On the Stability of a POC<sub>sp3</sub>OP-Type Pincer Ligand in Nickel(II) Complexes
作者:Jingjun Hao、Berline Mougang-Soumé、Boris Vabre、Davit Zargarian
DOI:10.1002/anie.201310386
日期:2014.3.17
We describe the results of a study on the stabilities of pincer‐type nickel complexes relevant to catalytic hydroalkoxylation and hydroamination of olefins, CC and CX couplings, and fluorination of alkyl halides. Complexes [(POCsp3OP)NiX] are stable for X=OSiMe3, OMes (Mes=1,3,5‐Me3C6H2), NPh2, and CCH, whereas the O(tBu) and N(SiMe3)2 derivatives decompose readily. The phenylacetylide derivative
我们描述在钳型镍的稳定性进行研究的结果,复合物相关的催化hydroalkoxylation和烯烃的加氢胺化,C C和C X联轴器,和烷基卤化物的氟化。配合物[(POC SP3 OP)NIX]是稳定X = OSiMe 3,OMes(MES = 1,3,5-ME 3 c ^ 6 ħ 2),NPH 2,和CC H,而O(吨丁基) N(SiMe 3)2衍生物容易分解。的苯基乙炔衍生物变换逐渐进入零价物种顺- [κ P,κ Ç,κ C' - (我镨2 POCH 2 CHCH 2)} 镍η 2,κ Ç,κ C' - (我镨2 P(O)CCPh)}]。同样地,尝试制备[(POC SP3 OP)NIF〕得到代替两性离子的三核物种[(η 3 -烯丙基)镍} 2 - μ,κ P,κ ø - (我镨2 PO)4的Ni}] 。这两种复合物的表征提供了分解过程的具体实例,这些分解过程可以通过简便的C来拆除POC