The Loss Of NH2O From The N-hydroxyacetamide Radical ... - NASA/ADS

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NASA/ADS

The loss of NH2O from the N-hydroxyacetamide radical cation CH3C(O)NHOH+

  • Jobst, Karl J.
    • ;
  • Burgers, Peter C.
    • ;
  • Ruttink, Paul J. A.
    • ;
  • Terlouw, Johan K.

Abstract

A previous study [Ch. Lifshitz, P.J.A. Ruttink, G. Schaftenaar, J.K. Terlouw, Rapid Commun. Mass Spectrom. 1 (1987) 61] shows that metastable N-hydroxyacetamide ions CH3C(O)NHOH+ (HA-1) do not dissociate into CH3CO+ + NHOH by direct bond cleavage but rather yield CH3CO+ + NH2OE The tandem mass spectrometry based experiments of the present study on the isotopologue CH3C(O)NDOD+ reveal that the majority of the metastable ions lose the NH2O radical as NHDO rather than ND2O. A mechanistic analysis using the CBS-QB3 model chemistry shows that the molecular ions HA-1 rearrange into hydrogen-bridged radical cations [OCC(H2)H...N(H)OH]+ whose acetyl cation component then catalyses the transformation NHOH --> NH2O prior to dissociation. The high barrier for the unassisted 1,2-H shift in the free radical, 43 kcal mol-1, is reduced to a mere 7 kcal mol-1 for the catalysed transformation which can be viewed as a quid-pro-quo reaction involving two proton transfers.

Publication: International Journal of Mass Spectrometry Pub Date: August 2006 DOI: 10.1016/j.ijms.2006.03.013 Bibcode: 2006IJMSp.254..127J Keywords:
  • Ion-catalysis;
  • Tandem mass spectrometry;
  • CBS-QB3 model chemistry;
  • Quid-pro-quo mechanism
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