Mechanism of C-F reductive elimination from palladium(IV) fluorides.
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.
Furuya
Takeru
T
Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, USA.
Benitez
Diego
D
Tkatchouk
Ekaterina
E
Strom
Alexandra E
AE
Tang
Pingping
P
Goddard
William A
WA
Ritter
Tobias
T
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
D008024:Ligands; D011725:Pyridines; D011804:Quinolines; D012996:Solutions; D012997:Solvents; D013449:Sulfonamides; D005461:Fluorine; D010165:Palladium; D002244:Carbon; C037219:quinoline; C023666:pyridine; D005459:Fluorides