Mechanism of carbon-fluorine bond activation by (C5Me5)Rh(PMe3)H-2

被引：142

作者：

Edelbach, BL ^{[1
]}

Jones, WD ^{[1
]}

机构：

[1] UNIV ROCHESTER,DEPT CHEM,ROCHESTER,NY 14627

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1997年 / 119卷 / 33期

关键词：

D O I：

10.1021/ja970723r

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The complex Cp*Rh(PMe3)H-2 (Cp* = C5Me5) reacts with C6F6, C6F5H, C12F10 or C10F8 in pyridine or 1:1 pyridine/benzene to give the C-F cleavage products Cp*Rh(PMe3)(aryl(F))H in high yield. Kinetic studies reveal that the reaction has autocatalytic character, and fluoride ion is shown to be responsible for the catalysis. The anion [Cp*Rh(PMe3)H](-) reacts rapidly with C12F10 or C10F8 to give the same C-F cleavage products as Cp*Rh(PMe3)H-2. A mechanism initiated by deprotonation of Cp*Rh(PMe3)H-2 followed by nucleophilic attack of the resulting anion on the polyfluoroaromatic with subsequent loss of fluoride is proposed. The fluoride ion continues the cycle by deprotonating Cp*Rh(PMe3)H-2.

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页码：7734 / 7742

页数：9

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