Antimony-substituted Keggin-type polyoxomolybdates: Polar crystals and catalytic oxidative dehydrogenation of alcohols

Alexander M. Khenkin, Linda J W Shimon, Ronny Neumann

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

An antimony-substituted polyoxomolybdate, [PSbIII(H2O) -Mo11O39]4-, of the α-Keggin structure, has been synthesized. Although the molecular structure is typical, we have found from the analysis of the X-ray diffraction data that the crystal is anisotropic with alignment of the molecular units so that the substituted antimony atoms are all directed along the polar c axis and on the same side of the molecular unit. UV/Vis, ESR and magnetic susceptibility data support a formulation of [PSbIII(H2O)Mo11O39]4- whereby there is partial electron delocalization with some formation (10-20%) of MoV. Oxidation of [PSbIII(H2O)Mo11O39]4- with ozone or bromine yields the oxidized species [PSbV(O)Mo11O39]4- and [PSbV(Br)Mo11O39]3-. In the anaerobic oxydehydrogenation of alcohols, [PSbV(O)Mo11O39]4- is more active than [PSbV(Br)Mo11O39]3-. Catalytic aerobic oxidation of benzylic alcohols to aldehydes was also possible with no over-oxidation and formation of carboxylic̈ acids.

Original languageEnglish
Pages (from-to)789-794
Number of pages6
JournalEuropean Journal of Inorganic Chemistry
Issue number3
Publication statusPublished - 2001

Keywords

  • Alcohols
  • Antimony
  • Dehydrogenations
  • Molybdenum
  • Polyoxometalates

ASJC Scopus subject areas

  • Inorganic Chemistry

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