Mono‐ and Perfluoroaryliodine(III) Cyano Compounds – Synthesis, Reactivity, and Structure

C 6 F 5 I(CN) 2 and x‐FC 6 H 4 I(CN) 2 (x = 2, 3, 4) were isolated from reactions of the corresponding aryliodine difluorides ArIF 2 and a stoichiometric excess of Me 3 SiCN in CCl 3 F (0 °C) or CH 2 Cl 2 (20 °C), respectively. In addition, x‐FC 6 H 4 I(CN) 2 compounds were synthesized in good yields on alternative routes, namely from 3‐ or 4‐FC 6 H 4 I(OC(O)CH 3 ) 2 or 4‐FC 6 H 4 I(OC(O)CF 3 ) 2 or from 4‐FC 6 H 4 IO and Me 3 SiCN in CH 2 Cl 2 at 20 °C. In the 1 : 1 reaction of C 6 F 5 IF 2 and Me 3 SiCN a lower temperature was necessary to suppress partial disubstitution and to obtain the first example of a new type of aryliodine(III) cyanide compounds, C 6 F 5 I(CN)F. 4‐FC 6 H 4 I(CN)F could be isolated from the equimolar reaction of 4‐FC 6 H 4 IF 2 and Me 3 SiCN in CH 2 Cl 2 even at 20 °C. The new products were characterized by multi‐NMR and Raman spectroscopy. The molecular structures of C 6 F 5 I(CN) 2 , 3‐ and 4‐FC 6 H 4 I(CN) 2 , C 6 F 5 I(CN)F, and 4‐FC 6 H 4 I(CN)F are discussed and compared with that of C 6 F 5 IF 2 . The reactivity of C 6 F 5 I(CN)F towards fluoride acceptors EF n (BF 3 , AsF 5 ) and R x EX −x (C 6 F 5 SiF 3 , C 6 H 5 SiF 3 , C 6 H 5 PF 4 , Me 3 SiCl, Me 3 SiC 6 F 5 ) were investigated and showed differing reaction patterns (fluoride abstraction, aryl transfer, chloride transfer). Besides the molecular entities C 6 F 5 I(CN)F and C 6 F 5 I(CN)Cl, the corresponding iodonium salts [C 6 F 5 (CN)I][BF 4 ] and [C 6 F 5 (CN)I][AsF 6 ] were isolated. The thermal stability of ArI(CN) 2 and ArI(CN)F, neat and in solution, as well as the reactivity of 4‐FC 6 H 4 I(CN) 2 towards the Lewis acid BF 3 are reported.