Influence of a Bridging Group and the Substitution Effect of Bis(1,2,4-triazine) N-Donor Extractants on Their Interactions with a Np-V Cation
文献类型：期刊论文
| 作者 | Yang X(杨霞); Liang YN(梁艳妮); Yang, X; Liang, YN; Ding, SD; Li, SJ; Chai, ZF; Wang, DQ; Chai ZF(柴之芳) ; Wang DQ(王东琪)
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| 刊名 | INORGANIC CHEMISTRY
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| 出版日期 | 2014 |
| 卷号 | 53期号:15页码:7848-7860 |
| 英文摘要 | The present theoretical study provides a realistic bonding characteristics of a variety of neptunyl complexes evaluation of the equilibrium structure, reaction modes, and formed with bis(triazinyl) N-donor extractants, which differ in their bridging groups such as pyridine, bipyridines, and orthophenanthroline, corresponding to the ligands (L) of tridentate bis(triazinyl)pyridines and tetradentate bis(triazinyl)-bipyridines and bis(triazinyl)-1,10-phenanthrolines (BTPhens), respectively. Our calculations show that coordination of [NpO2](+) to tetradentate ligands is more favorable than that to tridentate ones no matter in a gas, aqueous, or organic phase. The presence of nitrate ions can enhance the coordination ability of neptunyl and stabilize the neutral NpO2L(NO3) complexes in thermodynamics. Our studies indicate that the complexation reaction mode [NpO2(H2O)(n)](+) + L + NO3-) NpO2L(NO3) + nH(2)O is the most probable at the interface between water and the organic phase. The contribution of an orthophenanthroline bridging group is relatively more pronounced compared to its pyridine counterpart in ligand-exchange reaction. Complexation reactions of hydrated neptunyl with C2-BTPhen and BTPhen assisted by a nitrate ion are favorable thermodynamically, resulting from the least deformation of the ligand and strong complexation stability. The quantum theory of atoms-in-molecules and charge decomposition analysis suggest that electron delocalization and charge transfer are the main reasons responsible for stabilization of the tetradentate complexes and reveal a strong ionic feature of the Np-ligand bonds. Inspection of the frontier molecular orbitals reveals a distinct Sf orbital (Np) interaction with ligand atoms, implying the extent of f-based covalenc-y. Our study may facilitate the rational design of ligands toward the improvement of their binding ability with Np-V and more efficient separation of Np in spent nuclear fuels. |
| 学科主题 | Chemistry |
| 收录类别 | SCI |
| WOS记录号 | WOS:000339982400010 |
| 公开日期 | 2016-05-03 |
| 源URL | [http://ir.ihep.ac.cn/handle/311005/225034]  |
| 专题 | 高能物理研究所_院士 |
| 推荐引用方式 GB/T 7714 | Yang X,Liang YN,Yang, X,et al. Influence of a Bridging Group and the Substitution Effect of Bis(1,2,4-triazine) N-Donor Extractants on Their Interactions with a Np-V Cation[J]. INORGANIC CHEMISTRY,2014,53(15):7848-7860. |
| APA | 杨霞.,梁艳妮.,Yang, X.,Liang, YN.,Ding, SD.,...&王东琪.(2014).Influence of a Bridging Group and the Substitution Effect of Bis(1,2,4-triazine) N-Donor Extractants on Their Interactions with a Np-V Cation.INORGANIC CHEMISTRY,53(15),7848-7860. |
| MLA | 杨霞,et al."Influence of a Bridging Group and the Substitution Effect of Bis(1,2,4-triazine) N-Donor Extractants on Their Interactions with a Np-V Cation".INORGANIC CHEMISTRY 53.15(2014):7848-7860. |
入库方式： OAI收割
来源：高能物理研究所
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