Isomerization and dissociation of C2X5+ and C2X4+center dot ions (X = Cl, F) from chlorofluoroethanes in an ion trap mass spectrometer

The collision-induced dissociation of C2X5+ (C2O2F3+, C2Cl3F2+ and C2Cl4F+) and C2X4+. ions (C2ClF3+., C2Cl2F2+., and C2ClF3+.) 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 (MSn) 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 C2X5+ 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 CX3+ and CF2. Energetically, CF2 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 C2Cl2F3+ species derived from 1,1,1-trichlorotrifluoroethane, which should have initially the Cl2C+-CF3 structure). Similar behavior was observed with C2X4+. ions produced both from the three chlorofluoroethanes and from model alkenes (trifluorochloroethene and tetrachloroethene). The dissociation behavior of these C2X4+. species is characteristic of the ion composition, with no memory of the original neutral precursor structure. Specifically, C2Cl2F2+. ions dissociate uniquely via loss of CF2, C2ClF3+. ions eliminate preferentially CF, with CF2 loss being only a minor reaction, whereas C2Cl3F+. and C2Cl4+. dissociate exclusively via Cl elimination.