Abstract:The synthesis of bis-imino nickel(II) NNN pincer complexes of the type [NiCl 2 {C 5 H 3 N-2,6-(CHNAr f ) 2 }]; Ar f ¼ C 6 H 3 -2,3-F 2 (1), C 6 H 3 -2,5-F 2 (2), C 6 H 3 -3,4-F 2 (3), C 6 H 3 -3,5-F 2 (4), C 6 H 2 -2,3,4-F 3 (5), C 6 H 2 -2,3,6-F 3 (6), C 6 H 2 -2,4,5-F 3 (7), C 6 H 2 -2,4,6-F 3 (8), has been achieved and their reactivity in alkyl-and arylthiolation reactions of halobenzenes examined. The use of fluorinated substituents Ar f on the imines has allowed the tuning of the electronics in these complexes and the influence of these substituents and those of the disulfides in the thiolation reactions have been analyzed.