Decomposition Mechanism of 5,5′-Bis(tetrazole)-1,1′-dioIate(TKX-50) Anion Initiated by Intramolecular Oxygen Transfer
作者机构：Xi'an Modem Chemistry Research InstituteXi 'an 710065P.R.China School of Chemical EngineeringNanjing University of Science and Technology Nanjing 210094P.R.China
出 版 物：《Chemical Research in Chinese Universities》 (高等学校化学研究（英文版）)
年 卷 期：2019年第35卷第3期
页 面：485-489页
核心收录：
基 金：Supported by the Postgraduate Innovation Project of Jiangsu Province China
主 题：Thennal decomposition 5,5′-Bis(tetrazole)-1,1′-diolate(TKX-50) anion Activation energy barrier Density functional theory
摘 要：Density functional theory calculations at the B3LYP/6-31+G^** and B3LYP/6-311++G ^** levels were perfonned on thermal decomposition of 5,5′-bis(tetrazole)-1 ,r-diolate(TKX-50) anion with an intramolecular oxygen transfer being an initial step. Tlie results show that the intramolecular oxygen transfers are the rate-limiting steps for the decomposition of title anion with activation energies being in the range of 287-328 kJ/mol. Judged by the nucleus- independent chemical shift values, the formation of antiaromatic ring in transition state or the decrease of aromaticity of the tetrazole ring of the reactant makes somewhat contribution to the high potential energies of the rate-limiting transition states. However, the activation energies of the following N2 elimination tlirough various pathways are in a low range of 136-166 kJ/mol. The tetrazole ring acts as an electron donor or acceptor in difierent pathways to assist the bond nipture or group elimination. The rate constants in a temperature range of 500-2000 K for all the intramolecular oxygen transferring reactions were obtained. The corresponding linear relationships between InA and 1/T were established.
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