Abstract
The collision‐induced dissociation of C~2~X~5~^+^ (C~2~Cl~2~F~3~^+^, C~2~Cl~3~F~2~^+^ and C~2~Cl~4~F^+^) and C~2~X~4~^+·^ ions (C~2~ClF~3~^+·^, C~2~Cl~2~F~2~^+·^, and C~2~ClF~3~^+·^) derived from three chlorofluoroethanes (the isomeric 1,1,1‐ and 1,1,2‐trichlorotrifluoroethane and 1,1,1,2‐tetrachlorodifluoroethane) was investigated by means of multi‐stage mass spectrometric (MS^n^) experiments in an ion trap mass spectrometer. The observation of a common dissociation pattern for ions of any given elemental composition suggests that the experiments could not differentiate isomeric C~2~X~5~^+^ ions formed from different neutral precursors and originally having different structures. For any given elemental composition, a common dissociation pattern was observed, suggesting that energy barriers for isomer interconversion are lower than for dissociation. For ions containing two or more fluorine atoms, the major (in some cases unique) dissociation involves C—C cleavage to form CX~3~^+^ and CF~2~. Energetically, CF~2~ loss is always the most favorable reaction; mechanistically it implies, at least in some cases, rearrangement via halogen transfer from one carbon to the other (for example, in the case of the C~2~Cl~2~F~3~^+^ species derived from 1,1,1‐trichlorotrifluoroethane, which should have initially the Cl~2~C^+^—CF~3~ structure). Similar behavior was observed with C~2~X~4~^+·^ ions produced both from the three chlorofluoroethanes and from model alkenes (trifluorochloroethene and tetrachloroethene). The dissociation behavior of these C~2~X~4~^+·^ species is characteristic of the ion composition, with no memory of the original neutral precursor structure. Specifically, C~2~Cl~2~F~2~^+·^ ions dissociate uniquely via loss of CF~2~, C~2~ClF~3~^+·^ ions eliminate preferentially CF, with CF~2~ loss being only a minor reaction, whereas C~2~Cl~3~F^+·^ and C~2~Cl~4~^+·^ dissociate exclusively via Cl elimination. Copyright © 2002 John Wiley & Sons, Ltd.