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

29 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

Fingerprint

Antimony
Dehydrogenation
Alcohols
Oxidation
Crystals
Bromine
Ozone
Carboxylic Acids
Magnetic susceptibility
Aldehydes
Molecular structure
Paramagnetic resonance
X ray diffraction
Atoms
Electrons

Keywords

  • Alcohols
  • Antimony
  • Dehydrogenations
  • Molybdenum
  • Polyoxometalates

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Antimony-substituted Keggin-type polyoxomolybdates : Polar crystals and catalytic oxidative dehydrogenation of alcohols. / Khenkin, Alexander M.; Shimon, Linda J W; Neumann, Ronny.

In: European Journal of Inorganic Chemistry, No. 3, 2001, p. 789-794.

Research output: Contribution to journalArticle

@article{a1612470a2834a5897f59e4246b21801,
title = "Antimony-substituted Keggin-type polyoxomolybdates: Polar crystals and catalytic oxidative dehydrogenation of alcohols",
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.",
keywords = "Alcohols, Antimony, Dehydrogenations, Molybdenum, Polyoxometalates",
author = "Khenkin, {Alexander M.} and Shimon, {Linda J W} and Ronny Neumann",
year = "2001",
language = "English",
pages = "789--794",
journal = "European Journal of Inorganic Chemistry",
issn = "1434-1948",
publisher = "Wiley-VCH Verlag",
number = "3",

}

TY - JOUR

T1 - Antimony-substituted Keggin-type polyoxomolybdates

T2 - Polar crystals and catalytic oxidative dehydrogenation of alcohols

AU - Khenkin, Alexander M.

AU - Shimon, Linda J W

AU - Neumann, Ronny

PY - 2001

Y1 - 2001

N2 - 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.

AB - 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.

KW - Alcohols

KW - Antimony

KW - Dehydrogenations

KW - Molybdenum

KW - Polyoxometalates

UR - http://www.scopus.com/inward/record.url?scp=0035119226&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0035119226&partnerID=8YFLogxK

M3 - Article

SP - 789

EP - 794

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

SN - 1434-1948

IS - 3

ER -