A bis(thiophosphinoyl)methanediide palladium complex:: Coordinated dianion or nucleophilic carbene complex?

被引：112

作者：

Cantat, T ^{[1
]}

Mézailles, N ^{[1
]}

Ricard, L ^{[1
]}

Jean, Y ^{[1
]}

Le Floch, P ^{[1
]}

机构：

[1] Ecole Polytech, CNRS, UMR 7653, DCPH,Dept Chim,Lab Heteroelements & Coordinat, F-91128 Palaiseau, France

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2004年 / 43卷 / 46期

关键词：

carbenes; density functional calculations; palladium; phosphorus; sulfides;

D O I：

10.1002/anie.200461392

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

(Chemical equation presented). A question of identity: A palladium complex featuring a carbenic S,C,S-based pincer ligand is reported (see scheme). DFT calculations show that, unlike classical carbene complexes, coordination occurs through donation from a d orbital at the metal into the empty np orbital of the carbene fragment, with the nσ orbital essentially acting as a nonbonding orbital. The complex is shown to have nucleophilic character.

引用

页码：6382 / 6385

页数：4

共 47 条

[1] Sterically hindered iminophosphorane complexes of vanadium, iron, cobalt and nickel:: a synthetic, structural and catalytic study [J].