Alkyl‐ and Arylthiolation of Aryl Halides Catalyzed by Fluorinated Bis‐Imino‐Nickel NNN Pincer Complexes [NiCl₂{C₅H₃N‐2,6‐(CHNAr_<i>f</i>)₂}]

Abstract

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 =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.