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

Takeru Furuya, Diego Benítez, Ekaterina Tkatchouk, Alexandra E. Strom, Pingping Tang, William A. Goddard III, Tobias Ritter

2010J. Am. Chem. Soc., 132(11), 3793-3807285cited

Abstract

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 κ^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.

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Furuya, T., Benítez, D., Tkatchouk, E., Strom, A. E., Tang, P., III, W. A. G., & Ritter, T. (2010). Mechanism of C−F Reductive Elimination from Palladium(IV) Fluorides. *J. Am. Chem. Soc.*, *132*(11), 3793-3807. https://doi.org/10.1021/ja909371t