stable species in the gas phase has been established. This conclusion could be derived from a careful study of their collisional activation spectra, which show minor but characteristic dBerences. The ions studied were generated from various precursor ions in single or multiple fragmentation processes as well as via ion-molecule reactions. Their heats of formation vary from 925 to 1085Mmol-' according to MIND0/3 or from 925 to 1050 M mol-' according to MNDO calculations.
The loss of a hydrogen atom from ionEzed 2-methylpropanenitde is preceded by a drastic rearrangement of the molecular ion. The result of this fragmentation is the generation of two stable structurally different [C41&N]+ ions, formed via different pathways. Their structures can be established by a careful comparison of the metastable ion spectra, collision activation spectra and charge stripping spectra from the compound and its three deuterium labeled analogues and from [C4Hdy]+ ions generated from reference compounds via electron impact ionization or in selected ionlmolecule reactions.
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