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RESEARCH ARTICLE
Contents Vol 73(8)

Barrierless Reactions of Three Benzonitrile Radical Cations with Ethylene

Oisin J. Shiels A , P. D. Kelly A , Stephen J. Blanksby B , Gabriel da Silva C and Adam J. Trevitt https://orcid.org/0000-0003-2525-3162 A D
+ Author Affiliations
- Author Affiliations

A Molecular Horizons and School of Chemistry and Molecular Bioscience, University of Wollongong, Wollongong, NSW 2522, Australia.

B Central Analytical Research Facility, Institute for Future Environments, Queensland University of Technology, Brisbane, Qld 4001, Australia.

C Department of Chemical Engineering, The University of Melbourne, Melbourne, Vic. 3010, Australia.

D Corresponding author. Email: adamt@uow.edu.au

Australian Journal of Chemistry 73(8) 705-713 https://doi.org/10.1071/CH19606
Submitted: 24 November 2019  Accepted: 14 January 2020   Published: 13 May 2020

Abstract

Reactions of three protonated benzonitrile radical cations with ethylene are investigated. Product branching ratios and reaction kinetics, measured using ion-trap mass spectrometry, are reported and mechanisms are developed with support from quantum chemical calculations. Reactions proceed via pre-reactive van der Waals complexes with no energy barrier (above the reactant energy) and form radical addition and addition–elimination product ions. Rate coefficients are 4-dehydrobenzonitrilium: 1.72 ± 0.01 × 10−11 cm3 molecule−1 s−1, 3-dehydrobenzonitrilium: 1.85 ± 0.01 × 10−11 cm3 molecule−1 s−1, and 2-dehydrobenzonitrilium: 5.96 ± 0.06 × 10−11 cm3 molecule−1 s−1 (with ±50 % absolute uncertainty). A ring-closure mechanism involving the protonated nitrile substituent is proposed for the 2-dehydrobenzonitrilium case and suggests favourable formation of the protonated indenimine cation.


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