Journal article
Gas-phase reactions of aryl radicals with 2-butyne: Experimental and theoretical investigation employing the N-methyl-pyridinium-4-yl radical cation
AKY Lam, C Li, G Khairallah, BB Kirk, SJ Blanksby, AJ Trevitt, U Wille, RAJ O'Hair, G Da Silva
Physical Chemistry Chemical Physics | Published : 2012
DOI: 10.1039/c2cp22970f
Abstract
Aromatic radicals form in a variety of reacting gas-phase systems, where their molecular weight growth reactions with unsaturated hydrocarbons are of considerable importance. We have investigated the ion-molecule reaction of the aromatic distonic N-methyl-pyridinium-4-yl (NMP) radical cation with 2-butyne (CH 3CCCH 3) using ion trap mass spectrometry. Comparison is made to high-level ab initio energy surfaces for the reaction of NMP and for the neutral phenyl radical system. The NMP radical cation reacts rapidly with 2-butyne at ambient temperature, due to the apparent absence of any barrier. The activated vinyl radical adduct predominantly dissociates via loss of a H atom, with lesser amoun..
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Grants
Awarded by ARC via the ARC Centre of Excellence in Free Radical Chemistry and Biotechnology
Funding Acknowledgements
We thank the ARC for financial support via the ARC Centre of Excellence in Free Radical Chemistry and Biotechnology (CE0561607) and Discovery grants to A.J.T. (DP1094135) and G.d.S (DP110103889). We are also grateful for support from the ACS Petroleum Research Fund and the University of Melbourne Interdisciplinary Seed Funding Scheme. The authors gratefully acknowledge the generous allocation of computing time from both the Victorian Partnership for Advanced Computing (VPAC) and the NCI National Facility. The authors would also like to thank the ARC and VICS for funding of the LTQ-FT hybrid mass spectrometer instrument and William Alexander Donald for modifying the instrument to allow the study of ion-molecule reactions.