caa a22 4500 605511810 CHVBK 20210128100652.0 cr unu---uuuuu 210128e20151201xx s 000 0 eng 10.1007/s00894-015-2867-y doi (NATIONALLICENCE)springer-10.1007/s00894-015-2867-y Theoretical investigations on stability of pyridylpentazoles, pyridazylpentazoles, triazinylpentazoles, tetrazinylpentazoles, and pentazinylpentazole searching for a replacement of phenylpentazole as N5 − source [Elektronische Daten] [Xueli Zhang, Xuedong Gong] 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 = 7.5~35.7kJ mol-1) is larger than ΔE a,1 (E a,2(PhN5) - E a,2 = 4.6~15.5kJ 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 . Springer-Verlag Berlin Heidelberg, 2015 Source of N5 − nationallicence PhN5 nationallicence Stability nationallicence Thermodynamics nationallicence Density functional calculations nationallicence Zhang Xueli School of Chemical Engineering, Nanjing University of Science and Technology, 210094, Nanjing, China aut Gong Xuedong School of Chemical Engineering, Nanjing University of Science and Technology, 210094, Nanjing, China aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/12(2015-12-01), 1-7 1610-2940 21:12<1 2015 21 894 https://doi.org/10.1007/s00894-015-2867-y text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2867-y text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Zhang Xueli School of Chemical Engineering, Nanjing University of Science and Technology, 210094, Nanjing, China aut NATIONALLICENCE 700 1- Gong Xuedong School of Chemical Engineering, Nanjing University of Science and Technology, 210094, Nanjing, China aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/12(2015-12-01), 1-7 1610-2940 21:12<1 2015 21 894