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本文用INDO方法计算了希土冠醚配合物的分子构型、电子结构、电荷分布和键级,讨论了配位前后电荷分布特征,以及由于配位引起L→L_n电荷转移跟配合物电子结合能化学位移和配位活化的关系,解释了因冠醚内腔不同希土冠醚配合物呈现不同构型的内在原因。希土冠醚配合物的占据分子轨道以配位体轨道成分为主体(4f轨道除外),低空轨道以希土原子轨道成分为主体。其占据分子轨道可分为六组。冠醚环上引入苯环后配合物前线轨道呈现π键性质。其价键的主要贡献部份是5d轨道,其次是6p和6s。4f轨道基本上不参与成键。讨论了配合物的化学键性质及高配位数时稳定的因素。
In this paper, the molecular configuration, electronic structure, charge distribution and bond order of the crown earth ether complex were calculated by INDO method. The distribution of the charge before and after the coordination was discussed, and the electron transfer The relationships between chemical shifts and coordination activation explain the intrinsic causes of the different configurations of crown ether ethers due to different crown ethers. The dominant molecular orbitals of the rare earth crown ether complexes are dominated by ligand orbital components (except for the 4f orbit), and the low-altitude orbitals are dominated by the orbital orbitals of the earth. Its occupation of molecular orbit can be divided into six groups. The introduction of the benzene ring on the crown ether ring showed π-bond frontier orbital. The key contribution of its key part of the 5d track, followed by 6p and 6s. 4f track is basically not involved in the key. The chemical bond properties of the complex and the factors of stability at high coordination number are discussed.