The influence of structural features on facile McLafferty‐type, even‐electron rearrangements in tandem mass spectra of carboxylate anions

Abstract
In contrast to the well‐described McLafferty rearrangement in odd‐electron cations, relatively little has been reported on comparable rearrangements in even‐electron ions, especially negative ions. This work reports a systematic study using tandem mass spectrometry (MS/MS) fragment ion spectra of carboxylate anions having a suitably acidic proton in the γ position. The rearrangement process was studied in both ion trap and triple quadrupole mass spectrometers; characteristic enolate anions and stable neutral products were formed at low collision energies. The process has diagnostic and analytical potential in, for example, the analysis of peptides having C‐terminal serine residues and of 3‐hydroxy‐ or 3‐aminocarboxylic acids in complex mixtures. Copyright © 2006 John Wiley & Sons, Ltd.

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