化学学报 ›› 1994, Vol. 52 ›› Issue (6): 556-561. 上一篇    下一篇

研究论文

环丙基氮烯开, 闭环异构化反应理论研究

孙华斌;刘成卜;邓从豪   

  1. 山东大学化学院理论化学研究室
  • 出版日期:1994-06-15 发布日期:1994-06-15

Mechanism of the isomerization by ring opening and closing of singlet cyclopropyl nitrene

SUN HUABIN;LIU CHENGBU;DENG CONGHAO   

  • Online:1994-06-15 Published:1994-06-15

应用量子化学理论方法研究了单重态环丙基氮烯开, 闭环异构化反应, 找到了反应的过渡态, 发现该反应具有对旋-顺旋机理, 应用Woodward-Hoffmann讨论了这一反应机理, 计算了环丙基氮烯单重态和三重态的分裂能以及该反应的活化势垒和反应能量, 给出了反应物, 过渡态和产物的有机结构数据。

关键词: 反应机理, 环丙烷 P, 闭环反应, 开环反应, 伍德沃德-霍夫曼定则, 单重态, 三重态, 氮烯, 异构化, 国家教委高等学校博士学科点专项科研基金

The isomerization by ring opening and closing of singlet cyclopropyl nitrene has been studied using RHF method with STO-3G and 6-31G basis sets. The transition state has been obtained. The disrotation-conrotation mechanism has been proposed and discussed with Woodward-Hoffmann rules. Barrier height for the ring opening is 45.64kJ/mol. Triplet cyclopropyl nitrene is calculated which has lower energy than single one by 213.94 kJ/mol (6-31G level). The relative structure data have been given.

Key words: REACTION MECHANISM, CYCLOPROPANE P, RING CLOSURE REACTION, RING CLEAVAGE REACTION, WOODWARD-HOFFMANN RULE, SINGLET, TRIPLET, IMIDOGEN, ISOMERIZATION

中图分类号: