Catalytic Hydrodefluorination of Pentafluorobenzene by [Ru(NHC)-(PPh3)2(CO)H2]: A Nucleophilic Attack by a Metal-Bound Hydride Ligand Explains an Unusual ortho-Regioselectivity

被引：63

作者：

Panetier, Julien A. ^{[1
]}

Macgregor, Stuart A. ^{[1
]}

Whittlesey, Michael K. ^{[2
]}

机构：

[1] Heriot Watt Univ, Sch EPS, Edinburgh EH14 4AS, Midlothian, Scotland

[2] Univ Bath, Dept Chem, Bath BA2 7AY, Avon, England

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2011年 / 50卷 / 12期

基金：

英国工程与自然科学研究理事会;

关键词：

C-F activation; density functional calculations; fluoroarenes; hydrodefluorination; ruthenium; C-F ACTIVATION; FLUORINE BOND ACTIVATION; COMPLEXES; RHODIUM;

D O I：

10.1002/anie.201006789

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Secret revealed: The mechanism of the catalytic hydrodefluorination of pentafluorobenzene by the N-heterocyclic carbene complex [Ru(IMes)(PPh 3)2(CO)H2] has been investigated by DFT calculations. Two sets of novel pathways (concerted and stepwise) have been defined whereby a Ru H ligand can act as a nucleophile at the fluoroarene substrate. The most accessible pathway equates to the formation of 1,2,3,4-C6F4H2 and thus accounts for the unusual regioselectivity that is observed experimentally (see scheme). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

引用

页码：2783 / 2786

页数：4