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Structure, spectroscopy, and thermal decomposition of 5-chloro-1,2,3,4-thiatriazole: a He I photoelectron, infrared, and quantum chemical study

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Abstract

5-Chloro-1,2,3,4-thiatriazole has been investigated in the gas phase for the first time by mid-infrared and He I photoelectron spectroscopy. The ground-state geometry has been obtained from quantum chemical calculations at the CCSD(T) and B3LYP levels using aug-cc-pVTZ basis set. Ionization potentials have been determined and the electronic structure has been discussed within the frame of molecular orbital theory. IR and photoelectron spectroscopies, supported by quantum chemical calculations at the B3LYP and SAC-CI levels, provide a detailed investigation into the vibrational and electronic character of the molecule. Thermal stability of 5-chloro-1,2,3,4-thiatriazole has been studied both experimentally and theoretically. Flash vacuum thermolysis of the molecule produces fast quantitatively N2, ClCN, and sulfur. Theoretical calculations at the CCSD(T)//B3LYP level predict competitive decomposition routes, starting either with a retro-cycloaddition reaction leading to N2S and ClCN or with a ring opening to chlorothiocarbonyl azide intermediate, to produce finally N2, S, and ClCN. Calculations also predict that N2S is reactive and decomposes in bimolecular reactions to N2 and S2.

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Acknowledgments

We thank the Hungarian Scientific Research Fund for financial support to the project (grant no. OTKA K101164).

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Authors and Affiliations

  1. Institute of Chemistry, Eötvös Loránd University, Budapest 112, P.O. Box 32, 1518, Hungary

    Tibor Pasinszki, Dániel Dzsotján & Gábor Vass

  2. École Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, 11 Allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France

    Jean-Claude Guillemin

  3. Université européenne de Bretagne, Rennes, France

    Jean-Claude Guillemin

Authors
  1. Tibor Pasinszki
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  2. Dániel Dzsotján
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  3. Gábor Vass
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  4. Jean-Claude Guillemin
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Corresponding author

Correspondence to Tibor Pasinszki.

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The paper is dedicated to Magdolna Hargittai on the occasion of her 70th birthday.

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Pasinszki, T., Dzsotján, D., Vass, G. et al. Structure, spectroscopy, and thermal decomposition of 5-chloro-1,2,3,4-thiatriazole: a He I photoelectron, infrared, and quantum chemical study. Struct Chem 26, 1603–1610 (2015). https://doi.org/10.1007/s11224-015-0655-z

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  • DOI: https://doi.org/10.1007/s11224-015-0655-z

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