几个P-ylide反应机理的量子拓扑研究  

Quantum Topological Analysis of Two P-ylide Reactions

作　　者：曾艳丽[1] 郑世钧[1] 孟令鹏[1] 

机构地区：[1]河北师范大学计算量子化学研究所,石家庄050091

出　　处：《Chinese Journal of Chemical Physics》2001年第1期57-64,共8页化学物理学报（英文）

基　　金：河北省自然科学基金&&

摘　　要：采用MP2 (FC) / 6- 311++G(d ,p)对磷叶立德和类磷叶立德自由基反应机理进行了探讨。优化了中间体、过渡态和产物的几何构型 ,并采用内禀反应坐标法进行追踪。侧重从量子拓扑学的角度 ,对反应过程中各点进行电子密度拓扑分析 ,讨论了反应过程中化学键的断裂、生成和化学键的变化规律。上述两个反应都经历三员环过渡态 ,找到了这类反应的能量过渡态和结构过渡态。The reaction paths for P-ylide and P-ylide-like radical were discussed. The investigation of the topological properties of the chemical bonds was emphasized on. The following conclusions are given: After the energy transition states (ETS), Δ type transition structures appear in both of the two reactions. The mistakes in the previous paper by Brain F. Yates are pointed out and corrected: The Δ type transition structures are the “structure transition state” (ETS), not the “energy transition state” (STS). For the two exothermic elementary reactions, the structure transition states (STS) both appear after the energy transition states (ETS), which are consistent with the conclusions we have given before. According to the topological properties, the changing trends of the P 2-H 3 bonds and C 1-H 3 bonds are consistent in both the P-ylide and the P-ylide-like radical reactions.

关 键 词：磷叶立德 类磷叶立德自由基 结构过渡态 能量过渡态 有机反应中间体 反应机理 量子拓扑 

分 类 号：O641[理学—物理化学]