Polyoxometalate-catalyzed insertion of oxygen from O2 into tin-alkyl bonds

Alexander M. Khenkin, Irena Efremenko, Jan M L Martin, Ronny Neumann

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

The polyoxometalate H5PV2Mo10O 40 mediates the insertion of an oxygen atom from H5PV 2Mo10O40 into the tin-carbon bond of n-Bu 4Sn through its activation by electron transfer to yield 1-butanol and (n-Bu3Sn)2O. The reaction is initiated by electron transfer from n-Bu4Sn to H5PVV 2Mo10O40 to yield the ion pair n-Bu 4Sn•+-H5PVIVV VMo10O40. The H5PV IVVVMo10O40 moiety was identified by UV-vis and EPR. DFT calculations show that n-Bu4Sn •+-H5PVIVVVMo 10O40 is relatively unstable and forms more stable Bu + and Bu3Sn+ cations coordinated to the polyoxometalate, which were also identified by ESI-MS. Products are released at higher temperatures. In the presence of molecular oxygen as the terminal oxidant the reaction is catalytic.

Original languageEnglish
Pages (from-to)19304-19310
Number of pages7
JournalJournal of the American Chemical Society
Volume135
Issue number51
DOIs
Publication statusPublished - Dec 26 2013

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Tin
Electrons
Oxygen
1-Butanol
Molecular oxygen
Butenes
Oxidants
Discrete Fourier transforms
Paramagnetic resonance
Cations
Carbon
Positive ions
Chemical activation
Ions
Atoms
Temperature
polyoxometalate I

ASJC Scopus subject areas

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

Cite this

Polyoxometalate-catalyzed insertion of oxygen from O2 into tin-alkyl bonds. / Khenkin, Alexander M.; Efremenko, Irena; Martin, Jan M L; Neumann, Ronny.

In: Journal of the American Chemical Society, Vol. 135, No. 51, 26.12.2013, p. 19304-19310.

Research output: Contribution to journalArticle

Khenkin, Alexander M. ; Efremenko, Irena ; Martin, Jan M L ; Neumann, Ronny. / Polyoxometalate-catalyzed insertion of oxygen from O2 into tin-alkyl bonds. In: Journal of the American Chemical Society. 2013 ; Vol. 135, No. 51. pp. 19304-19310.
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