Synthesis, structure, and properties of {((t)Bu(2)PC(2)H(4)P(t)Bu(2))Ni}(2)(mu-eta(2):eta(2)-C6H6) and ((t)Bu(2)PC(2)H(4)P(t)Bu(2))Ni(eta(2)-C6F6)
Synthesis, structure, and properties of {((t)Bu(2)PC(2)H(4)P(t)Bu(2))Ni}(2)(mu-eta(2):eta(2)-C6H6) and ((t)Bu(2)PC(2)H(4)P(t)Bu(2))Ni(eta(2)-C6F6)
复制标题
DOI：
10.1021/om960389s
复制
发表时间：
1996-11-12
期刊：
影响因子：
2.8
通讯作者：
Seevogel, K
中科院分区：
文献类型：
--
作者：
Bach, I;Porschke, KR;Seevogel, K
((T)Bu(2)PC(2)H(4)P(T)Bu(2))NiMe(2)在苯中热分解或((T)Bu(2)H(4)P(T)Bu(2))NiCl2在四氢呋喃/苯中用镁还原得到单核((T)Bu(2)PC(2)H(4)P(T)Bu(2))Ni(ETA(2)-C6H6)(1)和双核{(T)Bu(2)PC(2)H(4)P(t)Bu(2))Ni}(2)(mu-eta(2)：eta(2)-C6H6)(2)处于平衡状态。X-射线结构分析表明，[(T)Bu(2)Pc(2)H(4)P(T)Bu(2))Ni-0]部分与环己三烯配体的相邻C=C键形成反表面配位。固体核磁共振和溶液核磁共振分析表明，2在固体中为静态结构，在溶液中为流动结构。用C6F6取代1或2中的苯配体得到单核((T)Bu(2)Pc(2)H(4)P(T)Bu(2))Ni(ETA(2)-C6F6)(5)，其分子结构也被报道。
Thermolysis of ((t)Bu(2)PC(2)H(4)P(t)Bu(2))NiMe(2) in benzene or reduction of ((t)Bu(2)PC(2)H(4)P(t)Bu(2))NiCl2 with Mg* in THF/benzene affords a solution of mononuclear ((t)Bu(2)PC(2)H(4)P(t)Bu(2))Ni(eta(2)-C6H6) (1) and dinuclear {((t)Bu(2)PC(2)H(4)P(t)Bu(2))Ni}(2)(mu-eta(2):eta(2)-C6H6) (2) in equilibrium. Complex 2 has been isolated; the X-ray structure analysis reveals an antifacial coordination of the [((t)Bu(2)PC(2)H(4)P(t)Bu(2))Ni-0] moieties to adjacent C=C bonds of a formal cyclohexatriene ligand. According to solid-state and solution NMR the structure of 2 is static in the solid and fluxional in solution. Displacement of the benzene ligand in 1 or 2 by C6F6 affords mononuclear ((t)Bu(2)PC(2)H(4)P(t)Bu(2))Ni(eta(2)-C6F6) (5) for which the molecular structure is also reported.