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Nucleophilic Addition of Nitrogen to Aryl Cations: Mimicking Titan Chemistry

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Journal of The American Society for Mass Spectrometry

Abstract

The reactivity of aryl cations toward molecular nitrogen is studied systematically in an ion trap mass spectrometer at 102 Pascal of nitrogen, the pressure of the Titan main haze layer. Nucleophilic addition of dinitrogen occurs and the nature of aryl group has a significant influence on the reactivity, through inductive effects and by changing the ground state spin multiplicity. The products of nitrogen activation, aryldiazonium ions, react with typical nitriles, aromatic amines, and alkynes (compounds that are relevant as possible Titan atmosphere constituents) to form covalently bonded heterocyclic products. Theoretical calculations at the level [DFT(B3LYP)/6-311++G(d,p)] indicate that the N2 addition reaction is exothermic for the singlet aryl cations but endothermic for their triplet spin isomers. The –OH and –NH2 substituted aryl ions are calculated to have triplet ground states, which is consistent with their decreased nitrogen addition reactivity. The energy needed for the generation of the aryl cations from their protonated precursors (ca. 340 kJ/mol starting with protonated aniline) is far less than that required to directly activate the nitrogen triple bond (the lowest energy excited state of N2 lies ca. 600 kJ/mol above the ground state). The formation of aza-aromatics via arene ionization and subsequent reactions provide a conceivable route to the genesis of nitrogen-containing organic molecules in the interstellar medium and Titan haze layers.

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Acknowledgments

The authors acknowledge funding for this research from NASA-PIDDP (grant number NNX12AB16G)

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  1. Chemistry Department, Purdue University, West Lafayette, IN, 47907, USA

    Anyin Li, Fred P. M. Jjunju & R. Graham Cooks

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  1. Anyin Li
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Correspondence to R. Graham Cooks.

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Dedicated to T. Pradeep on the occasion of his 50th birthday and in recognition of his contributions to ion and materials chemistry.

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Li, A., Jjunju, F.P.M. & Cooks, R.G. Nucleophilic Addition of Nitrogen to Aryl Cations: Mimicking Titan Chemistry. J. Am. Soc. Mass Spectrom. 24, 1745–1754 (2013). https://doi.org/10.1007/s13361-013-0710-1

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