Nickel Complexes Involved in the Isomerization of 2-Methyl-3-butenenitrile

The nickel(0) fragment [(P−P)Ni], where (P−P) = dcype (1,2-bis(dicyclohexylphosphino)ethane) or
dtbpe (1,2-bis(di-tert-butylphosphino)ethane), reacts with the cyano-olefins involved in the isomerization
process of 2-methyl-3-butenenitrile (2M3BN), producing the corresponding complex [(P−P)Ni(η2-C,C-cyano-olefin)]. In the case of 2M3BN and 3-pentenenitrile (3PN), the π-methylallyl metal complex was
observed in solution. All of the intermediates in the catalytic cycle were detected and characterized by
heteronuclear NMR spectroscopy; some of these were also characterized by single-crystal X-ray diffraction
studies. The initial catalytic behavior of this system for the isomerization of 2M3BN was studied also.

零价镍片段[(P−P)Ni]，其中(P−P)为dcype（1,2-双(二环己基膦基)乙烷）或dtbpe（1,2-双(二叔丁基膦基)乙烷），可与参与2-甲基-3-丁烯腈（2M3BN）异构化过程的氰基烯烃发生反应，生成相应配合物[(P−P)Ni(η²-C,C-氰基烯烃)]。针对2M3BN与3-戊烯腈（3PN）的反应体系，在溶液中观测到了π-甲基烯丙基金属配合物。催化循环中的所有中间体均通过异核核磁共振波谱法完成检测与表征，其中部分中间体还借助单晶X射线衍射研究得到了表征。本体系用于2M3BN异构化的初始催化性能也得到了研究。