【摘 要】
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The activation and functionalization of N-H bond by transition-metal complexes has been widely applied in modem synthetic organic chemistry.Besides precious metal complexes, more and more inexpensive
【机 构】
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山东大学化学与化工学院 济南250199
【出 处】
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中国化学会全国第十一届有机合成化学学术研讨会
论文部分内容阅读
The activation and functionalization of N-H bond by transition-metal complexes has been widely applied in modem synthetic organic chemistry.Besides precious metal complexes, more and more inexpensive and eco-friendly metal complexes such as iron, cobalt and nickel complexes are utilized in the activation of N-H bond.In our earlier work, the Nsp3-H bonds contained in benzarnide and 2-aminobenzophenone were successfully activated by electron-rich Co and Ni complexes.1,2 As a continuation, the reactions of a series of arylmethanimines with NiC1Me(PMe3)2 and NiMe2(PMe3)3 are discussed in this paper.The reactions of NiC1Me(PMe3)2 with fluorinated imine ligands 1 and 2 gave rise to complexes 3 and 4 as five-coordinated trigonal bipyramids (Scheme 1).The imine ligands interacted with the Ni centre via n-coordination and N-H bond was not cleavaged sufficiently.Due to the influence of steric hindrance, imine ligand 5 could not react with NiCIMe(PMe3)2.The activation of N-H bond was also realized from the reactions of NiMe2(PMe3)3 with imine ligangs 1, 2, 5, 6 and 7.As a result, four-coordinated binuclear nickel complexes 8, 9, 10, 11 and 12 were obtained in the yields of 56 ～ 71％ (Scheme 2).The structures showed that two nickel atoms were bridged by the N atom.
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