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Isomerization of olefins and substituted olefins catalyzed by nickel complexes *Journal of Catalysis Volume 30, Issue 3, September 1973, Pages 403-408 The addition of hydrogen cyanide to α-olefins catalyzed by nickel(0) complexes Brian W. Taylor and Harold E. Swift Journal of Catalysis Volume 26, Issue 2, August 1972, Pages 254-260 |
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djxun5896
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3楼2010-03-07 09:36:21
wanghuixxx
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摘要
| The catalytic activity of several Ni (diphosphine)2/acid homogeneous systems (acid = HCN, CF3COOH, CCl3COOH, and H2SO4) in the double bond and cistrans isomerizations of olefins has been tested with the following compounds: pentene-1, cis-pentene-2, trans-pentene-2, allyl benzene, allyl cyanide, allyl alcohol. The catalytic efficiency of the Ni(diphosphine)2/acid systems depends markedly on the nature both of the diphosphine and of the acid employed. When the diphosphine is 1,4-bis(diphenylphosphino)butane and ACID = HCN a particularly efficient catalytic system is formed in situ and only in the case of the allyl cyanide is the isomerization limited. During the isomerization of pentene-1, the stereoselectivity in the formation of the cis-2 and trans-2 isomers is quite dependent on the nature of the cocatalyst. It is proposed that a σ-alkyl mechanism is operating in the Ni(O)/CF3COOH system and a π-allyl one in the case of Ni(O)/HCN. |
2楼2010-03-06 19:23:34