A widely varying range of products in reactions of C6F5BrF2, C6F5IF2, and C6F5IF4 with Lewis acids of different strength

The relative fluoride donor ability: C6F5BrF2 > C6F5IF2 > C6F5IF4 was outlined from reactions with Lewis acids of graduated strength in different solvents. Fluoride abstraction from C6F5HalF2 with BF3·NCCH3 in acetonitrile (donor solvent) led to [C6F5HalF·(NCCH3)n][BF4]. The attempted generation of [C6F5BrF]+ from C6F5BrF2 and anhydrous HF or BF3 in weakly coordinating SO2ClF gave C6F5Br besides bromoperfluorocycloalkenes C6BrF7 and 1-BrC6F9. In reactions of C6F5IF2 with SbF5 in SO2ClF the primary observed intermediate (19F NMR, below 0 °C) was the 4-iodo-1,1,2,3,5,6-hexafluorobenzenium cation, which converted into C6F5I and 1-IC6F9 at 20 °C. The reaction of C6F5IF4 with SbF5 in SO2ClF below −20 °C gave the cation [C6F5IF3]+ which decomposed at 20 °C to C6F5I, 1-iodoperfluorocyclohexene, and iodoperfluorocyclohexane. Principally, the related perfluoroalkyl compound C6F13IF4 showed a different type of products in the fast reaction with AsF5 in CCl3F (−60 °C) which resulted in C6F14. Intermediate and final products of C6F5HalFn−1 (n = 3, 5) with Lewis acids were characterized by NMR in solution. Stable solid products were isolated and analytically characterized.

Graphical abstractResults of the interaction of C6F5HalFn−1 (n = 3, 5) with Lewis acids EFm depend on the acid strength of EFm, the coordinating property of the solvent, the thermal stability of the product, and the oxidation number of Hal. Figure optionsDownload full-size imageDownload as PowerPoint slide