title: Mechanism of C-F reductive elimination from palladium(IV) fluorides.
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 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.
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, USA.
authors.forename: Takeru
authors.initials: T
authors.lastname: Furuya
authors.forename: Diego
authors.initials: D
authors.lastname: Benitez
authors.forename: Ekaterina
authors.initials: E
authors.lastname: Tkatchouk
authors.forename: Alexandra E
authors.initials: AE
authors.lastname: Strom
authors.forename: Pingping
authors.initials: P
authors.lastname: Tang
authors.forename: William A
authors.initials: WA
authors.lastname: Goddard
authors.forename: Tobias
authors.initials: T
authors.lastname: Ritter
mesh_terms: D002244:Carbon / Q000737:chemistry*; D005459:Fluorides / Q000737:chemistry*; D005461:Fluorine / Q000737:chemistry*; D007700:Kinetics; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry; D011789:Quantum Theory; D011804:Quinolines / Q000737:chemistry; D012996:Solutions; D012997:Solvents / Q000737:chemistry; D013449:Sulfonamides / Q000737:chemistry; D013696:Temperature
chemical_list: D008024:Ligands; D011725:Pyridines; D011804:Quinolines; D012996:Solutions; D012997:Solvents; D013449:Sulfonamides; D005461:Fluorine; D010165:Palladium; D002244:Carbon; C037219:quinoline; C023666:pyridine; D005459:Fluorides