G for the thianthrene cation radical and the typical eight-line spectrum for VIV). Next, a precipitate is formed that shows by IR the incipient formation of the sulfoxide and by EPR a VO2+ moiety supported on the polyoxometalate. Dissolution of this precipitate releases the sulfoxide product. ET-OT oxidation of diethylsulfide yielded crystals containing [V(O)(OSEt2)x(solv)5-x]2+ cations and polyoxometalate anions. Under aerobic conditions, catalytic cycles can be realized with formation of mostly sulfoxide (90%) but also some disulfide (10%) via carbon-sulfide bond cleavage.

Original languageEnglish
Pages (from-to)11446-11448
Number of pages3
JournalJournal of the American Chemical Society
Volume132
Issue number33
DOIs
Publication statusPublished - Aug 25 2010

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sulfoxide
Oxygenation
Sulfides
Cations
Positive ions
Electrons
Oxygen
Paramagnetic resonance
Precipitates
Spectrum Analysis
Sulfoxides
Electron temperature
Ultraviolet spectroscopy
Disulfides
Anions
Dissolution
Negative ions
Spectroscopy
Ions
Oxidation

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Electron transfer-oxygen transfer oxygenation of sulfides catalyzed by the H5PV2Mo10O40 polyoxometalate. / Khenkin, Alexander M.; Leitus, Gregory; Neumann, Ronny.

In: Journal of the American Chemical Society, Vol. 132, No. 33, 25.08.2010, p. 11446-11448.

Research output: Contribution to journalArticle

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abstract = "The oxygenation of sulfides to the corresponding sulfoxides catalyzed by H5PV2Mo10O40 and other acidic vanadomolybdates has been shown to proceed by a low-temperature electron transfer-oxygen transfer (ET-OT) mechanism. First, a sulfide reacts with H 5PV2Mo10O40 to yield a cation radical-reduced polyoxometalate ion pair, R2 +·, H5PVIVVVMo10O40, that was identified by UV-vis spectroscopy (absorptions at 650 and 887 nm for PhSMe +· and H5PVIVVVMo 10O40) and EPR spectroscopy (quintet at g = 2.0079, A = 1.34 G for the thianthrene cation radical and the typical eight-line spectrum for VIV). Next, a precipitate is formed that shows by IR the incipient formation of the sulfoxide and by EPR a VO2+ moiety supported on the polyoxometalate. Dissolution of this precipitate releases the sulfoxide product. ET-OT oxidation of diethylsulfide yielded crystals containing [V(O)(OSEt2)x(solv)5-x]2+ cations and polyoxometalate anions. Under aerobic conditions, catalytic cycles can be realized with formation of mostly sulfoxide (90{\%}) but also some disulfide (10{\%}) via carbon-sulfide bond cleavage.",
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