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Reactions of [NH 3 +· , H2O] with carbonyl compounds: A McLafferty rearrangement within a complex?

  • G. van der Rest
  • L. B. Jensen
  • S. Abdel Azeim
  • P. Mourgues
  • H. E. Audier
Focus: McLafferty Rearrangement
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Revised:
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Abstract

The reactions of the water solvated ammonia radical cation [NH 3 ·+ , H2O] with a variety of aldehydes and ketones were investigated. The reactions observed differ from those of low energy aldehydes and ketones radical cations, although electron transfer from the keto compound to ionized ammonia is thermodynamically allowed within the terbody complexes initially formed. The main process yields an ammonia solvated enol with loss of water and an alkene. This process corresponds formally to a McLafferty fragmentation within a complex. With aldehydes, another reaction can take place, namely the transfer of the hydrogen from the CHO group to ammonia, leading to the proton bound dimer of ammonia and water, and to the NH 4 + cation. Comparison between the available experimental results leads to the conclusion that the McLafferty fragmentation occurs within the terbody complex initially formed, with no prior ligand exchange, the water molecule acting as a spectator partner.

Keywords

Enol Carbonyl Compound Isobutene Collision Induce Dissociation Neutral Reactant 
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 2004

Authors and Affiliations

  • G. van der Rest
    • 1
  • L. B. Jensen
    • 1
  • S. Abdel Azeim
    • 1
  • P. Mourgues
    • 1
  • H. E. Audier
    • 1
  1. 1.Laboratoire des Mécanismes Réactionnels, UMR 7651 CNRSEcole PolytechniquePalaiseau CedexFrance

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