Reactivity Trends in the Gas-Phase Addition of Acetylene to the N-Protonated Aryl Radical Cations of Pyridine, Aniline, and Benzonitrile
Oisin J Shiels, PD Kelly, Cameron C Bright, Berwyck LJ Poad, Stephen J Blanksby, Gabriel da Silva, Adam J Trevitt
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY | AMER CHEMICAL SOC | Published : 2021
A key step in gas-phase polycyclic aromatic hydrocarbon (PAH) formation involves the addition of acetylene (or other alkyne) to σ-type aromatic radicals, with successive additions yielding more complex PAHs. A similar process can happen for N-containing aromatics. In cold diffuse environments, such as the interstellar medium, rates of radical addition may be enhanced when the σ-type radical is charged. This paper investigates the gas-phase ion-molecule reactions of acetylene with nine aromatic distonic σ-type radical cations derived from pyridinium (Pyr), anilinium (Anl), and benzonitrilium (Bzn) ions. Three isomers are studied in each case (radical sites at the ortho, meta, and para positio..View full abstract
Awarded by Australian Research Council
A.J.T., S.J.B., and G.d.S. acknowledge project funding from the Australian Research Council Discovery Program (DP170101596). This work was supported by computational resources provided by the Australian Government through the National Computation Infrastructure under the National Computational Merit Allocation Scheme. 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. P.D.K. and O.J.S. acknowledge receipt of an Australian Government Research Training Program Scholarship. We are also grateful for the assistance of A. J. Turner and B. R. Burns in aspects of the experiment.