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Theoretical Investigation on the Mechanism and Design of Catalysts for Nitrolysis of Hexamine
Author(s) -
Shi Liangwei,
Zhao Gang,
Zhang Yazhu,
Zheng Changwu,
Qin Guangming,
Lü Jian
Publication year - 2010
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.201090264
Subject(s) - chemistry , catalysis , acetylation , nonane , mechanism (biology) , potential energy surface , nitro , computational chemistry , reaction mechanism , medicinal chemistry , organic chemistry , molecule , biochemistry , philosophy , alkyl , epistemology , gene
The mechanism of nitrolysis of hexamine (HA) by DFT method has been explored to understand the classical organic reaction and assist the design of new catalyst. The potential energy surface of NO + 2 was firstly investigated. A reasonable configuration evolution of NO + 2 during the process of its reaction with HA was figured out. The role of H + and NH + 4 for the nitrolysis of HA was analyzed and discussed. The route of nitrolysis reaction from HA to 1‐acetoxylmethene‐3‐nitro‐tetrazabicyclo[3,3,1]nonane intermediate is similar to that of acetylation of HA. The relative free energy calculation proves the priority of nitrolysis relative to acetylation. Two types of Lewis salts, M(OSO 2 CF 3 ) 3 and M[N(SO 2 CF 3 ) 2 ] 3 (M: Yb, Sm, Y, and Eu), are designed on the basis of discussed mechanism. The calculation for the key bond order in IM2[CH 2 R] model intermediates gives an indicator as the preferable catalyst. The experimental results support the theoretical conclusion.