Decomposition Mechanism of 5,5'-Bis(tetrazole)-1,1'-diolate(TKX-50) Anion Initiated by Intramolecular Oxygen Transfer

doi:10.1007/s40242-019-8332-1

高等学校化学研究 ›› 2019, Vol. 35 ›› Issue (3): 485-489.doi: 10.1007/s40242-019-8332-1

Decomposition Mechanism of 5,5'-Bis(tetrazole)-1,1'-diolate(TKX-50) Anion Initiated by Intramolecular Oxygen Transfer

ZHAO Shengxiang¹, ZHAO Ying², XING Xiaoling¹, JU Xuehai²

1. Xi'an Modern Chemistry Research Institute, Xi'an 710065, P. R. China;
2. School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. China

收稿日期:2018-10-15 修回日期:2019-01-22 出版日期:2019-06-01 发布日期:2019-02-25
通讯作者: JU Xuehai E-mail:xhju@njust.edu.cn
基金资助:
Supported by the Postgraduate Innovation Project of Jiangsu Province, China.

Decomposition Mechanism of 5,5'-Bis(tetrazole)-1,1'-diolate(TKX-50) Anion Initiated by Intramolecular Oxygen Transfer

ZHAO Shengxiang¹, ZHAO Ying², XING Xiaoling¹, JU Xuehai²

1. Xi'an Modern Chemistry Research Institute, Xi'an 710065, P. R. China;
2. School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. China

Received:2018-10-15 Revised:2019-01-22 Online:2019-06-01 Published:2019-02-25
Contact: JU Xuehai E-mail:xhju@njust.edu.cn
Supported by:
Supported by the Postgraduate Innovation Project of Jiangsu Province, China.

摘要/Abstract

摘要： Density functional theory calculations at the B3LYP/6-31+G^** and B3LYP/6-311++G^** levels were performed on thermal decomposition of 5,5'-bis(tetrazole)-1,1'-diolate(TKX-50) anion with an intramolecular oxygen transfer being an initial step. The 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 nu- cleus-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 through various pathways are in a low range of 136-166 kJ/mol. The tetrazole ring acts as an electron donor or acceptor in different pathways to assist the bond rupture 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 lnk and 1/T were established.

关键词: Thermal decomposition, 5,5'-Bis(tetrazole)-1,1'-diolate(TKX-50) anion, Activation energy barrier, Density functional theory

Abstract: Density functional theory calculations at the B3LYP/6-31+G^** and B3LYP/6-311++G^** levels were performed on thermal decomposition of 5,5'-bis(tetrazole)-1,1'-diolate(TKX-50) anion with an intramolecular oxygen transfer being an initial step. The 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 nu- cleus-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 through various pathways are in a low range of 136-166 kJ/mol. The tetrazole ring acts as an electron donor or acceptor in different pathways to assist the bond rupture 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 lnk and 1/T were established.

Key words: Thermal decomposition, 5,5'-Bis(tetrazole)-1,1'-diolate(TKX-50) anion, Activation energy barrier, Density functional theory

ZHAO Shengxiang, ZHAO Ying, XING Xiaoling, JU Xuehai. Decomposition Mechanism of 5,5'-Bis(tetrazole)-1,1'-diolate(TKX-50) Anion Initiated by Intramolecular Oxygen Transfer[J]. 高等学校化学研究, 2019, 35(3): 485-489.

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Decomposition Mechanism of 5,5'-Bis(tetrazole)-1,1'-diolate(TKX-50) Anion Initiated by Intramolecular Oxygen Transfer

Decomposition Mechanism of 5,5'-Bis(tetrazole)-1,1'-diolate(TKX-50) Anion Initiated by Intramolecular Oxygen Transfer

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