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Electrochemical Reduction of Pentafluorophenylxenonium, ‐diazonium, ‐iodonium, ‐bromonium, and ‐phosphonium Salts
Author(s) -
Datsenko S.,
Ignat'ev N.,
Barthen P.,
Frohn H.J.,
Scholten T.,
Schroer T.,
Welting D.
Publication year - 1998
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/(sici)1521-3749(199810)624:10<1669::aid-zaac1669>3.0.co;2-p
Subject(s) - phosphonium , electrochemistry , reduction (mathematics) , chemistry , diazonium compounds , organic chemistry , electrode , mathematics , geometry
Cyclic voltammetry measurements on pentafluorophenylonium compounds of [C 6 F 5 X] + Y – type with X = Xe, N 2 , C 6 F 5 Br, C 6 F 5 I, and (C 6 F 5 ) 3 P were carried out. In these series [C 6 F 5 Xe] + shows the lowest and [(C 6 F 5 ) 4 P] + the highest reduction potential. One electron reduction of [C 6 F 5 Xe] + and [C 6 F 5 N 2 ] + followed by the loss of Xe or N 2 , respectively, leads to the generation of the [C 6 F 5 ] · radical. Favoured following reactions of the [C 6 F 5 ] · 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 (C 6 F 5 ) 3 P, C 6 F 5 Br, or C 6 F 5 I, respectively. These molecules undergo further reductions. The low reduction potential of [C 6 F 5 Xe] + 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.