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

Journal of the American Society for Mass Spectrometry
S VivekanandaFrantisek Turecek

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 (approximately 56%) occurs as loss of the hydroxyl H atom forming oxolan-3-one (2). The competing ring cleavages by O[bond]C-2 and C-4[bond]C-5 bond dissociations combined account for approximately 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 C(2)H(3)O and C(2)H(4)O 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 ...Continue Reading

References

Oct 1, 1996·Journal of Mass Spectrometry : JMS·V Q Nguyen, F Turecek
Jun 14, 2001·Journal of the American Chemical Society·J K WolkenF Turecek
Feb 19, 2002·Chemical Reviews·Wendy Knapp Pogozelski, Thomas D. Tullius
Feb 19, 2002·Chemical Reviews·Cynthia J. Burrows, James G. Muller
Mar 13, 2003·Journal of the American Chemical Society·Frantisek Turecek, Erik A Syrstad
Jul 1, 1992·Journal of the American Society for Mass Spectrometry·F TurecekS A Shaffer
Dec 1, 1991·Journal of the American Society for Mass Spectrometry·C WesdemiotisF W McLafferty

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