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化学学报
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化学学报 ›› 2006, Vol. 64 ›› Issue (20): 2071-2078. 上一篇    下一篇

研究论文

Ru(II)催化有机叠氮与炔反应机理的理论研究

周玉炳1, 柯卓锋2, 赵存元*,2   

  1. (1河西学院化学系 张掖 734000)
    (2中山大学化学与化学工程学院 广州 510275)
  • 投稿日期:2006-01-11 修回日期:2006-05-22 发布日期:2006-10-28
  • 通讯作者: 赵存元

A Theoretical Study on the Mechanism of Ruthenium(II)-catalyzed Reaction of Organic Azide with Alkyne

ZHOU Yu-Bing1; KE Zhuo-Feng2; ZHAO Cun-Yuan*,2   

  1. (1 Department of Chemistry, Hexi University, Zhangye 734000)
    (2 School of Chemistry & Chemical Engineering, Sun Yat-Sen Univer-sity, Guangzhou 510275)
  • Received:2006-01-11 Revised:2006-05-22 Published:2006-10-28
  • Contact: ZHAO Cun-Yuan

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采用密度泛函理论, 对在Ru(II)催化剂存在下, 有机叠氮化合物和末端炔的反应机理作了深入理论研究. 在B3LYP/LANL2DZ水平上, 对该反应体系中势能面各驻点的几何构型进行了全优化计算, 并经振动频率分析确定了过渡态和中间体, 通过内禀反应坐标(IRC)的计算, 确认了反应物、中间体、过渡态和产物的相关性. 对多个反应通道的协同反应以及分步反应进行了研究. 结果表明: 协同反应通道Ic和分步反应通道IIc是反应能垒较低的反应通道, 活化自由能较其它反应通道低, 有利于1,5-二取代1,2,3-三唑的生成, 具有特定的区域选择性, 与实验结果吻合.

关键词: 密度泛函理论, Ru(II)催化, 叠氮, 炔, 反应机理

The mechanisms of the ruthenium(II)-catalyzed reaction of organic azide with terminal alkyne have been investigated using density functional theory. All the stationary points on the potential energy surfaces were fully optimized at the B3LYP/LANL2DZ level of theory. The reactants, intermediates, transition states and products in the reaction pathways were examined by frequency analysis at the same level of theory. Intrinsic reaction coordinate (IRC) calculations were performed to confirm that the optimized transition states correctly connect the relevant reactants and products. The investigation of the concerted and stepwise reaction channels shows that the concerted channel Ic and the stepwise channel IIc are favored over other channels to produce 1,5-disubstituted 1,2,3-triazole, which is in good agreement with experimental re-sults.

Key words: density functional theory, ruthenium(II)-catalyzed, azide, alkyne, reaction mechanism