Highly Efficient Separation of Actinides from Lanthanides by a Phenanthroline-Derived Bis-triazine Ligand
Highly Efficient Separation of Actinides from Lanthanides by a Phenanthroline-Derived Bis-triazine Ligand
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DOI：
10.1021/ja203378m
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发表时间：
2011-08-24
影响因子：
15
通讯作者：
Simonin, Jean-Pierre
中科院分区：
文献类型：
--
作者：
Lewis, Frank W.;Harwood, Laurence M.;Simonin, Jean-Pierre
本文报道了邻菲咯啉四齿双三嗪配体的合成、镧系元素络合和从硝酸溶液中萃取镧系元素(III)放射性示踪剂。与2，2‘-联吡啶相比，该配体具有显著的高效率、高选择性和快速的萃取动力学，可将Am(III)和Cm(III)与稀土元素分离。用X射线结晶学和力场计算分别确定了该配体与Eu(III)和Yb(III)的1：2双配合物的结构。Eu(III)双配合物是第一个用结晶学表征的四齿双三嗪配体的1：2双配合物。在几种稀释剂中，采用旋转膜池技术进行动力学测量，证实了较快的萃取速度。金属离子萃取动力学的改善与配位体在相界面具有较高的表面活性有关。用邻菲咯啉单元取代联吡啶单元对配体性质的改善远远超过仅基于配体设计的预期。
The synthesis, lanthanide complexation, and solvent extraction of actinide(III) and lanthanide(III) radiotracers from nitric acid solutions by a phenanthroline-derived quadridentate bis-triazine ligand are described. The ligand separates Am(III) and Cm(III) from the lanthanides with remarkably high efficiency, high selectivity, and fast extraction kinetics compared to its 2,2'-bipyridine counterpart. Structures of the 1:2 bis-complexes of the ligand with Eu(III) and Yb(III) were elucidated by X-ray crystallography and force field calculations, respectively. The Eu(III) bis-complex is the first 1:2 bis-complex of a quadridentate bis-triazine ligand to be characterized by crystallography. The faster rates of extraction were verified by kinetics measurements using the rotating membrane cell technique in several diluents. The improved kinetics of metal ion extraction are related to the higher surface activity of the ligand at the phase interface. The improvement in the ligand's properties on replacing the bipyridine unit with a phenanthroline unit far exceeds what was anticipated based on ligand design alone.