Rapid Intermolecular Carbon−Fluorine Bond Activation of Pentafluoropyridine at Nickel(0): Comparative Reactivity of Fluorinated Arene and Fluorinated Pyridine Derivatives

Reaction of hexafluorobenzene with Ni(COD) 2 (COD = 1,5,-cyclooctadiene) in the presence of triethylphosphine or with Ni(PEt 3 ) 4 at room temperature results in very slow formation of trans -Ni(PEt 3 ) 2 (C 6 F 5 )F ( 1 ). The X-ray crystal structure reveals a molecular complex with approximately square-planar coordination at nickel, a Ni−F distance of 1.836(5) Å and a Ni−C distance of 1.878(7) Å. Analogous reactions with pentafluoropyridine and 2,3,5,6-tetrafluoropyridine proceed much faster. Both reactions yield C−F activation products analogous to 1 in which a single regioisomer is dominant. The crystal structure of trans -Ni(PEt 3 ) 2 (C 5 HF 3 N)F ( 3 ) shows that the trifluoropyridyl ligand is metalated at the 2-position. The Ni−F and Ni−C distances are 1.856(2) and 1.869(4) Å, respectively. In the structures of both 1 and 3, the plane of the aryl ring is perpendicular to the nickel coordination plane. These structures provide the first values of nickel-fluorine distances at square-planar Ni(II). The reaction of Ni(COD) 2 with PEt 3 and 3,5-dichloro-2,4,6-trifluoropyridine yields exclusively trans -Ni(PEt 3 ) 2 (C 5 ClF 3 N)Cl ( 4 ), the product of C−Cl activation with the metal at the 3-position of the ring. The corresponding reaction with 2,3,4,5,6,-pentafluorostyrene results in rapid formation of the alkene coordination product, Ni(PEt 3 ) 2 (η 2 -CH 2 CHC 6 F 5 ) ( 6 ). The crystal structure of 6 shows the typical trigonal Ni(0) geometry with the coordinated atoms almost perfectly coplanar with the nickel. The Ni−C distances average 1.960(6) Å; the P−Ni−P angle is 115.0(1)°. Reaction with pentafluorobenzene and methoxypentafluorobenzene yield C−F activation products very slowly with little regioselectivity. The studies reported in this paper demonstrate that intermolecular C−F activation of a fluoroaromatic can take place rapidly and in good yield at a first row transition metal through the suitable choice of substrate.