摘要
采用分子片近似模型,应用量子化学UB3LYP方法在6-31G*和6-311G*水平上,对具有代表性的偶氮烷解离成自由基的反应进行了系统的理论研究和结构解析.研究表明,偶氮烷R-N=N-R′解离成自由基的反应机理,是采取两个C-N键同步解离,还是分步解离,是由偶氮烷的结构特征和取代基R和R′所形成的自由基R.和R′.的稳定性所决定,若R.和R′.共轭性越强越稳定,则两键解离途径越有利.另外还总结了能够实现两键(三体)解离的偶氮烷分子具有的特征.
The model of molecular fragments and the approximation of virtual three-atom were employed to investigate systematically and analyze the structure characteristics on the thermal decomposition of azoalkanes in ground state using UB3LYP method at 6-31G^＊ and 6-311G^＊ levels.The results show that the reaction micro-paths of azoalkanes R-N=N-R′ cleaving to free radicals,i.e.whether azoalkanes lose nitrogen by simultaneous cleavage of both C-N bonds or whether they proceed via a diazenyl radical,have been determined from structure characteristics of their molecules and the stability of formed free radical R and R′·;the more strong conjugated effect of R and R′,the more profitably it cleaves.The general rule and the molecular characteristics of azoalkanes that could represent two-bond（three-body） cleavage reaction were also summarized systematically.
出处
《曲靖师范学院学报》
2010年第3期1-14,共14页
Journal of Qujing Normal University
基金
国家自然科学基金项目(20763007)
云南省科技厅应用基础研究基金项目(2006C0083M)阶段性研究成果
