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Theoretical study on the tautomerization of 1,5-diaminotetrazole (DAT)

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Abstract

The tautomerization pathways and kinetics of 1,5-diaminotetrazole (DAT) have been investigated by means of second-order Møller-Plesset perturbation theory (MP2) and coupled-cluster theory, with single and double excitations including perturbative corrections for triple excitations (CCSD(T)). Five possible tautomers, namely 4-hydro-1-amino-5-imino-tetrazole (a), 2,5-diamino-tetrazole (b), 1,5-diamino-tetrazole (c), 2-hydro-1-imino-5-amino-tetrazole (d), and 2,4-dihydro-1,5-diimino-tetrazole (e) were identified. The structures of the reactants, transition states, and products along with the tautomerism pathways were optimized by the MP2 method using the 6-311G** basis set, and the energies were refined using CCSD(T)/6-311G**. The minimum-energy path (MEP) information for DAT was obtained at the CCSD(T)/6-311G**//MP2/6-311G** level of theory. Therein, reaction 2 (c → b) is an amino-shift reaction, while reaction 1 (c → a), reaction 3 (c → d), reaction 4 (a → e), and reaction 5 (d → e) are reactions of hydrogen-shift tautomerization. The calculated results show that 2,5-diaminotetrazole (b) with the minimum energy (taking c as a standard) among five tautomers, is the energetically preferred tautomer of DAT in the gas phase. In addition, the energy barrier of reaction 2 is 71.65 kcal · mol−1 in the gas phase, while reaction 1 takes place more easily with an activation barrier of 61.53 kcal · mol−1 also as compared to 63.71 kcal · mol−1 in reaction 3. Moreover, the tautomerization of reaction 4 requires the largest energy barrier of 83.29 kcal · mol−1, which is obviously bigger than reaction 5 with a value of 73.78 kcal · mol−1. Thus, the hydrogen-shift of c to a is the easiest transformation, while the tautomerization of a to e is the hardest one. Again, the rate constants of tautomerization have been obtained by TST, TST/Eckart, CVT, CVT/SCT, and CVT/ZCT methods in the range 200-2500 K, and analysis indicated that variational effects are small over the whole temperature range, while tunneling effects are significant in the lower temperature range.

Figure 3 shows the tautomers and reactions of the tautomerism of 1,5-diaminotetrazole (DAT) using the MP2/6-311G**. And the adiabatic ground-state potential energy curves (V G a ) and the classical potential barriers (V MEP) of the reactions also have been performed in detail. Results show that the tautomers coexisting with c, tautomers a and d are expected to be most easily derived from c experimentally. While b is the most stable, but is difficult to interchange with c. Again e is the least stable, and the V G a of the transformation from c to e is the largest, so the probability of this reaction occurring is low. All of the V MEP(s) and V G a (s) curves are similar in shape, with their maxima located at the same position (s=0), which implies that the variational effect in calculating the rate constants of the reactions will be small. Schematic representation of tautomers and reactions of DAT using the MP2/6-311G** level of theory

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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) of National Natural Science Foundation of China and Chinese Academy of Engineering Physics.

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Authors and Affiliations

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

    Piao He, Jian-Guo Zhang, Li-Na Feng, Kun Wang & Tong-Lai Zhang

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

    Li-Na Feng

  3. Department of Chemistry, Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK

    Kun Wang

  4. School of Chemistry, Beijing Institute of technology, Beijing, People’s Republic of China, 100081

    Shao-Wen Zhang

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  1. Piao He
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Correspondence to Jian-Guo Zhang.

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He, P., Zhang, JG., Feng, LN. et al. Theoretical study on the tautomerization of 1,5-diaminotetrazole (DAT). J Mol Model 20, 2457 (2014). https://doi.org/10.1007/s00894-014-2457-4

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