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Effect of Counteranions on the Extraction and Complexation of Trivalent Lanthanides with Tetradentate Phenanthroline-Derived Phosphonate Ligands
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-11-20 , DOI: 10.1021/acs.inorgchem.0c02728
Xiao Yang 1 , Lei Xu 1 , Yuxun Hao 1 , Ruixue Meng 1 , Xingwang Zhang 1 , Lecheng Lei 1 , Chengliang Xiao 1
Affiliation  

Soft–hard-donor-combined ligands are a type of promising extractant for actinide and lanthanide separation. In this work, the effects of counteranions (Cl, NO3, and ClO4) on the extraction and complexation behaviors of a recently reported tetradentate phenanthroline-derived phosphonate (POPhen) ligand toward lanthanides were thoroughly investigated using solvent extraction, NMR titration, UV–vis titration, and single-crystal X-ray diffraction measurements. It is found that C4-POPhen showed excellent extraction and selectivity toward heavy lanthanides [Lu(III)] compared to light lanthanides, particularly with the counterion of ClO4 and at low acidity. NMR titration studies demonstrated that both 1:1 and 1:2 Lu(III)/C4-POPhen complexes were formed in a CD3OD solution with all three counteranions and the 1:2 species was easier to form in a complexation of C4-POPhen with Lu(ClO4)3 under the same conditions. Furthermore, the stability constants of Nd(III) complexation with C4-POPhen in the counteranions of Cl, NO3, and ClO4 systems were determined through UV–vis titration, and a much larger value of log β of complexes was found in the ClO4 system, which was in good agreement with the results of solvent extraction. In addition, the structures of C2-POPhen complexation with Ln(NO3)3/Ln(ClO4)3 in the solid state were clearly unraveled by the single-crystal X-ray diffraction technique. This work demonstrated that the solvent extraction and complexation mechanisms of POPhen ligands with Ln(III) were significantly affected by the counteranions from both the solution and solid-state aspects, which might shed light on the lanthanide/actinide separation.

中文翻译:

抗衡阴离子对四齿菲咯啉衍生的膦酸酯配体萃取和络合三价镧系元素的影响

软-硬供体结合的配体是一种有前途的萃取剂,可用于act系元素和镧系元素的分离。在这项工作中,使用溶剂萃取,NMR彻底研究了抗衡阴离子(Cl ,NO 3 和ClO 4 )对最近报道的四齿菲咯啉衍生的膦酸酯(POPhen)配体对镧系元素的萃取和络合行为的影响。滴定,UV-vis滴定和单晶X射线衍射测量。研究发现,与轻质镧系元素相比,C4-POPhen对重镧系元素[Lu(III)]的萃取和选择性极好,尤其是与ClO 4 酸度低。NMR滴定研究表明,在CD 3 OD溶液中,所有三种抗衡阴离子均形成1:1和1:2 Lu(III)/ C4-POPhen络合物,而在C4-络合物中更容易形成1:2物种在相同条件下具有Lu(ClO 43的POPhen 。此外,钕(III)络合与C4-POPhen在Cl组成的抗衡阴离子的稳定常数-,NO 3 - ,和C10 4 -系统是通过紫外-可见滴定法测定,和配合物的日志β的更大值在ClO 4中发现系统,与溶剂萃取的结果非常吻合。另外,通过单晶X射线衍射技术清楚地阐明了C2-POPhen与Ln(NO 33 / Ln(ClO 43的固态络合的结构。这项工作表明,POPhen配体与Ln(III)的溶剂萃取和络合机理从溶液和固态两个方面都受到抗衡阴离子的显着影响,这可能有助于镧系元素/ act系元素的分离。
更新日期:2020-12-07
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