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Theoretical studies on the tautomerism and intramolecular hydrogen shifts of 5-Amino-tetrazole in the gas phase

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Abstract

The tautomerism and intramolecular hydrogen shifts of 5-amino-tetrazole in the gas phase were studied in the present work. The minimum energy path (MEP) information of 5-amino-tetrazole was obtained at the CCSD(T)/6–311G**//MP2/6–311G** level of theory. The six possible tautomers of 1H, 4H-5-imino-tetrazole (a), 1H-5-amino-tetrazole (b), 2H-5-amino-tetrazole (c), 1H, 2H-5-imino-tetrazole (d), the mesoionic form (e) and 2H, 4H-5-imino-tetrazole (f) were investigated. Among these tautomers, there are 2 amino- forms, 3 imino- forms, and 1 mesoionic structure form. In all the tautomers, 2-H form (c) is the energetically preferred one in the gas phase. In the imino- tautomers, the energy value of the compound d is similar as that of the compound f but it is higher than the energy value of the compound a. The potential energetic surface (PES) and kinetics for five reactions have been investigated. Reaction 2 (b→c) was hydrogen shifts only in which the 1-H and 2-H rearrangement. This means that the reaction 2 (b→c) is energetically favorable having an activation barrier of 45.66 kcal·mol−1 and the reaction energies (ΔE) is only 2.67 kcal·mol−1. However, the reaction energy barrier for tautomerism of reaction 1 (b→e) is 54.90 kcal·mol−1. Reaction 1 (b→a), reaction 3 (c→d), and reaction 5 (c→f) were amino- →imino- tautomerism reactions. The energy barriers of amino- →imino- tautomerism reactions required are 59.39, 65.57, 73.61 kcal·mol−1 respectively in the gas phase. The calculated values of rate constants using TST, TST/Eckart, CVT, CVT/SCT and CVT/ZCT methods using the optimized geometries obtained at the MP2/6–311G** level of theory show the variational effects are small over the whole temperature range, while tunneling effects are big in the lower temperature range for all tautomerism reactions.

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Acknowledgments

The authors would like to thank Professor D. G. Truhlar for providing the POLYRATE 8.2 program. The project was supported by the NSAF Foundation (No. 10776002) and the 111 project (B07012) in China.

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Authors and Affiliations

  1. State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing, 100081, People’s Republic of China

    Jian-Guo Zhang, Li-Na Feng, Tong-Lai Zhang, Li Yang & Man Wu

  2. Shanxi Fenxi Heavy Industry Co., Ltd., Taiyuan, 030027, People’s Republic of China

    Li-Na Feng

  3. Institute of Chemical Materials, Chinese Academy of Engineering Physics (CAEP), Mianyang, 621900, People’s Republic of China

    Yuan-Jie Shu

  4. School of Science, Beijing Institute of Technology, Beijing, 100081, People’s Republic of China

    Shao-Wen Zhang

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  1. Jian-Guo Zhang
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Correspondence to Jian-Guo Zhang.

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Zhang, JG., Feng, LN., Shu, YJ. et al. Theoretical studies on the tautomerism and intramolecular hydrogen shifts of 5-Amino-tetrazole in the gas phase. J Mol Model 15, 67–77 (2009). https://doi.org/10.1007/s00894-008-0374-0

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  • DOI: https://doi.org/10.1007/s00894-008-0374-0

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