几种过渡金属混配配合物的构型和量子化学研究

对几种五配位的过渡金属配合物晶体结构构型进行了详细讨论,通过扭曲角的计算证明它们均为正三角双锥(TBP)和正向四方锥(TP)的过渡构型。运用AM1量子化学计算方法,对混配体的一些物理化学参数,特别是配位N原子轨道对前线轨道的贡献进行了研究。结果表明,配位N原子轨道对前线轨道的贡献不大,而且也不影响配位构型的变化。计算还表明大多数以三(2-苯并咪唑亚甲基)胺为配体的过渡金属配合物均具有扭曲的三角双锥构型,而铜配合物的构型随协同配体的不同,在正三角双锥和正向四方锥之间的变化范围很大,这是由于铜离子较强的John-Teller效应造成的。

Configurations and Quantum Chemical Studies of Transitional Metal Mixed Complexes

The five-donated crystal configurations of several transition metal complexes are discussed in detail. Their distorted directions (towards TBP or TP) and distorted degree are illustrated through the torsional angles. Some physico-chemical parameters and contributions of atomic orbitals (AO) of coordinated nitrogen atoms to the molecular orbitals (MO) are also studied by AM1quantum chemical calculation. All of the results show that AOs of the coordinated N atoms do not contribute much to the frontier MOs as well as the configurations. As to most complexes with tris(2-benzimidazylmethyl)amine ligands, their configurations are all distorted towards TBP. When copper(II) complexes are concerned, the case is quite different because of the Jahn-Teller effect.