A β-diketiminato-nickel(II) synthon for nickel(I) complexes
A β-diketiminato-nickel(II) synthon for nickel(I) complexes
复制标题
DOI：
10.1021/om050544f
复制
发表时间：
2005-11-21
期刊：
影响因子：
2.8
通讯作者：
Stephan, DW
中科院分区：
文献类型：
--
作者：
Bai, GC;Wei, PR;Stephan, DW
在甲苯中与K/Na合金反应还原了化合物（Nacnac）Ni(mu-Br)(2)Li(THF)(2) (Nacnac = (HC(CMeNC6H3(i-Pr)（2))(2)）。所得产物[(Nacnac)Ni)(2)(mu-eta(3):eta(3)-C(6)H（5)MeA(1)）被表征为Ni（II）物质，其中电子从Ni转移到甲苯。该化合物与多种供体反应生成Ni(I)配合物。例如，化合物1与膦、腈、乙炔、烯烃和酮反应生成顺磁性配合物（Nacnac）Ni(PCy3)(2)、（Nacnac）Ni(Ph2PCH2-PPh2)(3)、（Nacnac）Ni(NCPh)(4)、（Nacnac）Ni(eta(2)- me3siccsime3)-(6)、（Nacnac）Ni(eta(2)- h2ccph2)(7)和（Nacnac）Ni(OCPh2)(8)。在1与二甲基氟烯的相关反应中，电子从金属到配体的转移可以通过形成双金属物质[(Nacnac)Ni(eta(3):eta(3)-C5H4CMe2))(2)](9)来证明。报道了1-9的晶体结构，并讨论了这些产物的键合和反应性。
The compound (Nacnac)Ni(mu-Br)(2)Li(THF)(2) (Nacnac = (HC(CMeNC6H3(i-Pr)(2))(2)) was reduced by reaction with K/Na alloy in toluene. The resulting product [((Nacnac)Ni)(2)(mu-eta(3):eta(3)-C(6)H(5)MeA (1) was characterized and is best described as a Ni(II) species in which electron transfer from Ni to toluene has occurred. This compound reacts with a variety of donors to give Ni(I) complexes. For example, compound 1 reacts with phosphines, nitriles, acetylenes, olefins, and ketones to give the paramagnetic complexes (Nacnac)Ni(PCy3) (2), (Nacnac)Ni(Ph2PCH2-PPh2) (3), (Nacnac)Ni(NCPh) (4), (Nacnac)Ni(eta(2)-PhCCPh) (5), (Nacnac)Ni(eta(2)-Me3SiCCSiMe3)-(6), (Nacnac)Ni(eta(2)-H2CCPh2) (7), and (Nacnac)Ni(OCPh2) (8). In the related reaction of 1 with dimethylfulvene, electron transfer from metal to ligand is evidenced by the formation of the dimetallic species [((Nacnac)Ni(eta(3):eta(3)-C5H4CMe2))(2)] (9). The crystal structures of 1-9 are reported, and the bonding and reactivity of these products are discussed.