Alkyl- and Arylthiolation of Aryl Halides Catalyzed by Fluorinated Bis-Imino-Nickel NNN Pincer Complexes [NiCl2{C5H3N-2,6-(CHNArf)2}]

The synthesis of bis‐imino nickel(II) NNN pincer complexes of the type [NiCl2{C5H3N‐2,6‐(CHNArf)2}]; Arf=C6H3‐2,3‐F2 (1), C6H3‐2,5‐F2 (2), C6H3‐3,4‐F2 (3), C6H3‐3,5‐F2 (4), C6H2‐2,3,4‐F3 (5), C6H2‐2,3,6‐F3 (6), C6H2‐2,4,5‐F3 (7), C6H2‐2,4,6‐F3 (8), has been achieved and their reactivity in alkyl‐ and arylthiolation reactions of halobenzenes examined. The use of fluorinated substituents Arf 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.