Modeling deoxyribose radicals by neutralization-reionization mass spectrometry. Part 2. Preparation, dissociations, and energetics of 3-hydroxyoxolan-3-yl radical and cation

  • Shetty Vivekananda
  • Martin Sadílek
  • Xiaohong Chen
  • Luke E. Adams
  • František Tureček
Focus: McLafferty Rearrangement

Abstract

The title radical (1) is generated in the gas-phase by collisional neutralization of carbonyl-protonated oxolan-3-one. A 1.5% fraction of 1 does not dissociate and is detected following reionization as survivor ions. The major dissociation of 1 (∼56%) occurs as loss of the hydroxyl H atom forming oxolan-3-one (2). The competing ring cleavages by O-C-2 and C-4-C-5 bond dissociations combined account for ∼42% of dissociation and result in the formation of formaldehyde and 2-hydroxyallyl radical. Additional ring-cleavage dissociations of 1 resulting in the formation of C2H3O and C2H4O cannot be explained as occurring competitively on the doublet ground (X) electronic state of 1, but are energetically accessible from the A and higher electronic states accessed by vertical electron transfer. Exothermic protonation of 2 also produces 3-oxo-(1H)-oxolanium cation (3 +) which upon collisional neutralization gives hypervalent 3-oxo-(1H)-oxolanium radical (3). The latter dissociates spontaneously by ring opening and expulsion of hydroxy radical. Experiment and calculations suggest that carbohydrate radicals incorporating the 3-hydroxyoxolan-3-yl motif will prefer ring-cleavage dissociations at low internal energies or upon photoexcitation by absorbing light at ∼590 and ∼400 nm.

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Copyright information

© American Society for Mass Spectrometry 2004

Authors and Affiliations

  • Shetty Vivekananda
    • 1
  • Martin Sadílek
    • 1
  • Xiaohong Chen
    • 1
  • Luke E. Adams
    • 1
  • František Tureček
    • 1
  1. 1.Department of ChemistryUniversity of WashingtonSeattleUSA

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