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

32 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

ASJC Scopus subject areas

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

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