Journal article

Reaction of Aromatic Peroxyl Radicals with Alkynes: A Mass Spectrometric and Computational Study Using the Distonic Radical Ion Approach

Cong H Li, George N Khairallah, Adrian KY Lam, Richard AJ O'Hair, Benjamin B Kirk, Stephen J Blanksby, Gabriel da Silva, Uta Wille

Chemistry - An Asian Journal | WILEY-V C H VERLAG GMBH | Published : 2013


The reaction of the aromatic distonic peroxyl radical cations N-methyl pyridinium-4-peroxyl (PyrOO(.+)) and 4-(N,N,N-trimethyl ammonium)-phenyl peroxyl (AnOO(.+)), with symmetrical dialkyl alkynes 10a-c was studied in the gas phase by mass spectrometry. PyrOO(.+) and AnOO(.+) were produced through reaction of the respective distonic aryl radical cations Pyr(.+) and An(.+) with oxygen, O(2). For the reaction of Pyr(.+) with O(2) an absolute rate coefficient of k(1)=7.1×10(-12) cm(3) molecule(-1) s(-1) and a collision efficiency of 1.2% was determined at 298 K. The strongly electrophilic PyrOO(.+) reacts with 3-hexyne and 4-octyne with absolute rate coefficients of k(hexyne)=1.5×10(-10) cm(3) ..

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Funding Acknowledgements

This work was supported by the Australian Research Council under the Centre of Excellence Scheme and the American Chemical Society Petroleum Research Fund. Support by the National Computational Infrastructure Facility and the Victorian Life Sciences Computation Initiative is gratefully acknowledged. We thank Alistair Grevis-James for his support.