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

• DOI: 10.1021/ja909371t
• Publication Date: 2010-03-02T19:54:53Z
• Authors: Takeru Furuya; Diego Benitez; Ekaterina Tkatchouk; Alexandra E. Strom; Pingping Tang; William A. Goddard; Tobias Ritter
• Keywords: Sulfonamides; Magnetic Resonance Spectroscopy; Pyridines; Temperature; 610; Fluorine; 540; Ligands; 01 natural sciences; Carbon; 0104 chemical sciences; Solutions; Fluorides; Kinetics; Quinolines; Solvents; Quantum Theory; Oxidation-Reduction; Palladium

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.