Aryl carbon-chlorine (Ar-Cl) and aryl carbon-fluorine (Ar-F) bond cleavages by rhodium porphyrins

被引：15

作者：

Qian, Ying Ying ^{[1
]}

Lee, Man Ho ^{[1
]}

Yang, Wu ^{[1
]}

Chan, Kin Shing ^{[1
]}

机构：

[1] Chinese Univ Hong Kong, Dept Chem, Shatin, Hong Kong, Peoples R China

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2015年 / 791卷

关键词：

Rhodium porphyrin; Carbon-chlorine bond activation; Carbon-fluorine bond activation; OXIDATIVE ADDITION; AROMATIC HALIDES; COMPLEXES; ACTIVATION; MECHANISM; HYDRODEHALOGENATION; CHLOROBENZENE; REACTIVITY; CHEMISTRY; LIGANDS;

D O I：

10.1016/j.jorganchem.2015.05.039

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Aryl carbon-chlorine (Ar-Cl) bond cleavage has been achieved with rhodium(III) tetrakis-4-tolylporphyrin chloride (Rh(ttp)Cl) to give Rh(ttp)Ar. For 4-chlorofluorobenzene, the aryl carbon-fluorine (Ar-F) bond cleavage competes with the ArCl bond cleavage. Mechanistic investigations show that the Ar-Cl bond cleavage goes through metalloradical ipso-substitution mechanism, while the ArF bond cleavage goes through nucleophilic aromatic substitution. The selectivity of the Ar-F or Ar-Cl bond cleavage can be controlled by tuning the temperature and substrate concentration. (C) 2015 Elsevier B.V. All rights reserved.

引用

页码：82 / 89

页数：8

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