Unraveling the complexation mechanism of actinide(III) and lanthanide(III) with a new tetradentate phenanthroline-derived phosphonate ligand,Inorganic Chemistry Frontiers

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Unraveling the complexation mechanism of actinide(III) and lanthanide(III) with a new tetradentate phenanthroline-derived phosphonate ligand
Inorganic Chemistry Frontiers ( IF 6.1 ) Pub Date : 2020-03-16 , DOI: 10.1039/d0qi00200c
Lei Xu _{1,

2,

3,

4} , Ning Pu _{4,

5,

6,

7,

8} , Gaoyang Ye _{4,

5,

6,

7,

8} , Chao Xu _{4,

5,

6,

7,

8} , Jing Chen _{4,

5,

6,

7,

8} , Xingwang Zhang _{1,

2,

3,

4} , Lecheng Lei _{1,

2,

3,

4} , Chengliang Xiao _{1,

2,

3,

4}

Affiliation

The extraction and complexation of trivalent Am(III) and lanthanide(III) with a new phenanthroline-derived phosphonate ligand, tetrabutyl-(1,10-phenanthrolin-2,9-diyl)phosphonate (C4-POPhen), were investigated by solvent extraction, absorption spectroscopy, NMR titration, luminescence spectroscopy, and theoretical computation. Selective extraction of Am(III) over Eu(III) from highly acidic HNO₃ solution (up to 3.0 M) with good selectivity and a fast extraction rate was achieved by using the C4-POPhen ligand. The 1 : 2 metal/ligand complex was found to be the predominant species in the extracted organic phase by a slope analysis method. NMR titration results demonstrated that only a 1 : 1 complex of C4-POPhen with Ln(NO₃)₃ was formed in a CH₃OH system, while two complexes (1 : 1 and 1 : 2) were found when using Ln(ClO₄)₃ as the metal salts instead of Ln(NO₃)₃. The stability constants of the C4-POPhen/Am(III) and C4-POPhen/Ln(III) complexes in CH₃OH with perchlorate and nitrate were determined by absorption spectroscopy. The Am(III) complexes exhibited higher complexation ability than Ln(III), which was consistent with the extraction results. DFT calculations also suggested that the Am–N bonds in C4-POPhen/Am(III) complexes had a higher degree of covalence than the Eu–N bonds in C4-POPhen/Eu(III) complexes, revealing the underlying driving force for the extraction selectivity of Am(III) over Eu(III) by C4-POPhen. These results indicate that phenanthroline-derived phosphate ligands may serve as promising candidates for separation of trivalent actinides over lanthanides from highly active nuclear waste.

中文翻译：

揭示of素（III）和镧系元素（III）与新的四齿菲咯啉衍生的膦酸酯配体的络合机理

用溶剂研究了三价Am（III）和镧系元素（III）与新邻菲咯啉衍生的膦酸酯配体四丁基-（1,10-菲咯啉-2,9-二基）膦酸酯（C4-POPhen）的提取和络合。提取，吸收光谱，NMR滴定，发光光谱和理论计算。从高酸性HNO _3中选择性萃取Eu（III）之上的Am（III）通过使用C4-POPhen配体，可实现具有良好的选择性和快速提取速率的高纯溶液（最高3.0 M）。通过斜率分析法发现1：2的金属/配体络合物是提取的有机相中的主要物质。NMR滴定结果表明，在CH ₃ OH系统中仅形成了C4-POPhen与Ln（NO ₃）_3的1：1配合物，而使用Ln（ClO）时发现了两种配合物（1：1和1：1：2）。₄）₃作为金属盐代替Ln（NO ₃）₃。C4-POPhen / Am（III）和C4-POPhen / Ln（III）配合物在CH _3中的稳定性常数通过吸收光谱法测定具有高氯酸盐和硝酸盐的OH。Am（III）配合物比Ln（III）表现出更高的络合能力，这与提取结果一致。DFT计算还表明，C4-POPhen / Em（III）配合物中的Am–N键比C4-POPhen / Eu（III）配合物中的Eu–N键具有更高的共价度，从而揭示了潜在的驱动力。C4-POPhen对Am（III）对Eu（III）的萃取选择性这些结果表明，菲咯啉衍生的磷酸盐配体可作为从高活性核废料中分离镧系元素上的三价act系元素的有前途的候选者。

更新日期：2020-04-24

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