Consecutive C–F Bond Activation of Hexafluorobenzene and Decafluorobiphenyl

The reaction of [Ni 2 ( i Pr 2 Im) 4 (COD)] ( 1 ) { i Pr 2 Im = 1,3‐bis(isopropyl)imidazolin‐2‐ylidene} with hexafluorobenzene and decafluorobiphenyl results at room temperature in the formation of the products of a C–F bond activation reaction, i.e. [Ni( i Pr 2 Im) 2 (F)(C 6 F 5 )] ( 2 ) and [Ni( i Pr 2 Im) 2 (F)(C 12 F 9 )] ( 4 ). The reactions of 2 and 4 with 1 or the reactions of hexafluorobenzene and decafluorobiphenyl with 1 equiv. or excess of dinuclear 1 (stoichiometric ratio nickel/substrate > 2:1) at higher temperatures afford the complexes of a consecutive C–F bond‐activation reaction, [1,4‐{Ni( i Pr 2 Im) 2 (F)} 2 (C 6 F 4 )] ( 3 ) and [4,4′‐{Ni( i Pr 2 Im) 2 (F)} 2 (C 12 F 8 )] ( 5 ). Complexes 3 and 5 cleanly react in THF at room temperature with chlorotrimethylsilane and (isopropyl)(trimethylsilyl)selenane under elimination of fluorotrimethylsilane to yield the corresponding chloro and selenolato complexes [1,4‐{Ni( i Pr 2 Im) 2 (X)} 2 (C 6 F 4 )] [X = Cl ( 6 ), i PrSe ( 7 )] and [4,4′‐{Ni( i Pr 2 Im) 2 (X)} 2 (C 12 F 8 )] [X = Cl ( 8 ), i PrSe ( 9 )].