物理化学学报 >> 2011, Vol. 27 >> Issue (11): 2565-2570.doi: 10.3866/PKU.WHXB20111127

理论与计算化学 上一篇    下一篇

镁卟啉与氮、氧杂环化合物的相互作用

许惠英1, 王维2   

  1. 1. 浙江树人大学生物与环境工程学院, 杭州 310015;
    2. 镇海环境监测站, 浙江宁波 315200
  • 收稿日期:2011-07-04 修回日期:2011-09-04 发布日期:2011-10-27
  • 通讯作者: 许惠英 E-mail:xuhy65@163.com
  • 基金资助:

    浙江省教育厅科研项目(Y200803060)资助

Interaction between Mg-Porphyrin and Nitrogen, Oxygen Heterocyclic Compounds

XU Hui-Ying1, WANG Wei2   

  1. 1. College of Biology & Environment Engineering, Zhejiang Shuren University, Hangzhou 310015, P. R. China;
    2. Zhenhai Environmental Monitoring Station, Ningbo 315200, Zhejiang Province, P. R. China
  • Received:2011-07-04 Revised:2011-09-04 Published:2011-10-27
  • Contact: XU Hui-Ying E-mail:xuhy65@163.com
  • Supported by:

    The project was supported by the Program of Education Department of Zhejiang Province, China (Y200803060).

摘要: 以镁卟啉为主体化合物, 模拟了生物体内常见的氮、氧杂环客体与主体化合物之间的相互作用. 研究结果表明: 镁卟啉与氮、氧杂环化合物的相互作用引起了镁卟啉中的镁原子与卟吩环不共面, 且二面角越小不共面程度越大. 自然键轨道(NBO)理论分析表明氮、氧孤对电子和金属镁的空孤对轨道的相互作用对复合物的稳定性贡献很大. 使用约化密度梯度(RDG)函数等值面图和散点图可视化分析了配位相互作用和周边氢键作用的位置及强度. 概念密度泛函(DFT)理论参数表明所形成的复合物比主体化合物的热力学稳定性小而反应活性高. 芳香性计算表明含氧杂环客体与主体的相互作用使复合物中的卟吩环具有反芳香性, 而含氮杂环客体与主体的相互作用使复合物中卟吩环呈现区域性芳香性.

关键词: 镁卟啉, 约化密度梯度函数等值面图, 配位相互作用, 自然键轨道理论, 芳香性

Abstract: The interaction between nitrogen-oxygen heterocyclic compounds and a host (magnesium porphyrin) was investigated. The results showed that the magnesium atoms in the magnesium porphyrin and porphin ring were not coplanar and at a smaller dihedral angle the extent of its non-coplanar nature increased. Natural bond orbital (NBO) analysis indicated that the interaction between the lone pair of electrons on the nitrogen and oxygen atoms and the unoccupied lone pair orbital of magnesium contributes significantly to the stability of the complexes. The reduced density gradient (RDG) isosurface map and the scatter diagram indicated the location and intensity of the axial coordination interactions and the surrounding hydrogen bonding interactions. The conceptual density functional theory (DFT) parameter indicated that the complex compounds are less thermodynamically stable than magnesium porphyrin, however, they have higher reactivity. Aromatic calculations revealed that the interaction between the oxygen-containing heterocycles and the host compound made the porphin ring in the complexes anti-aromatic while the interaction between the nitrogen-containing heterocyclic and the host made the porphin ring in the complexes regionally aromatic.

Key words: Magnesium porphyrin, RDG iso-surface map, Coordination interaction, Natural bond orbital, Aromaticity

MSC2000: 

  • O641