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 ArlF(2) and a stoichiometric excess of Me(3)SiCN in CCl(3)F (0 degrees C) or CH(2)Cl(2) (20 degrees C), respectively. In addition, x-FC(6)H(4)I(CN)(2) compounds were synthesized in good yields oil alternative 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 degrees 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 distribution 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 degrees 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(n-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 Arl(CN)(2) and Arl(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.