Quantum Chemistry Study of Uranium(VI), Neptunium(V), and Plutonium(IV,VI) Complexes with Preorganized Tetradentate Phenanthrolineamide Ligands

	Quantum Chemistry Study of Uranium(VI), Neptunium(V), and Plutonium(IV,VI) Complexes with Preorganized Tetradentate Phenanthrolineamide Ligands
	Xiao CL(肖成梁); Wu QY(吴群燕); Wang CZ(王聪芝); Xiao, CL; Wu, QY; Wang, CZ; Zhao, YL; Chai, ZF; Shi, WQ; Zhao YL(赵宇亮)
刊名	INORGANIC CHEMISTRY
	2014
卷号	53 期号:20 页码:10846-10853
英文摘要	The preorganized tetradentate 2,9-diamido-1,10-phenanthroline ligand with hardsoft donors combined in the same molecule has been found to possess high selectivity toward actinides in an acidic aqueous solution. In this work, density functional theory (DFT) coupled with the quasi-relativistic small-core pseudopotential method was used to investigate the structures, bonding nature, and thermodynamic behavior of uranium(VI), neptunium(V), and plutonium(IV,VI) with phenanthrolineamides. Theoretical optimization shows that Et-Tol-DAPhen and Et-Et-DAPhen ligands are both coordinated with actinides in a tetradentate chelating mode through two N donors of the phenanthroline moiety and two O donors of the amide moieties. It is found that [AnO(2)L(NO3)](n+) (An = U-VI, Np-V, Pu-VI; n = 0, 1) and PuL(NO3)(4) are the main 1:1 complexes. With respect to 1:2 complexes, the reaction [Pu(H2O)(9)](4+) (aq) + 2L(org) + 2NO(3)(-) (aq) -> [PuL2(NO3)(2)](2+) (org) + 9H(2)O(aq) might be another probable extraction mechanism for Pu-IV. From the viewpoint of energy, the phenanthrolineamides extract actinides in the order of Pu-IV > U-VI > Pu-VI > Np-V, which agrees well with the experimental results. Additionally, all of the thermodynamic reactions are more energetically favorable for the Et-Tol-DAPhen ligand than the Et-Et-DAPhen ligand, indicating that substitution of one ethyl group with one tolyl group can enhance the complexation abilities toward actinide cations (anomalous aryl strengthening).
学科主题	Chemistry
收录类别	SCI
WOS记录号	WOS:000343527700012
公开日期	2016-05-03
内容类型	期刊论文
源URL	[http://ir.ihep.ac.cn/handle/311005/225037]
专题	高能物理研究所_院士高能物理研究所_多学科研究中心
推荐引用方式 GB/T 7714	Xiao CL,Wu QY,Wang CZ,et al. Quantum Chemistry Study of Uranium(VI), Neptunium(V), and Plutonium(IV,VI) Complexes with Preorganized Tetradentate Phenanthrolineamide Ligands[J]. INORGANIC CHEMISTRY,2014,53(20):10846-10853.
APA	肖成梁.,吴群燕.,王聪芝.,Xiao, CL.,Wu, QY.,...&石伟群.(2014).Quantum Chemistry Study of Uranium(VI), Neptunium(V), and Plutonium(IV,VI) Complexes with Preorganized Tetradentate Phenanthrolineamide Ligands.INORGANIC CHEMISTRY,53(20),10846-10853.
MLA	肖成梁,et al."Quantum Chemistry Study of Uranium(VI), Neptunium(V), and Plutonium(IV,VI) Complexes with Preorganized Tetradentate Phenanthrolineamide Ligands".INORGANIC CHEMISTRY 53.20(2014):10846-10853.