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

Alexander M. Khenkin, Gregory Leitus, Ronny Neumann

Research output: Contribution to journalArticle

84 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

    Fingerprint

ASJC Scopus subject areas

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

Cite this