Testing a simple approach for theoretical evaluation of radiolysis products in extraction systems. A case of N,O-donor ligands for Am/Eu separation

Matveev, Petr I.; Mitrofanov, Artem; Петров, В. Г.; Zhokhov, S. S.; Smirnova, A. A.; Ustynyuk, Yu. A.; Kalmykov, Stepan N.

doi:10.1039/c7ra11622e

Cited by 15 publications

(8 citation statements)

References 38 publications

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“…However, the extraction rates of BTBP-type ligands for actinides were relatively slow. ,, In order to overcome this shortcoming, a type of preorganized phenanthroline-derived ligand, 2,9-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-1,10-phenanthroline (BTPhen), was developed. As was reported that CyMe 4 -BTPhen exhibited a very strong selective extraction ability and fast extraction rates for Am(III) over Eu(III) ( D > 1000; separation factor SF Am/Eu > 200) in a highly acidic HNO 3 solution. ,,, Thus, we can see that in these triazine-type ligands the N-hetercyclic cores have a huge impact on the separation of actinides over lanthanides. ,,, Additionally, it was reported that the amide ligands with rigid phenanthroline skeletons had a stronger extraction ability and higher selectivity toward trivalent actinides over lanthanides compared with pyridine- or bipyridine-skeleton-based amide-type ligands. ,− With the introduction of an amide group into the ligands, the carbonyl moiety can promote ligand coordination with the lanthanides and greatly weaken the protonation reaction of the ligands. The D Eu(III) values are in the range from 2 to 20 for pyridine-derived N -methyl- N -phenyl-2-(1 H -benzimidazol-2-yl)pyridine-6-carboxamide, and D Eu(III) varies from 0.01 to 0.2 for 2-(2-pyridyl)benzimidazole .…”

Section: Introductionmentioning

confidence: 60%

“…5,21,22,29 Thus, we can see that in these triazine-type ligands the N-hetercyclic cores have a huge impact on the separation of actinides over lanthanides. 20,22,39,40 Additionally, it was reported that the amide ligands with rigid phenanthroline skeletons had a stronger extraction ability and higher selectivity toward trivalent actinides over lanthanides compared with pyridine-or bipyridine-skeleton-based amide-type ligands. 21,41−44 With the introduction of an amide group into the ligands, the carbonyl moiety can promote ligand coordination with the lanthanides and greatly weaken the protonation reaction of the ligands.…”

Section: ■ Introductionmentioning

confidence: 99%

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Influence of a N-Heterocyclic Core on the Binding Capability of N,O-Hybrid Diamide Ligands toward Trivalent Lanthanides and Actinides

Meng

Yang

et al. 2021

Inorg. Chem.

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N,O-hybrid diamide ligands with N-heterocyclic skeletons are one of the promising extractants for the selective separation of actinides over lanthanides in a highly acidic HNO3 solution. In this work, three hard–soft donor mixed diamide ligands, pyridine-2,6-diylbis(pyrrolidin-1-ylmethanone) (Pyr-PyDA), 2,2′-bipyridine-6,6′-diylbis(pyr-rolidine-1-ylmethanone) (Pyr-BPyDA), and (1,10-phenanthroline-2,9-diyl)bis(pyrrolidin-1-ylmethanone) (Pyr-DAPhen), were synthesized and used to probe the influence of N-heterocyclic cores on the complexation and extraction behaviors with trivalent lanthanides and actinides. 1H NMR titration experiments demonstrated that 1:1 metal-to-ligand complexes were mainly formed between the three ligands and lanthanides, but 1:2 type complexes were also formed between tridentate Pyr-PyDA and Lu(III). The stability constants (log β) of these three ligands with two typical lanthanides, Nd(III) and Eu(III), were determined through spectrophotometric titration. It is found that Pyr-DAPhen formed the most stable complexes, while Pyr-PyDA formed the most unstable complexes with lanthanides, which coincided well with the following solvent extraction results. The solid-state structures of 1:1 type complexes of these three ligands with La(III), Nd(III), and Er(III) in nitrate media were identified by a single-crystal X-ray diffraction technique. Nd(III) and Er(III) were 10-coordinated with Pyr-PyDA, Pyr-BPyDA, and Pyr-DAPhen via one ligand molecule and three nitrate ions. La(III), because of its larger ionic radius, was 11-coordinated with Pyr-DAPhen through one ligand molecule, three nitrate ions, and one methanol molecule. Solvent extraction experiments showed that the preorganized phenanthroline-derived Pyr-DAPhen had the best extraction performance for trivalent actinide among the three ligands tested. This work provides some experimental insights into the design of more efficient ligands for trivalent actinide separation by adjusting the N-heterocyclic cores.

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Section: Introductionmentioning

confidence: 60%

Section: ■ Introductionmentioning

confidence: 99%

Influence of a N-Heterocyclic Core on the Binding Capability of N,O-Hybrid Diamide Ligands toward Trivalent Lanthanides and Actinides

Meng

Yang

et al. 2021

Inorg. Chem.

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“…This approach may be of use for reducing the Brönsted basicity of the synthesized ligands. However, the presence of chlorine atoms is undesirable in terms of the resistance of the extractants to radiolysis [ 11 , 12 ].…”

Section: Introductionmentioning

confidence: 99%

First Example of Fluorinated Phenanthroline Diamides: Synthesis, Structural Study, and Complexation with Lanthanoids

et al. 2022

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An efficient approach to the synthesis of diamides of 4,7-difluoro-1,10-phenanthroline-2,9-dicarboxylic acid was elaborated. Direct nucleophilic substitution with 4,7-dichloro-1,10-phenanthroline precursors opened access to difluoro derivatives in high yield. As a result, four new fluorinated ligands were prepared in up to 88% yield. Their structure was proved by a combination of spectral methods and X-ray data. A set of lanthanoid complexes was prepared to demonstrate the utility of new ligands. The structure of the complexes was studied in solid state (IR-spectroscopy, X-ray diffraction) and in solution (NMR-spectroscopy).

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“…24,25 Thus, we can see that in these triazine-type ligands, the N-heterocyclic cores massively affect the partition of actinides over lanthanides. 26,27 Moreover, it has been observed from previous studies that amide ligands with phenanthroline skeletons have a stronger extraction capacity and higher selectivity toward trivalent actinides over lanthanides compared with the pyridine-or bipyridineskeleton-based amide-type ligands. 28,29 With the introduction of an amide group into the ligands, the carbonyl moiety can improve the ligand's coordination with lanthanides and significantly hinder the protonation of the ligands.…”

Section: Introductionmentioning

confidence: 99%

Preorganization of N,O-hybrid phosphine oxide chelators for effective extraction of trivalent Am/Eu ions – a computational study

Ebenezer

Solomon

2022

New J. Chem.

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Testing a simple approach for theoretical evaluation of radiolysis products in extraction systems. A case of N,O-donor ligands for Am/Eu separation

Abstract: Here we present experimental confirmation of the theoretical calculation of organic ligands' radiolytic degradation.

Cited by 15 publications

References 38 publications

Influence of a N-Heterocyclic Core on the Binding Capability of N,O-Hybrid Diamide Ligands toward Trivalent Lanthanides and Actinides

Influence of a N-Heterocyclic Core on the Binding Capability of N,O-Hybrid Diamide Ligands toward Trivalent Lanthanides and Actinides

First Example of Fluorinated Phenanthroline Diamides: Synthesis, Structural Study, and Complexation with Lanthanoids

Preorganization of N,O-hybrid phosphine oxide chelators for effective extraction of trivalent Am/Eu ions – a computational study

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