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

作者：Takeru Furuya, Diego Benítez, Ekaterina Tkatchouk, Alexandra E. Strom, Pingping Tang, William A. Goddard, Tobias Ritter · 发表于：Journal of the American Chemical Society · 年份：2010 · DOI：10.1021/ja909371t · 被引用次数：292 · 研究领域：Fluorine in Organic Chemistry、Inorganic Fluorides and Related Compounds、Catalytic Cross-Coupling Reactions

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-sulfonamide can support Pd(IV) and has the appropriate geometry and electronic structure to induce reductive elimination.