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Theoretical investigations on stability of pyridylpentazoles, pyridazylpentazoles, triazinylpentazoles, tetrazinylpentazoles, and pentazinylpentazole searching for a replacement of phenylpentazole as N5 − source

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Abstract

Stabilities of pyridylpentazoles, pyridazylpentazoles, triazinylpentazoles, tetrazinylpentazoles, and pentazinylpentazole were studied using density functional theory to assess their potentials as the source of pentazole anion (N5 −) for replacement of phenylpentazole (PhN 5 ). Replacing the aryl group of PhN 5 by six-member heterocycle weakens pentazole ring. Compared to PhN 5 , title molecules have longer N-N bonds and lower activation energy (E a,1) needed for the N5 ring breaking. E a,1 decreases with the increasing number of nitrogen atoms of heterocycle. The ortho nitrogen of heterocycle most obviously lowers the stability of pentazole. The central C-N bond dissociation energies (BDEs) of title molecules are lower than that of PhN 5 . For the molecule with 0~1 ortho-nitrogen, H rearrangement happens during the central C-N bond breaking. The energy (E a,2) required for H rearrangement is considerably smaller than the corresponding BDE. ΔE a,2 (E a,2(PhN5) - E a,2 = 7.5~35.7 kJ mol-1) is larger than ΔE a,1 (E a,2(PhN5) - E a,2 = 4.6~15.5 kJ mol-1), while ΔE a,2/E a,2(PhN5) (2~9.5 %) is smaller than ΔE a,1/E a,1(PhN5) ( 4.4~15.0 %). The larger ΔE a,1/E a,1(PhN5) suggests that title molecules can not be the better N5 − than PhN 5 .

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  1. School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, China

    Xueli Zhang & Xuedong Gong

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  1. Xueli Zhang
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  2. Xuedong Gong
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Correspondence to Xuedong Gong.

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Zhang, X., Gong, X. Theoretical investigations on stability of pyridylpentazoles, pyridazylpentazoles, triazinylpentazoles, tetrazinylpentazoles, and pentazinylpentazole searching for a replacement of phenylpentazole as N5 − source. J Mol Model 21, 318 (2015). https://doi.org/10.1007/s00894-015-2867-y

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