Computational chemical analysis of Eu(iii) and Am(iii) complexes with pnictogen-donor ligands using DFT calculations
Computational chemical analysis of Eu(iii) and Am(iii) complexes with pnictogen-donor ligands using DFT calculations
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DOI：
10.1039/c8dt01973h
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发表时间：
2018-11-14
影响因子：
4
通讯作者：
Nakashima, Satoru
中科院分区：
文献类型：
--
作者：
Kimura, Taiki;Kaneko, Masashi;Nakashima, Satoru
用密度泛函方法计算了(CH3)(2)X-CH2-X(CH3)(2)(X=N，P，As和Sb)与Eu(III)和Am(III)的配合物。我们研究了络合物的优化结构和络合物形成反应中的吉布斯能量差。结果表明，N-和P-供体配体对Eu(III)离子表现出较高的选择性，其中P-供体配体的选择性最高。PNictogen供体配体对Am(III)/Eu(III)选择性的趋势与硬软酸碱规则中软酸分类的趋势相似。Mulliken的自旋布居分析表明，金属离子与Pnitogen原子之间的成键性质与Am(III)/Eu(III)的选择性有关。特别是，金属离子的f轨道电子参与共价性对选择性起着重要作用。
We demonstrated density functional calculations of Eu(iii) and Am(iii) complexes with pnictogen-donor (X) ligands, (CH3)(2)X-CH2-CH2-X(CH3)(2) (X = N, P, As and Sb). We investigated the optimized structures of the complexes and the Gibbs energy differences in the complex formation reactions. The results indicated that the N- and P-donor ligands exhibit Am(iii) ion selectivity over Eu(iii) ions; especially, the P-donor ligand showed the highest selectivity. The tendency of the Am(iii)/Eu(iii) selectivity by the pnictogen-donor ligands was found to be comparable to that of the soft acid classification in the hard and soft acids and bases rule. Mulliken's spin population analysis indicated that the bonding properties between the metal ion and the pnictogen atoms correlated with the Am(iii)/Eu(iii) selectivity. In particular, the participation of f-orbital electrons of the metal ion in the covalency was indicated to play an important role in the selectivity.