高等学校化学学报

高等学校化学学报

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非血红素配合物[FeⅣ(O)(TMC)(NCMe)]2+与[FeⅣ(O)(TMCS)]+的几何结构、电子结构、成键性和反应活性比较

王一, 王永, 韩克利   

  1. 中国科学院大连化学物理研究所分子反应动力学国家重点实验室, 大连 116023
  • 收稿日期:2008-10-13 修回日期:1900-01-01 出版日期:2008-12-10 发布日期:2008-12-10
  • 通讯作者: 韩克利

Comparison Between [FeⅣ(O)(TMC)(NCMe)]2+ and [FeⅣ(O)(TMCS)]+ Non-heme Complexes of Geometric, Electronic Structures, Bonding and Reactivities

WANG Yi, WANG Yong, HAN Ke-Li*   

  1. State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
  • Received:2008-10-13 Revised:1900-01-01 Online:2008-12-10 Published:2008-12-10
  • Contact: HAN Ke-Li

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被引次数

4

摘要： 采用密度泛函理论计算了[FeⅣ(O)(TMC)(NCMe)]2+ 和[FeⅣ(O)(TMCS)]+的电子结构、反应活性和Fe—O的成键性. 几何构型的优化采用非限制性的B3LYP混合密度泛函方法, 重原子Fe的优化采用是LanL2dZ基组, C, H, O, N和S的优化采用TZV基组, 理论计算结果与实验结果相符. 通过对轨道系数和键级的分析发现, TMC配位基对Fe—O的π键几乎没有影响. 由于竖直方向的硫甲基配位基的轨道与Fe的3d轨道具有较强的重迭, 而乙腈配位基作为轴向配体时, 这种重迭则小得多, 导致了两种配合物在电子结构和反应活性上存在一定的差别.

关键词: 非血红素, 轨道系数, 电子结构, 密度泛函理论计算

Abstract: Density functional theory(DFT) calculations were carried out to elucidate the electronic structures, Fe—O bondings and reactivities of six-coordinated [FeⅣ(O)(TMC)(NCMe)]2+ and [FeⅣ(O)(TMCS)]+ complexes. The geometric parameters calculated by a hybrid functional UB3LYP with LanL2DZ(Fe) and TZV(rest) basis set were in agreement with the experimental data. Analysis of the orbital coefficients and the bond orders showed that the TMC ligand does not have any equivalent orbitals that are affecting the Fe—O π bond. Due to the strong mixing of the iron 3d orbitals with the σ orbital of the thiolate ligand orbitals and a much less mixing with the acetonitrile as an axial ligand, the electronic properties of [FeⅣ(O)(TMC)(NCMe)]2+ and [FeⅣ(O)(TMCS)]+ are different and the Fe—O bond length of the [FeⅣ(O)(TMCS)]+ complex is longer than that of the [FeⅣ(O)(TMC)(NCMe)]2+ complex.

Key words: Non-heme, Orbital coefficient, Electronic structure, Density functional theory calculation

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