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Theoretical studies on the stability of salts formed by 3-substituted 6-nitraminotetrazines with different cations

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Abstract

A series of energetic salts based on the cations NH4 +, NH3OH+, N2H5 + and C(NH2)3 + and the anions of 6-nitraminotetrazine and its 3-substituted derivatives of –NH2, –N3, –ONO2, –NF2 or –NO2 was studied using dispersion-corrected density functional theory (DFT-D). In comparison with salts of unsubstituted 6-nitraminotetrazine, –NH2 substitution strengthens the hydrogen bonding interaction and other intramolecular interactions (such as charge transfer, binding energy, second-order perturbation energy and dispersion energy), –N3 has tiny effects on these interactions, and other groups weaken these interactions, with weakening decreasing in the order –NO2 > –NF2 > –ONO2. The ability of the cations to produce strong intramolecular interactions decreases in the order NH3OH+ > N2H5 + > NH4 + > C(NH2)3 +, which is contrary to the order of the basicity of bases. Stronger intramolecular interactions lead to more stable salts. All substituent groups improved the chemical stability except –ONO2, while cations had no effect on chemical stability. All substituent groups were helpful in improving aromaticity, in the sequence –ONO2 > –NF2 > –NO2 > –N3 > –NH2.

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Acknowledgments

Thanks to the 086 Project for supporting this research.

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Authors and Affiliations

  1. Department of Chemistry, Nanjing University of Science and Technology, Nanjing, 210094, People’s Republic of China

    Xueli Zhang, Junqing Yang & Xuedong Gong

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  1. Xueli Zhang
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  2. Junqing Yang
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  3. Xuedong Gong
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Correspondence to Xuedong Gong.

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Zhang, X., Yang, J. & Gong, X. Theoretical studies on the stability of salts formed by 3-substituted 6-nitraminotetrazines with different cations. J Mol Model 20, 2521 (2014). https://doi.org/10.1007/s00894-014-2521-0

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