Zhang Xueli, Gong Xuedong
Department of Chemistry, Nanjing University of Science and Technology, XiaoLingWei 200, Nanjing, 210094, China.
J Mol Model. 2016 May;22(5):106. doi: 10.1007/s00894-016-2971-7. Epub 2016 Apr 15.
The alkali metal (M=Li, Na, and K) para-substituted (M-1), meta-substituted (M-2) or ortho-substituted (M-3) derivatives of phenylpentazole (PhN5) were studied using density functional theory. The substituted metals improve the energy barrier for decomposition of the N5 ring of PhN5 by 19.3 ∼ 65.0 kJ/mol. M-3 has the ionic N-M bond, which is not found for M-1 and M-2. M-1 and M-2 have similar electrostatic potentials and dispersion interactions between metal and N5 ring. The comparable intramolecular interactions of M-1 and M-2 lead to similar N5 ring stability. Compared to M-1 and M-2, M-3 has a more negative charge on N5 ring and stronger dispersion interaction. The stronger intramolecular interactions of M-3 result in the higher N5 ring stability. For M-1 and M-2, different metals have slight affects on N5 ring stability. For M-3, N5 ring stability decreases in the order of Li > Na > K. The substituted metal lowers E(g) of PhN5.
利用密度泛函理论研究了苯基戊唑（PhN5）的碱金属（M = Li、Na和K）对位取代（M - 1）、间位取代（M - 2）或邻位取代（M - 3）衍生物。取代金属使PhN5的N5环分解的能垒提高了19.3～65.0 kJ/mol。M - 3具有离子型N - M键，而M - 1和M - 2没有。M - 1和M - 2在金属与N5环之间具有相似的静电势和色散相互作用。M - 1和M - 2类似的分子内相互作用导致N5环稳定性相似。与M - 1和M - 2相比，M - 3的N5环上电荷更负，色散相互作用更强。M - 3更强的分子内相互作用导致N5环稳定性更高。对于M - 1和M - 2，不同金属对N5环稳定性影响较小。对于M - 3，N5环稳定性按Li > Na > K的顺序降低。取代金属降低了PhN5的E(g)。
