Perfluoroalkyl Bromides and Iodides

[(C6F5)2IF2][BF4], the First Salt with the Electrophilic Cation [(C6F5)2IF2]+: Synthesis, Reactivity, and Structure

“…Under these conditions only one fluorine is substituted by C 6 F 5 specifically (eqs. (1,2)). IF (2) The bonds in the hypervalent IF 4 unit of IF 5 are best described as a 5c-8e system with highly polar I-F subunits (partial charges: iodine 3.17, fluorine Ϫ0.65; NBO, RHF, LANL2DZ).…”

“…(1,2)). IF (2) The bonds in the hypervalent IF 4 unit of IF 5 are best described as a 5c-8e system with highly polar I-F subunits (partial charges: iodine 3.17, fluorine Ϫ0.65; NBO, RHF, LANL2DZ). In C 6 F 5 IF 4 with the electron withdrawing C 6 F 5 group in the axial position the partial charge (NBO, RHF, LANL2DZ) on iodine (2.95) and fluorine (Ϫ0.69) is diminished slightly relative to IF 5 .…”

“…An excess of approximately 2 equiv. of low basic tri(organyl)pnictanes R 3 E (R ϭ C 6 F 5 , E ϭ P, As, Sb, Bi) were reacted with [(C 6 F 5 ) 2 fluorine was observed (eq. (9)) and no electrophilic transfer of the aryl group (eq.…”

“…Historically, IF 5 was incidentally discovered when I 2 was reacted with AgF by Gore [1], already 16 years before the first discovery of elemental fluorine. Since more than half a century IF 5 is applied in industry, e. g. in the production of perfluoroalkyliodides from CF 2 ϭCF 2 [2]. Up to now a relative small number of organo derivatives [3] and only some prototypic examples of perfluoroorgano derivatives of IF 5 with the general formula RIF 4 are known as there are Alkyl F IF 4 [4Ϫ10], Alkenyl F IF 4 [10], and Aryl F IF 4 [10Ϫ15] compounds.…”

“…He obtained the [(Ar) 2 IF 2 ] ϩ ions from [(Ar) 2 IO] ϩ ions by substitution of oxygen by fluorine using SF 4 as reagent. The starting materials, [(Ar) 2 IO]X salts, were prepared by "self-condensation" [17] (a disproportionation reaction), which is the base catalysed reaction of two ArIO molecules. This procedure cannot be implemented on perfluoroaryl compounds like C 6 F 5 IO, because the latter is an insoluble solid and decomposes already at 89°C (DTA).…”