Theoretical study on thermal decomposition of azoisobutyronitrile in ground state  

作　　者：SUN Chengke1,2, ZHAO Hongmei1 & LI Zonghe1 1. Department of Chemistry, Beijing Normal University, Beijing 100875, China 2. Department of Chemistry, Qujing Normal College, Qujing 655000, China 

出　　处：《Science China Chemistry》2004年第5期373-380,共8页中国科学（化学英文版）

基　　金：This work was supported by the National Natural Science Foundation of China(Grant No.29773007);the Natural Science Foundation of Qujing Normal College(Grant No.200009).

摘　　要：The thermal decomposition mechanisms of azoisobutyronitrile (AIBN) in the ground state have been investigated systematically. Based on the potential energy surfaces (PES) of various possible dissociation paths obtained using the semiempirical AM1 method with partial optimization, the density function theory B3LYP/6-311G* method was employed to optimize the geometric parameters of the reactants, the intermediates, the products and the transition states, which were further confirmed by the vibrational analysis. The obtained results show that the re- action process of the two-bond (three-body) simultaneous cleavage Me2(CN)C─ N=N─ C(CN)Me2? 2Me2(CN)C?+N2 is much more favorable than the reaction process of the two one- bond asynchronous cleavage Me2(CN)CN=N─C(CN)Me2 ? Me2(CN)CN=N?+ Me2(CN)C?? Me2(CN)C?+ N2. It was suggested that the electron shrinking effect of double bond (─N=N─) in AIBN and the stabilities of the Me2(CN)C?radical as well as N2 molecule are main factors of leading to the reaction proceeding in the former pathway. The calculation results were consistent with all the experimental facts.The thermal decomposition mechanisms of azoisobutyronitrile (AIBN) in the ground state have been investigated systematically. Based on the potential energy surfaces (PES) of various possible dissociation paths obtained using the semiempirical AM1 method with partial optimization, the density function theory B3LYP/6-311G* method was employed to optimize the geometric parameters of the reactants, the intermediates, the products and the transition states, which were further confirmed by the vibrational analysis. The obtained results show that the reaction process of the two-bond (three-body) simultaneous cleavage Me2(CN)C-N=N-C(CN)Me2→2Me2(CN)C·+N2 is much more favorable than the reaction process of the two one-bond asynchronous cleavage Me2(CN)CN=N-C(CN)Me2→Me2(CN)CN=N·+Me2(CN)C·→Me2(CN)C·+N2. It was suggested that the electron shrinking effect of double bond (?N=N?) in AIBN and the stabilities of the Me2(CN)C· radical as well as N2 molecule are main factors of leading to the reaction proceeding in the former pathway. The calculation results were consistent with all the experimental facts.

关 键 词：azoisobutyronitrile  radicals  thermal decomposition  DENSITY function theory (DFT). 

分 类 号：O621.2[理学—有机化学]