Theoretical study of the semihydrogenation of alkynes catalyzed by Pd(0) complexes: Is a zwitterionic pathway possible?

被引：20

作者：

Dedieu, A

Humbel, S

Elsevier, C

Grauffel, C

机构：

[1] Univ Strasbourg 1, CNRS, UMR 7551, Lab Chim Quant, F-67000 Strasbourg, France

[2] Fac Sci & Tech St Jerome, ENSSPICAM, UMR 6516, F-13397 Marseille 20, France

[3] Univ Amsterdam, Inst Mol Chem Coordinat & Organomet Chem, NL-1018 WV Amsterdam, Netherlands

来源：

THEORETICAL CHEMISTRY ACCOUNTS | 2004年 / 112卷 / 04期

关键词：

H-2 heterolytic splitting; density functional theory calculations; homogeneous catalysis; hydrogenation;

D O I：

10.1007/s00214-004-0588-x

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Density functional theory B3LYP calculations have been carried out for the Pd(diimine)(C2H2)+H-2-->Pd(diimine)(C2H4) reaction, which is the key reaction in the semihydrogenation of alkynes homogeneously catalyzed by (diimine)palladium(0) complexes. The results show that a H-2 heterolytic addition across one Pd-N bond opens a feasible zwitterionic pathway for the catalytic process, and accounts for the pairwise transfer of the two hydrogen atoms inferred from parahydrogen induced polarization NMR experiments.

引用

页码：305 / 312

页数：8

共 42 条

[1] Ab initio study of the structural, energetic, bonding, and IR spectroscopic properties of complexes with dihydrogen bonds [J].