化学学报 ›› 2009, Vol. 67 ›› Issue (15): 1784-1790. 上一篇    下一篇

研究论文

双β-二酮配体配位性的理论研究

罗世霞a 张笑一*,a 朱淮武a 胡继伟b 卫 钢*,c

  

  1. (a贵州师范大学化学与材料科学学院 贵阳 550001)
    (b贵州省山地环境信息系统和生态环境保护重点实验室 贵阳 550001)
    (c CSIRO Materials Science and Engineering, PO Box 218, Lindfield, NSW2070, Australia)

  • 收稿日期:2008-10-05 修回日期:2009-05-11 出版日期:2009-08-14 发布日期:2009-08-14
  • 通讯作者: 张笑一

Theoretical Studies on Complexation of Bis-β-diketonato Ligands

Luo, Shixiaa Zhang, Xiaoyi*,a Zhu, Huaiwua Hu, Jiweib Wei, Gang*,c

  

  1. (a School of Chemistry and Materials Science, Guizhou Normal University, Guiyang 550001)
    (b Guizhou Provincial Key Laboratory for Information System of Mountainous Areas and Protection of Ecological
    Environment, Guiyang 550001)
    (c CSIRO Materials Science and Engineering, PO Box 218, Lindfield, NSW2070, Australia)
  • Received:2008-10-05 Revised:2009-05-11 Online:2009-08-14 Published:2009-08-14
  • Contact: Zhang, Xiaoyi

基于自洽反应场(SCRF)中的极化连续介质模型(PCM), 采用密度泛函理论B3LYP/6-31G**计算了以二硫醚和芳环为桥基的两类双β-二酮配体的空间构型和电子结构, 结合其配合物晶体结构数据, 研究配体分子电子结构与配位性的关联性. 结果表明, 配体分子的几何构型、前线轨道、偶极矩和电荷布居, 与配合物构型、活性配位原子和配位形式(单核或多核、分子内或分子间)之间的关联性与一致性十分有意义. 配体的理论计算研究可以在一定层次上为配合物几何结构特征和配位特性提供合理的分析与预测.

关键词: 双β-二酮配体, 配位性, 密度泛函理论, 电子结构

By applying density functional theory (DFT), the relationships between the electron structures and the complexation of the two types of bis-β-diketone ligands (dithiol-γ-linked or alkyl-γ-linked) were investigated, based on the polarized continuum model (PCM) of the self-consistent reaction field (SCRF). Using the model B3LYP/6-31G**, the geometries of the ligands were optimized and the electron structure changes calculated. The calculation results, in comparison with the crystal data of the complexes, indicated that there were clear correlativity and consistency of the geometries, frontier orbitals, dipole moments and net charges of the ligands with the geometries, active atoms, and forms (mono- or poly-nuclear, inter- or intra-molecular) of the complexes. It is therefore demonstrated that the theoretical calculations of ligands can provide a reasonable analysis and prediction for the geometries and complexation of complexes.

Key words: bis-β-diketone ligand, complexation, density functional theory, electron structure

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