Journal article

Barrierless Reactions of Three Benzonitrile Radical Cations with Ethylene

Oisin J Shiels, PD Kelly, Stephen J Blanksby, Gabriel da Silva, Adam J Trevitt

Australian Journal of Chemistry | CSIRO Publishing | Published : 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..

View full abstract

University of Melbourne Researchers

Grants

Awarded by Australian Research Council


Funding Acknowledgements

AJT, SJB, and GDS acknowledge project funding from the Australian Research Council Discovery Program (DP170101596). The authors also acknowledge the generous allocation of computing resources by the National Computational Infrastructure National Facility (Canberra, ACT, Australia) under the Merit Allocation Scheme. PDK acknowledges receipt of an Australian Government Research Training Program Scholarship.