| Abstract: | Using the relative abundance of metastable ions, collisional activation spectra, field ionization kinetic measurements, isotopic labelling, appearance energy and kinetic energy release data, it is shown that linear alkyne radical cations with more than six carbon atoms do not isomerize to equilibrating structures prior to decomposition. At the shortest ion lifetimes the molecular ions of linear alkynes decompose mainly by simple β-bond fission which allows an unequivocal localization of the triple bond. At medium ion lifetimes fragmentation occurs predominantly via a McLafferty rearrangement, while at long ion lifetimes competing alkyl losses prevail. These alkyl losses occur via cyclic intermediates leading to thermochemically stable cycloalkenyl ions. All these reactions occur with a high specificity with respect to the carbon and hydrogen atoms involved and are preceded by little or no hydrogen exchange reactions. |
