Activation of nitrous oxide and selective epoxidation of alkenes catalyzed by the manganese-substituted polyoxometalate, [MNIII 2ZnW(Zn2W9 O34)2]10-

Revital Ben-Daniel, Lev Weiner, Ronny Neumann

Research output: Contribution to journalArticle

95 Citations (Scopus)

Abstract

A manganese(III)-substituted polyoxometalate of the "sandwich" structure, [MnIII 2ZnW(ZnW9O34)2]10-, catalyzed the highly selective (>99.9%) epoxidation of alkenes, such as 1-octene, 2-octene, and cyclohexene with nitrous oxide. Reactions occurred in homogeneous media at 150 °C under 1 atm N2O. The epoxidation had a linear reaction profile; turnover frequencies of 0.5-1.4 h-1 were measured. The reactions were also stereoselective; for example, cis-stilbene gave cis-stilbene oxide. From ESR spectroscopy, it was shown that a Mn(II) octahedral species is reversibly formed by reaction between the original Mn(III) polyoxometalate and N2O. Therefore, it would appear that a Mn(V)-oxo active species is not formed; it is possible that the activation of nitrous oxide was by its oxidation by the Mn(III) polyoxometalate.

Original languageEnglish
Pages (from-to)8788-8789
Number of pages2
JournalJournal of the American Chemical Society
Volume124
Issue number30
DOIs
Publication statusPublished - Jul 31 2002

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Epoxidation
Nitrous Oxide
Alkenes
Manganese
Olefins
Chemical activation
Oxides
Stilbenes
Sandwich structures
Paramagnetic resonance
Spectrum Analysis
Spectroscopy
Oxidation
polyoxometalate I

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Activation of nitrous oxide and selective epoxidation of alkenes catalyzed by the manganese-substituted polyoxometalate, [MNIII 2ZnW(Zn2W9 O34)2]10- . / Ben-Daniel, Revital; Weiner, Lev; Neumann, Ronny.

In: Journal of the American Chemical Society, Vol. 124, No. 30, 31.07.2002, p. 8788-8789.

Research output: Contribution to journalArticle

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abstract = "A manganese(III)-substituted polyoxometalate of the {"}sandwich{"} structure, [MnIII 2ZnW(ZnW9O34)2]10-, catalyzed the highly selective (>99.9{\%}) epoxidation of alkenes, such as 1-octene, 2-octene, and cyclohexene with nitrous oxide. Reactions occurred in homogeneous media at 150 °C under 1 atm N2O. The epoxidation had a linear reaction profile; turnover frequencies of 0.5-1.4 h-1 were measured. The reactions were also stereoselective; for example, cis-stilbene gave cis-stilbene oxide. From ESR spectroscopy, it was shown that a Mn(II) octahedral species is reversibly formed by reaction between the original Mn(III) polyoxometalate and N2O. Therefore, it would appear that a Mn(V)-oxo active species is not formed; it is possible that the activation of nitrous oxide was by its oxidation by the Mn(III) polyoxometalate.",
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