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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Structural study of trivalent lanthanide and actinide complexes formed upon solvent extraction
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Structural study of trivalent lanthanide and actinide complexes formed upon solvent extraction

机译：溶剂萃取后形成的三价镧系元素和act系元素配合物的结构研究

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The coordination of the trivalent 4f ions, Ln = Nd3+, Eu3+ and Yb3+, as well as the trivalent 5f ion, Am3+, with diamide and dialkylphosphoric acid extractants, individually and in combination, was studied by use of X-ray absorption spectroscopy. These studies provide metrical information about the interatomic interactions between the f-ions (M3+) and the ligands, dihexylphosphoric acid (HDHP) and N, N'-dimethyl- N,N'-dioctylhexylethoxymalonamide (DMDOHEMA), that is of practical relevance to the control of metal - ligand binding in liquid - liquid extraction systems for the separation of trivalent actinide ions, An(3+), from trivalent lanthanide ions, Ln(3+). Through systematic variations of extraction conditions and extractant combinations, we have found that the HDHP complexes with M3+ involve MO6 coordination and distant M center dot center dot center dot P interactions, whereas the DMDOHEMA complexes with M3+ involve MO8 coordination. The combination of the EXAFS results with ancillary extraction data and IR results facilitates descriptions of the stoichiometries and structures of the molecular species formed in solution upon liquid - liquid extraction and leads to a new understanding of the binary extraction systems in terms of the strength and selectivity of An(3+)- vs. Ln(3+)-ligand interactions. This fundamental structure information affords insight into solvent extraction processes that are of contemporary and practical importance in heavy element chemistry and to environmentally related issues arising from the separation and disposal of radioactive materials, particularly actinides and selected fission products, in the field of nuclear waste reprocessing research.
机译：通过X射线吸收光谱研究了三价4f离子Ln = Nd3 +，Eu3 +和Yb3 +以及三价5f离子Am3 +与二酰胺和二烷基磷酸萃取剂的配位关系。这些研究提供了有关f离子（M3 +）与配体，二己基磷酸（HDHP）和N，N'-二甲基-N，N'-二辛基己基乙氧基丙二酰胺（DMDOHEMA）之间的原子间相互作用的度量信息。液-液萃取系统中金属-配体结合的控制，用于从三价镧系元素离子Ln（3+）分离三价act系离子An（3+）。通过对萃取条件和萃取剂组合的系统变化，我们发现具有M3 +的HDHP配合物涉及MO6配位和远处的M中心点中心点中心点中心点P相互作用，而具有M3 +的DMDOHEMA配合物则涉及MO8配位。 EXAFS结果与辅助提取数据和IR结果的结合，有助于描述液-液萃取过程中溶液中形成的分子种类的化学计量和结构，并从强度和选择性方面使人们对二元萃取系统有了新的认识（3 +）-与Ln（3 +）-配体相互作用的关系。这些基本的结构信息可洞悉在重元素化学中具有当代意义和实际意义的溶剂萃取过程，以及在核废料再处理领域中由于放射性物质（尤其是act系元素和某些裂变产物）的分离和处置而引起的与环境相关的问题。研究。

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