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The collisional activation spectra of a variety of tetraalkyl phosphonium and trialkyl sulfonium ions generated by field desorption are reported. The fragmentation behaviour of the onium ions is compared with that of ammonium ions, reported earlier [4] and the corresponding open shell amine, phosphine and sulfide molecular ions. Cleavage of the heteroatom -carbon bond, with or without hydrogen rearrangement (i.e. alkyl and alkane loss) leads to prominent fragment ions in all onium ions. Pronounced heterolytic cleavage of this bond was only observed in sulfonium ions. No direct ɑ-cleavage of the cation is observed, however, ɑ-cleavage can occur in a second step after elimination of a substituent. This process leads to the base peak with ammonium ions, occurs less frequently in sulfonium ions and cannot be observed unequivocally in phosphonium ions. In addition, the collisional activatiou spectra of phenylalkyl phosphonium ions and chlorine containing quaternary phosphonium ions are discussed. It is demonstrated that collisional activation in conjunction with field desorption is a useful technique for the structure elucidation of onium cations

Collisional Activation Spectra of Quaternary Phosphonium and Tertiary Sulfonium Cations Produced by Field Desorption