Journal article

Mass Spectrometric and Computational Studies on the Reaction of Aromatic Peroxyl Radicals with Phenylacetylene Using the Distonic Radical Ion Approach

George N Khairallah, Richard AJ O'Hair, Uta Wille

Journal of Physical Chemistry A | AMER CHEMICAL SOC | Published : 2014


Product and mechanistic studies were performed for the reaction of aromatic distonic peroxyl radical cations 4-PyrOO(•+) and 3-PyrOO(•+) with phenylacetylene (7) in the gas phase using mass spectrometric and computational techniques. PyrOO(•+) was generated through reaction of the respective distonic aryl radical cation Pyr(•+) with O2 in the ion source of the mass spectrometer. For the reaction involving the more electrophilic 4-PyrOO(•+), a rate coefficient of k1 = (2.2 ± 0.6) × 10(-10) cm(3) molecule(-1) s(-1) was determined at 298 K, while a value of k2 = (8.2 ± 2.1) × 10(-11) cm(3) molecule(-1) s(-1) was obtained for the reaction involving the less electrophilic 3-PyrOO(•+). This highli..

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Awarded by Australian Research Council under the Centre of Excellence

Funding Acknowledgements

This work was supported by the Australian Research Council under the Centre of Excellence (CE0561607) and the Discovery (DP1096134) program and by computational resources through the National Computational Merit Allocation Scheme and the School of Chemistry of The University of Melbourne. We thank Dr. Catrin Goeschen for support.