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The reaction of [Ni(Mes 2 Im) 2 ] ( 1 ) (Mes 2 Im = 1,3-dimesityl-imidazolin-2-ylidene) with polyfluorinated arenes as well as mechanistic investigations concerning the insertion of 1 and [Ni( i Pr 2 Im) 2 ] ( 1ipr ) ( i Pr 2 Im = 1,3-diisopropyl-imidazolin-2-ylidene) into the C-F bond of C 6 F 6 is reported. The reaction of 1 with different fluoroaromatics leads to formation of the nickel fluoroaryl fluoride complexes trans -[Ni(Mes 2 Im) 2 (F)(Ar F )] (Ar F = 4-CF 3 -C 6 F 4  2 , C 6 F 5  3 , 2,3,5,6-C 6 F 4 N 4 , 2,3,5,6-C 6 F 4 H 5 , 2,3,5-C 6 F 3 H 2  6 , 3,5-C 6 F 2 H 3  7 ) in fair to good yields with the exception of the formation of the pentafluorophenyl complex 3 (less than 20%). Radical species and other diamagnetic side products were detected for the reaction of 1 with C 6 F 6 , in line with a radical pathway for the C-F bond activation step using 1 . The difluoride complex trans -[Ni(Mes 2 Im) 2 (F) 2 ] ( 9 ), the bis(aryl) complex trans -[Ni(Mes 2 Im) 2 (C 6 F 5 ) 2 ] ( 15 ), the structurally characterized nickel(i) complex trans -[Ni I (Mes 2 Im) 2 (C 6 F 5 )] ( 11 ) and the metal radical trans -[Ni I (Mes 2 Im) 2 (F)] ( 12 ) were identified. Complex 11 , and related [Ni I (Mes 2 Im) 2 (2,3,5,6-C 6 F 4 H)] ( 13 ) and [Ni I (Mes 2 Im) 2 (2,3,5-C 6 F 3 H 2 )] ( 14 ), were synthesized independently by reaction of trans -[Ni(Mes 2 Im) 2 (F)(Ar F )] with PhSiH 3 . Simple electron transfer from 1 to C 6 F 6 was excluded, as the redox potentials of the reaction partners do not match and [Ni(Mes 2 Im) 2 ] + , which was prepared independently, was not detected. DFT calculations were performed on the insertion of [Ni( i Pr 2 Im) 2 ] ( 1ipr ) and [Ni(Mes 2 Im) 2 ] ( 1 ) into the C-F bond of C 6 F 6 . For 1ipr , concerted and NHC-assisted pathways were identified as having the lowest kinetic barriers, whereas for 1 , a radical mechanism with fluoride abstraction and an NHC-assisted pathway are both associated with almost the same kinetic barrier.

chemical science

Coligand role in the NHC nickel catalyzed C–F bond activation: investigations on the insertion of bis(NHC) nickel into the C–F bond of hexafluorobenzene