THE INSERTION OF ACETYLENE INTO THE PALLADIUM CARBON BOND OF SQUARE-PLANAR PD(II) COMPLEXES - A THEORETICAL INVESTIGATION
THE INSERTION OF ACETYLENE INTO THE PALLADIUM CARBON BOND OF SQUARE-PLANAR PD(II) COMPLEXES - A THEORETICAL INVESTIGATION
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DOI：
10.1016/0022-328x(94)88164-2
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发表时间：
1994-09-20
影响因子：
2.3
通讯作者：
DEDIEU, A
中科院分区：
文献类型：
--
作者：
DEVAAL, P;DEDIEU, A
本文对[PdCl（NH_3）（CH_2）（C_2H_2）]模型体系中乙炔插入Pd-C键进行了从头算SCF、CAS-SCF和CI计算。乙炔被发现绑定相当弱的钯原子和插入与17千卡mol-1的活化势垒。过渡态的几何形状对应于乙炔的单键配位。没有中间体似乎参与反应路径，至少对于C2 H2系统。本文简要分析了一个氢原子被多个吸电子取代基取代和一个CH基团被金属有机体取代的影响，并结合等瓣C_3H_5 ~+有机体系中已知的各种异构体的几何构型研究了反应的立体化学过程。
Ab-initio SCF, CAS-SCF and CI calculations have been carried out for the acetylene insertion into the Pd-C bond of the [PdCl(NH3)(CH2)(C2H2)] Model system. The acetylene is found to bind quite weakly to the palladium atom and inserts with an activation barrier of 17 kcal mol-1. The geometry of the transition state corresponds to a monohapto coordination of the acetylene. No intermediate seems to be involved on the reaction path, at least for the C2H2 system. The effects of substitution of one hydrogen atom by more electron attracting substituents and of a CH group by a metal organic entity are briefly analysed, The stereochemical course of the reaction is also investigated in connection with the geometry of the various isomers known for the isolobal C3H5+ organic system.