Generation of a Ni 3 Phosphinidene Cluster from the Ni(0) Synthon, Ni(η 3 -CPh 3 ) 2
Generation of a Ni 3 Phosphinidene Cluster from the Ni(0) Synthon, Ni(η 3 -CPh 3 ) 2
复制标题
从 Ni(0) Synthon 生成 Ni 3 磷亚膦簇，Ni(η 3 -CPh 3 ) 2
DOI：
10.1021/acs.organomet.0c00095
复制
发表时间：
2020
期刊：
影响因子：
2.8
通讯作者：
Hayton, Trevor W.
中科院分区：
文献类型：
--
作者：
Touchton, Alexander J.;Wu, Guang;Hayton, Trevor W.
在-25 °C下，在THF中的NiCl 2与2当量的Li（CPh 3）反应，以中等产率形成Ni（η3-CPh 3）2（1）。配合物1进行了充分的表征，其中包括通过X射线晶体学分析。在固体状态下，1的特征是其三苯甲基配体的η 3结合模式，导致的结构使人联想到典型的Ni（II）有机金属，双（η3-烯丙基）镍。配合物1是一种优良的Ni（0）合成子。例如，1与过量的CO反应导致形成Ni（CO）4和Gomberg二聚体。类似地，1与4当量的PPh 3反应导致形成Ni（PPh 3）4（2）。据推测，其用作Ni（0）源的能力源自三苯甲基自由基的相对高的稳定性，这导致易于均裂的弱Ni-C键。最后，1与2当量的PPh 3反应，试图形成更大的Ni簇，导致以中等产率形成[Ni 3（μ3-PPh 2）2（PPh 3）3]（3）。它的磷和膦配体是由PPh 3配体的形式还原得到的。
Reaction of NiCl2in THF with 2 equiv of Li(CPh3) at −25 °C results in formation of Ni(η3-CPh3)2(1) in moderate yield. Complex1was fully characterized, which included analysis by X-ray crystallography. In the solid state,1features an η3binding mode of its trityl ligands, resulting in a structure that is reminiscent of the archetypal Ni(II) organometallic, bis(η3-allyl)nickel. In addition, complex1has proved to be an excellent Ni(0) synthon. For example, reaction of1with excess CO resulted in formation of Ni(CO)4along with Gomberg’s dimer. Similarly, reaction of1with 4 equiv of PPh3resulted in formation of Ni(PPh3)4(2). Presumably, its ability to function as a Ni(0) source is derived from the relatively high stability of the trityl radical, which results in weak Ni–C bonds that are susceptible to homolytic cleavage. Finally, reaction of1with 2 equiv of PPh3, in an attempt to form a larger Ni cluster, resulted in formation of [Ni3(μ3-PPh)(μ-PPh2)2(PPh3)3] (3) in moderate yield. Its phosphide and phosphinidene ligands are derived from the formal reduction of the PPh3ligand.