Reactions of (Nonafluorocyclohexen‐1‐yl)xenon(II) Hexafluoroarsenate with Halide Anions

The products of the reaction between the electrophilic alkenylxenonium cation [1‐Xe + –C 6 F 9 ] and the halide anions I − , Br − , Cl − and F − depend on the hardness of the halide anion. With the soft halides I − and Br − Xe(II) is formally displaced by halogen as well in basic MeCN as in superacidic (AHF 1 ), whereas with hard fluoride and chloride no reaction takes place in AHF. In MeCN F − initiates the formation of alkenyl radicals, which abstract hydrogen from the solvent, whereas Cl − exhibits borderline character: RH and RCl formation. Possible reaction paths are discussed. The reactivity of the arylxenonium cation [C 6 F 5 Xe] + in AHF toward halide ions is reported and the relative electrophilicity of the cations [C 6 F 5 Xe] + and [1‐Xe + –C 6 F 9 ] is determined by the competitive reaction with Cl − . In addition the synthesis of cyclohexene 1‐CF 3 –C 6 F 9 from C 6 F 5 CF 3 and XeF 2 is performed and its electrophilicity is compared with that of the aromatic compound C 6 F 5 CF 3 .