TY - JOUR
T1 - Activation of nitrous oxide and selective epoxidation of alkenes catalyzed by the manganese-substituted polyoxometalate, [MNIII2ZnW(Zn2W9 O34)2]10-
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.
UR - http://www.scopus.com/inward/record.url?scp=0037205924&partnerID=8YFLogxK
U2 - 10.1021/ja0259077
DO - 10.1021/ja0259077
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C2 - 12137519
AN - SCOPUS:0037205924
SN - 0002-7863
VL - 124
SP - 8788
EP - 8789
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 30
ER -