Journal of The American Society for Mass Spectrometry

, Volume 29, Issue 9, pp 1848–1860 | Cite as

Comparing Positively and Negatively Charged Distonic Radical Ions in Phenylperoxyl Forming Reactions

  • Peggy E. Williams
  • David L. Marshall
  • Berwyck L. J. Poad
  • Venkateswara R. Narreddula
  • Benjamin B. Kirk
  • Adam J. Trevitt
  • Stephen J. BlanksbyEmail author
Focus: Application of Photons and Radicals for MS: Research Article


In the gas phase, arylperoxyl forming reactions play a significant role in low-temperature combustion and atmospheric processing of volatile organic compounds. We have previously demonstrated the application of charge-tagged phenyl radicals to explore the outcomes of these reactions using ion trap mass spectrometry. Here, we present a side-by-side comparison of rates and product distributions from the reaction of positively and negatively charge tagged phenyl radicals with dioxygen. The negatively charged distonic radical ions are found to react with significantly greater efficiency than their positively charged analogues. The product distributions of the anion reactions favor products of phenylperoxyl radical decomposition (e.g., phenoxyl radicals and cyclopentadienone), while the comparable fixed-charge cations yield the stabilized phenylperoxyl radical. Electronic structure calculations rationalize these differences as arising from the influence of the charged moiety on the energetics of rate-determining transition states and reaction intermediates within the phenylperoxyl reaction manifold and predict that this influence could extend to intra-molecular charge-radical separations of up to 14.5 Å. Experimental observations of reactions of the novel 4-(1-carboxylatoadamantyl)phenyl radical anion confirm that the influence of the charge on both rate and product distribution can be modulated by increasing the rigidly imposed separation between charge and radical sites. These findings provide a generalizable framework for predicting the influence of charged groups on polarizable radicals in gas phase distonic radical ions.

Graphical Abstract


Distonic ions Phenyl radicals Peroxyl radicals Ion-molecule reactions Reaction kinetics Electronic structure calculations 



The data reported in this paper were obtained at the Central Analytical Research Facility (CARF) operated by the Institute for Future Environments at the Queensland University of Technology. Access to CARF is supported by generous funding from the Science and Engineering Faculty (QUT). A.J.T., B.L.J.P., and S.J.B. acknowledge financial support from the Australian Research Council (ARC) through the Discovery Project scheme (DP140101237 and DP170101596). The authors also acknowledge the generous allocation of computing resources by the NCI National Facility (Canberra, Australia) under Merit Allocation Scheme.

Supplementary material

13361_2018_1988_MOESM1_ESM.docx (643 kb)
ESM 1 Additional experimental details, mass spectra and computational archive data are provided as supporting information. An archive of the raw data files used to create some of the figures in this manuscript can be accessed at 643 kb)


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Copyright information

© American Society for Mass Spectrometry 2018

Authors and Affiliations

  • Peggy E. Williams
    • 1
    • 2
  • David L. Marshall
    • 1
  • Berwyck L. J. Poad
    • 1
  • Venkateswara R. Narreddula
    • 1
  • Benjamin B. Kirk
    • 3
  • Adam J. Trevitt
    • 3
  • Stephen J. Blanksby
    • 1
    Email author
  1. 1.Central Analytical Research Facility, Institute for Future EnvironmentsQueensland University of TechnologyBrisbaneAustralia
  2. 2.Failure and Materials Analysis Branch, Flight Systems DivisionNaval Surface Warfare Center CraneCraneUSA
  3. 3.School of ChemistryUniversity of WollongongWollongongAustralia

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