摘要
在B3LYP/aug-cc-pvDZ水平上研究了叠氮基-1,4-四嗪分子构型、电子结构及叠氮-四唑异构化反应历程.采用NBO和AIM方法分析了异构化过程中各原子电荷和电子拓扑性质.结果表明:叠氮-四唑异构化反应始于叠氮基失去直线构型,叠氮基终端上的N9原子向环上N2原子接近,N2原子上的孤对电子进攻叠氮基,最终在N2和N9原子间成键形成四唑异构体.叠氮基中N—N—N键角的弯曲,闭环过程中电子的重新分布等因素使得反应具有较高的活化能.
B3LYP/aug-cc-pvDZ level of theory is applied to study the molecular structures,electronic structures and azido-tetrazole isomerization of azido-tetrazine in this paper.NBO and AIM analyses are applied to investigate the atomic charge and the bonding properties of molecules.The results show that the reaction proceeds initially through loss of the linearity of the azido group,with the terminal nitrogen N9 atom of the azide group approaching to the nitrogen atom N2 of the ring.This step is then followed by the attack of the lone pair on N2 to the azido group,leading to formation of the bond between N2 and N9.The bending of the N—N—N angle in the azido and the redistribution of electron density associated to these events give rise to a large activation energy for the reaction.
出处
《四川师范大学学报（自然科学版）》
CAS
CSCD
北大核心
2010年第1期83-88,共6页
Journal of Sichuan Normal University（Natural Science）
基金
国家自然科学基金(20373045)资助项目
