Reactivity Trends in the Gas-Phase Addition of Acetylene to the N-Protonated Aryl Radical Cations of Pyridine, Aniline, and Benzonitrile.

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 positions). Using a room temperature ion trap, second-order rate coefficients, product branching ratios, and reaction efficiencies are measured. The rate coefficients increase from para to ortho positions. The second-order rate coefficients can be sorted into three groups: low, between 1 and 3 × 10-12 cm3 molecule-1 s-1 (3Anl and 4Anl); intermediate, between 5 and 15 × 10-12 cm3 molecule-1 s-1 (2Bzn, 3Bzn, and 4Bzn); and high, between 8 and 31 × 10-11 cm3 molecule-1 s-1 (2Anl, 2Pyr, 3Pyr, and 4Pyr); and 2Anl is the only radical cation with a rate coefficient distinctly different from its isomers. Quantum chemical calculations, using M06-2X-D3(0)/6-31++G(2df,p) geometries and DSD-PBEP86-NL/aug-cc-pVQZ energies, are deployed to rationalize reactivity trends based on the stability of prereactive complexes. The G3X-K method guides the assignment of product ions following adduct formation. The rate coefficient trend can be rationalized by a simple model based on the prereactive complex forward barrier height.

Molecular Weight Growth in the Gas-Phase Reactions of Dehydroanilinium Radical Cations with Propene.

Protonated aniline-one of the simplest nitrogen-bearing aromatic molecules-is speculated to be present within Titan's atmosphere, where it could play a role in molecular weight growth chemistry. To investigate this possibility, this paper examines the reactions of propene with distonic radical cations derived from protonated aniline. The reaction kinetics, products, and branching ratios of these distonic radical cations (i.e., 2-, 3-, and 4-dehydroanilinium radical cations) are measured in the gas phase using ion-trap mass spectrometry, and calculations (M06-2X/6-31G(2df,p) and G3X-K) are used to rationalize the results. The reaction efficiencies for the 2-, 3-, and 4-dehydroanilinium radical cations are reported as 30.7 (±3.1)%, 2.4 (±0.5)%, and 2.1 (±0.4)%, respectively (with ±50% absolute accuracy). The 4- and 3-dehydroanilinium radical cations undergo addition of propene followed by either (i) methyl radical loss forming ammonio styrene cations (m/z 120) or (ii) ethylene loss pathways forming the ammonio benzyl radical cation (m/z 107). The 4-dehydroanilinium reaction favors methyl loss over ethylene loss, whereas the reverse is true for 3-dehydroanilinium. In contrast, the 2-dehydroanilinium radical cation reacts with propene to purportedly form amino tropylium cation (m/z 106) with ethyl radical loss and methyl amino tropylium cation (m/z 120) with methyl radical loss. The energies of all minima and transition states leading to predicted dissociation products are below the energy of the initial reactants providing plausible pathways at the low temperatures of Titan's atmosphere.

Highly efficient gas-phase reactivity of protonated pyridine radicals with propene.

Small nitrogen containing heteroaromatics are fundamental building blocks for many biological molecules, including the DNA nucleotides. Pyridine, as a prototypical N-heteroaromatic, has been implicated in the chemical evolution of many extraterrestrial environments, including the atmosphere of Titan. This paper reports on the gas-phase ion-molecule reactions of the three dehydro-N-pyridinium radical cation isomers with propene. Photodissociation ion-trap mass spectrometry experiments are used to measure product branching ratios and reaction kinetics. Reaction efficiencies for 2-dehydro-N-pyridinium, 3-dehydro-N-pyridinium and 4-dehydro-N-pyridinium with propene are 70%, 47% and 41%, respectively. The m/z 106 channel is the major product channel across all cases and assigned 2-, 3-, and 4-vinylpyridinium for each reaction. The m/z 93 channel is also significant and assigned the 2-, 3-, and 4-N-protonated-picolyl radical cation for each case. H-Abstraction from propene is not competitive under experimental conditions. Potential energy schemes, at the M06-2X/6-31(2df,p) level of theory and basis set, are described to assist in rationalising observed product branching ratios and elucidating possible reaction mechanisms. Reaction barriers to the production of vinylpyridinium (m/z 106) + CH3 are the lowest identified for the 3- and 4-dehydro-N-pyridinium reactions, in support of the observed dominance of the m/z 106 ion signal. Ethylene loss via ring-mediated H-transfer along the propyl group is found to be the lowest energy pathway for the 2-dehydro-N-pyridinium reaction, suggesting a preference toward m/z 93 (N-protonated-picolyl radical cation) over the experimentally observed products. Entropic bottle-necks along the m/z 93 pathway however, associated with ring-mediated H-atom transfer, are responsible for the dominance of m/z 106 in the 2-dehydro-N-pyridinium + propene reaction. For all three isomers, computed barriers for all observed reaction channels were below the entrance channel, suggesting these reactions can contribute to molecular weight growth in extraterrestrial environments with accelerated reaction rates in low temperature regions of space.