Cleavage of carbon-carbon bonds in alkyl cyanides using nickel(0)

被引:146
作者
García, JJ
Arévalo, A
Brunkan, NM
Jones, WD
机构
[1] Univ Nacl Autonoma Mexico, Fac Quim, Mexico City 04510, DF, Mexico
[2] Univ Rochester, Dept Chem, Rochester, NY 14627 USA
关键词
D O I
10.1021/om049700t
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The reaction of the complex [(dippe)NiH](2) (1) with a variety of alkyl cyanides afforded nickel(0) compounds of the type [(dippe)Ni(eta(2)-RCN)], where R, = Me, Et, Pr, Pr-i, Bu-t, cyclopropyl, cyclobutyl, adamantyl (2-9, respectively). When compounds 2-9 were warmed to yield oxidative addition products, the thermal reaction proceeded only in the case of 2 to produce [(dippe)Ni(Me)(CN)](10). Photochemical activation did produce oxidative addition products from compounds 2-8, which rapidly evolved to the beta-elimination products of the organic moiety in most cases and to the formation of [(dippe)Ni(CN)(2)] (11). Reaction of 1 with acetonitrile in the presence of BPh3 gives [(dippe)Ni(eta(2)-MeCNBPh3)](12), which does not undergo thermal C-CN cleavage upon heating. X-ray crystal structures are reported for 10-12.
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页码:3997 / 4002
页数:6
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