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From the mass-analysed ion kinetic energy spectra of labelled ions, kinetic energy releases and thermodynamic data, it is proved that protonated n-propylbenzene (1) isomerizes into protonated isopropylbenzene (2). It is also shown that the dissociation of the less energetic metastable ions of (2), leading to ]iso-C3H,I+ and (C,H,J+ product ions, is preceded by H exchange. This H exchange involves two interconverting ioweutral complexes [C6H6, is0-C3H7') (2n) and [C6H7+, CjH6] (2a).Y Scheme 1