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Cyclic voltammetry measurements on pentafluorophenylonium compounds of [C6F5X]+ Y– type with X = Xe, N2, C6F5Br, C6F5I, and (C6F5)3P were carried out. In these series [C6F5Xe]+ shows the lowest and [(C6F5)4P]+ the highest reduction potential. One electron reduction of [C6F5Xe]+ and [C6F5N2]+ followed by the loss of Xe or N2, respectively, leads to the generation of the [C6F5]· radical. Favoured following reactions of the [C6F5]· radical are the abstraction of hydrogen from MeCN or dimerisation. After the first reduction step the other onium cations split off the pentafluorophenyl element molecule such as (C6F5)3P, C6F5Br, or C6F5I, respectively. These molecules undergo further reductions. The low reduction potential of [C6F5Xe]+ is in contrast to former measurements on partially fluorinated or chlorinated phenylxenonium cations. A plausible explaination for the different behaviour of these Xe–C compounds in electrochemical reduction processes is given.

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