meso-Ni2Cl4(P4-Ph) complexes based on the much stronger chelating tetraphosphine ligand with 1,2-phenylene chelate rings also react readily with water to form a hydroxide-bridged bimetallic complex, but further reaction and fragmentation chemistry is inhibited by the much stronger chelate effect present. [Ni2(μ-OH)Cl2(meso-P4-Ph)]+ has been crystallographically and spectroscopically characterized along with some
摘要NMR研究表明,rac-和meso-Ni2Cl4(P4),P4 =(Et2PCH2CH2)(Ph)PC
H2P(Ph)(CH2C Et2),双
金属配合物容易在不同的有机溶剂(
丙酮,
乙腈,
DMSO)中与
水反应解离
氯化物,最有可能形成氢氧化物桥联的双
金属配合物[Ni2(μ-OH)Cl2(P4)] +。内消旋双
金属络合物非常容易与外部螯合的膦之一发生离解,从而导致
镍原子之一的损失。四
膦配体与剩余的
镍中心配位形成[NiCl(κ3-meso-P4)] +,然后可以与
氯化物反应生成NiCl2(κ2-meso-P4)。然后,这些单
金属配合物的内消旋非对映异构体相互反应,形成双P4配位的双
金属配合物[Ni2(μ-Cl)(meso-P4)2] 3+,其晶体结构已得到表征。尽管在两个
镍中心周围存在四个
双膦(
乙烷)螯合物,[Ni2(μ-Cl)(meso-P4)2] 3+容易碎裂,并且可以通过加热转化回前体