Mechanism of C-F Reductive Elimination from Palladium(IV) Fluorides

被引：241

作者：

Furuya, Takeru ^{[1
]}

Benitez, Diego ^{[2
]}

Tkatchouk, Ekaterina ^{[2
]}

Strom, Alexandra E. ^{[1
]}

Tang, Pingping ^{[1
]}

Goddard, William A., III ^{[2
]}

Ritter, Tobias ^{[1
]}

机构：

[1] Harvard Univ, Dept Chem & Chem Biol, 12 Oxford St, Cambridge, MA 02138 USA

[2] CALTECH, Mat & Proc Simulat Ctr, Pasadena, CA 91125 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2010年 / 132卷 / 11期

关键词：

FORM CARBON-CARBON; CRYSTAL X-RAY; O BOND; COUPLING REACTION; DIORGANOPALLADIUM(II) COMPLEXES; DENSITY FUNCTIONALS; OXIDATIVE ADDITION; PD(II) COMPLEXES; BUTYL ETHERS; ARYL-IODIDE;

D O I：

10.1021/ja909371t

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The first systematic mechanism study of C-F reductive elimination from a transition metal complex is described. C-F bond formation from three different Pd(IV) fluoride complexes was mechanistically evaluated. The experimental data suggest that reductive elimination occurs from cationic Pd(IV) fluoride complexes via a dissociative mechanism. The ancillary pyridyl-sulfonamide ligand plays a crucial role for C-F reductive elimination, likely due to a kappa(3) coordination mode, in which an oxygen atom of the sulfonyl group coordinates to Pd. The pyridyl-suflonamide can support Pd(IV) and has the appropriate geometry and electronic structure to induce reductive elimination.

引用

页码：3793 / 3807

页数：15

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