Activation of nitrous oxide and selective epoxidation of alkenes catalyzed by the manganese-substituted polyoxometalate, [MNIII2ZnW(Zn2W9 O34)2]10-

Revital Ben-Daniel; Lev Weiner; Ronny Neumann

doi:10.1021/ja0259077

Activation of nitrous oxide and selective epoxidation of alkenes catalyzed by the manganese-substituted polyoxometalate, [MN^III₂ZnW(Zn₂W₉ O₃₄)₂]^10-

Revital Ben-Daniel
, Lev Weiner
, Ronny Neumann^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

109 Scopus citations

Abstract

A manganese(III)-substituted polyoxometalate of the "sandwich" structure, [Mn^III₂ZnW(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 language	English
Pages (from-to)	8788-8789
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	124
Issue number	30
DOIs	https://doi.org/10.1021/ja0259077
State	Published - 31 Jul 2002
Externally published	Yes

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title = "Activation of nitrous oxide and selective epoxidation of alkenes catalyzed by the manganese-substituted polyoxometalate, [MNIII2ZnW(Zn2W9 O34)2]10-",

abstract = "A manganese(III)-substituted polyoxometalate of the {"}sandwich{"} structure, [MnIII2ZnW(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.",

author = "Revital Ben-Daniel and Lev Weiner and Ronny Neumann",

year = "2002",

month = jul,

day = "31",

doi = "10.1021/ja0259077",

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AU - Ben-Daniel, Revital

AU - Weiner, Lev

AU - Neumann, Ronny

PY - 2002/7/31

Y1 - 2002/7/31

N2 - A manganese(III)-substituted polyoxometalate of the "sandwich" structure, [MnIII2ZnW(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.

AB - A manganese(III)-substituted polyoxometalate of the "sandwich" structure, [MnIII2ZnW(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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ER -

Activation of nitrous oxide and selective epoxidation of alkenes catalyzed by the manganese-substituted polyoxometalate, [MN^III₂ZnW(Zn₂W₉ O₃₄)₂]^10-

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