α-Glycyl cation, radical, and anion (H2NCH+/·/−COOH): Generation and characterization in the gas phase

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Abstract

The title species are synthesized in the gas phase and their unimolecular chemistry is determined by a combination of tandem mass spectrometry methods. Dissociative electron ionization of the α-amino acids valine, leucine, isoleucine, or serine produces the α-glycyl cation, H2NCH+COOH, in high yield and purity. At threshold, this ion dissociates by CO loss to form the proton-bound complex HC≡N…H+…OH2 via a tight 1,4-H migration that is associated with a high reverse barrier. After collisional activation, additional channels open, most notably the formation of the complementary and structure-characteristic fragments H2NCH+· (ionized aminocarbene) and +COOH and the elimination of OH·. Charge reversal and neutralization—reionization of H2NCH+COOH conclusively show that α-glycyl anion, H2NCH−COOH, and α-glycyl radical, H2NCH·COOH, are stable species residing in deep potential energy wells. In the microsecond time window of the experiments, a small fraction of the α-glycyl radical decomposes by sequential elimination of H2O and CO. The α-glycyl anions arising by charge reversal of the cation or reionization of the radical partly undergo rearrangement losses of H2 and H2O, direct cleavages to −COOH, OH−, and H2N−, and consecutive fragmentation of these primary product anions.

Keywords

Charge Reversal Glycyl Fragment Anion Glycyl Radical Aminocarbene 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
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Copyright information

© American Society for Mass Spectrometry 1999

Authors and Affiliations

  1. 1.Department of ChemistryThe University of AkronAkronUSA

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