Computational study of the mechanism of cyclometalation by palladium acetate

被引：631

作者：

Davies, DL ^{[1
]}

Donald, SMA

Macgregor, SA

机构：

[1] Univ Leicester, Dept Chem, Leicester LE1 7RH, Leics, England

[2] Heriot Watt Univ, Sch Engn & Phys Sci, Edinburgh EH14 4AS, Midlothian, Scotland

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2005年 / 127卷 / 40期

关键词：

D O I：

10.1021/ja052047w

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Various mechanisms for the cyclometalation of dimethylbenzylamine by palladium acetate have been studied by DFT calculations. Contrary to previous suggestions, the rate-limiting step is the electrophilic attack of the palladium on an ortho arene C-H bond to form an agostic complex rather than a Wheland intermediate. The cyclometalated product is then formed by intramolecular deprotonation by acetate via a six-membered transition state; this step has almost no activation barrier. Copyright © 2005 American Chemical Society.

引用

页码：13754 / 13755

页数：2

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