Theoretical Studies on Structures and Properties of Pentazine,1,2,4,5-Tetrazine and s-Triazine Derivatives with Nitrogen - Containing Substitutents

Abstract:

B3LYP /aug-cc-pvdz level of theory, combined with NBO and G3 methods, is applied to study substituent effects on the geometries, bond dissociation energies and high energetic density material properties of 27 kinds of derivatives designed by substituted hydrogen atoms of pentazine, 1,2,4,5-tetrazine and s-triazine, of which the hydrogen atoms are substituted by CN, -NO₂, -NH₂, -N₃, -N₂H, -NHNH₂, -N₄H and-N₄H₃ groups. The relatively small heats of formation are observed for the derivatives substituted by-NH₂, -H, -NO₂ and-NHNH₂. The order of heats of formation for the derivatives containing the same substituent is: pentazine > 1,2,4,5-tetrazine >s-triazine. For the derivatives substituted by-CN, -N₂H and-N₄H₃, heats of formation are 860~1124 kJ/mol,in which heats of formation of 1,2,4,5-tetrazine derivatives are larger. For derivatives substituted by-N₃ and-N₄H, their heats of formation are 974 1735 kJ/mol, which are the highest in all derivatives. The order of heats of formation is: s-triazine derivative > 1,2,4,5-tetrazine derivative > pentazine derivative. The normalized heats of formation of these pentazine derivatives substituted by-CN-N₃ ,- N₂H and N₄H and 1,2,4,5-tetrazine derivatives substituted by-CN-N₃ and N₄H are 93 109 kJ, which is higher than that of triazido-s-triazine and diazido-s-tetrazine derived from Hiskey. Our observations indicate that the higher heats of formation of substituent molecules have, the higher ones the substitutive derivatives. By means of the data of dissociation energy, it can be found that the heats of formation of derivatives substituted by N₃, -N₂H and CN are greater, and they are also more stable. It is possile for them to become energetic materials with high-energy and low sensitivity.

• Periodical: Applied Mechanics and Materials (Volumes 395-396)
• Pages: 104-115
• DOI: https://doi.org/10.4028/www.scientific.net/AMM.395-396.104
• Online since: September 2013
• Authors: Xiao Qin Liang, Yan Zheng, Bi Qin Wang, Xue Mei Pu
• Keywords: 5-Tetrazine, Energetic Materials, Heat of Formation, Nitrogen-Containing Substitutents, Pentazine, s-Triazine

References

[1] Z. G. Feng: Progress In Chemistry Vol. 12 (2000), p.171.

[2] J. C. Bottaro: Chemistry & Industr Vol. 7 (1996), p.249.

[3] F. A. Cotton and G. Wilkinson: Advanced Inorganic Chemistry(Wiley, New York, 1988).

[4] M. H.V. Huynh, M. A. Hiskey, E. L. Hartline, D. P. Montoya and R. Gilardi: Angew. Chem. Int. Ed. Vol. 43 ( 2004) , p.4924.

DOI: 10.1002/anie.200460366

[5] J. Michl and J. Gladysz: Chem. Rev. Vol. 89 (1989) , p.973.

[6] X.Q. Liang, X. M. Pu, Y. J. Shu and A. M. Tian: Acta Chim. Sinica Vol. 64(2006) , p.2057(in chinese).

[7] X. Q. Liang, X. M. Pu and A.M. Tian: THEOCHEM Vol. 860(2008) , p.86.

[8] K. K. Innes, I. G. Ross andW. R. Moomaw: J. Mol. Spectry Vol. 132(1988) , p.492.

[9] C. I. Williams and M. A. Whitehead: THEOCHEM Vol. 393(1997) , p.9.

[10] W. Z. Wang and P Hobza: ChemPhysChem Vol. 9(2008) , p.1003.

[11] H. O. Ho andW. K. Li: THEOCHEM Vol. 723(2005) , p.195.

[12] J. Beheshtian, A.A. Peyghan and Z. Bagheri: Computational and Theoretical Chemistry Vol. 992(2012) , p.164.

[13] N. Saracoglu: Tetrahedron Vol. 63(2007) , p.4199.

[14] T. Wei, W. H. Zhu, J. J. Zhang and H. M. Xiao: J. Hazard. Mater. Vol. 179(2010) , p.581.

[15] D.E. Chavez and M. A. Hiskey: J. Pyrotech. Vol. 7( 1998) , p.11.

[16] D.E. Chavez and M.A. Hiskey: J. Energ. Mater. Vol. 17(1999) , p.357.

[17] W. J. Blank: Reaction Mechanism of Melamine Resins. J. Coat. Technol. Vol. 51(1979) , p.61.

[18] K. Xu, D. M. Ho and R. A. Pascal: .J. Am. Chem. Soc. Vol. 116(1994) , p.105.

[19] F. Wang, H. C. Du, J. Y. Zhang and X. D. Gong: J. Phys. Chem. C. Vol. 116(2012) , p.6745.

[20] L. B. Munday, P. W. Chung, B. M. Rice and S. Solares: J. Phys. Chem. B Vol. 115(2011) , p.4378.

[21] P. Simoƒes, A. Portugal and J. Campos: Thermochim. Acta, Vol. 298(1997) , p.95.

[22] A. A. Korkin and R. J. Bartlett: J. Am. Chem. Soc. Vol. 118(1996) , p.12244.

[23] R. G. Parr and W. Yang: Density-Functional Theory of Atoms and Molecules, (Oxford University Press, New York 1989).

[24] C. Lee, W. Yang and R. G. Parr: Phys. Rev. B. Vol. 37(1988) , p.785.

[25] D. E. Woon and T. H. Dunning: J. Chem. Phys. Vol. 98(1993) , p.1358.

[26] A. E. Reed, L. A. Curtiss and F. Weinhold: Chem. Rev. Vol. 88(1988) , p.899.

[27] J. P. Foster and F. Weinhold: J. Am. Chem. Soc. Vol. 102(1980) , p.7211.

[28] A. Nicolaides and L. Radom: Mol. Phys. Vol. 88(1996) , p.7759.

[29] A. E. Reed, R. B. Weinstock, and F. Weinhold: J. Chem. Phys. Vol. 83(1985) , p.735.

[30] M.J. Frisch, G.W. Trucks, H.B. Schlegel, et. al. : Gaussian, Inc.: Pittsburgh, PA, (2009).

[31] P. Politzer, J. S. Murray and M. C. Concha, J. Phys. Chem. A. Vol. 102(1998) , p.6697.

[32] B. S. Jursic: J. Chem. Phys. Vol. 106(1997) , p.2555.

[33] J. Zhang, H. M. Xiao and X. D. Gong: J. Phys. Org. Chem. Vol. 14(2001) , p.583.

[34] J. Zhang, H. M. Xiao and X. D. Gong: Inter. J. Quantum. Chem. Vol. 86(2002) , p.305.

[35] S.G. Lias, J. F. Bartmess, J. L. Holmes, R.G. Levin and W.G. Mallard: J. Phys. Chem. Ref. Data Suppl. No. 1(American Institute of Physics, Inc: New York 1988).