Synergistic Solvent Extraction of Lanthanoids with Traditional Ligands (4-Acylpyrazolone and Bidentate Nitrogen Bases) in a Nontraditional Diluent Confirmed by Slope Analysis and NMR

The synergistic solvent extraction of La(III), Eu(III) and Lu(III) with a chelating extractant, 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one (HL), and neutral bidentate heterocyclic amines, such as 1,10-phenanthroline (S1 (phen)) or 2,2′-bipyridine (S2 (bipy)) in an ionic liquid of the imidazolium...

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Main Authors: Maria Atanassova, Nina Todorova, Svetlana Simova
Format: Article
Language:English
Published: MDPI AG 2025-02-01
Series:Molecules
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Online Access:https://www.mdpi.com/1420-3049/30/4/786
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author Maria Atanassova
Nina Todorova
Svetlana Simova
author_facet Maria Atanassova
Nina Todorova
Svetlana Simova
author_sort Maria Atanassova
collection DOAJ
description The synergistic solvent extraction of La(III), Eu(III) and Lu(III) with a chelating extractant, 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one (HL), and neutral bidentate heterocyclic amines, such as 1,10-phenanthroline (S1 (phen)) or 2,2′-bipyridine (S2 (bipy)) in an ionic liquid of the imidazolium family [C<sub>1</sub>C<sub>4</sub>im<sup>+</sup>][Tf<sub>2</sub>N<sup>−</sup>] was investigated. Synergistic effects have been observed to result from the formation of a ternary complex in the organic phase, particularly in cases where the ligand S is a neutral synergistic agent. Examples include La(L)<sub>2</sub>(S2)<sub>2</sub>, Eu(L)<sub>3</sub>(S2) and Lu(L)<i><sub>x</sub></i>(S2)<sub>2</sub>, as well as La(L)<sub>3</sub>(S1)<sub>2</sub>, Eu(L)<sub>2</sub>(S1) and Lu(L)<sub>3</sub>(S1)<i><sub>x</sub></i>). The parameters of the solvent extraction process were determined and the influence of the synergistic agent on the extraction process was discussed. Additionally, the synergistic increase and separation factors were determined. The equilibrated organic phases were analyzed using <sup>1</sup>H NMR spectroscopy to elucidate the synergism in an extraction mechanism. The role of the ionic diluent in complexation processes and selectivity was investigated with the employment of the two synergistic agents for various metal s-, p-, d- and f-cations in the periodic table, with almost 22 metal ions.
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spelling doaj-art-856d61c0a88a42d7a39a646e16f709402025-08-20T02:03:28ZengMDPI AGMolecules1420-30492025-02-0130478610.3390/molecules30040786Synergistic Solvent Extraction of Lanthanoids with Traditional Ligands (4-Acylpyrazolone and Bidentate Nitrogen Bases) in a Nontraditional Diluent Confirmed by Slope Analysis and NMRMaria Atanassova0Nina Todorova1Svetlana Simova2Department of General and Inorganic Chemistry, University of Chemical Technologies and Metallurgy, 8 Kliment Okhridski Blvd., 1756 Sofia, BulgariaDepartment of General and Inorganic Chemistry, University of Chemical Technologies and Metallurgy, 8 Kliment Okhridski Blvd., 1756 Sofia, BulgariaInstitute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev Street, Block 9, 1113 Sofia, BulgariaThe synergistic solvent extraction of La(III), Eu(III) and Lu(III) with a chelating extractant, 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one (HL), and neutral bidentate heterocyclic amines, such as 1,10-phenanthroline (S1 (phen)) or 2,2′-bipyridine (S2 (bipy)) in an ionic liquid of the imidazolium family [C<sub>1</sub>C<sub>4</sub>im<sup>+</sup>][Tf<sub>2</sub>N<sup>−</sup>] was investigated. Synergistic effects have been observed to result from the formation of a ternary complex in the organic phase, particularly in cases where the ligand S is a neutral synergistic agent. Examples include La(L)<sub>2</sub>(S2)<sub>2</sub>, Eu(L)<sub>3</sub>(S2) and Lu(L)<i><sub>x</sub></i>(S2)<sub>2</sub>, as well as La(L)<sub>3</sub>(S1)<sub>2</sub>, Eu(L)<sub>2</sub>(S1) and Lu(L)<sub>3</sub>(S1)<i><sub>x</sub></i>). The parameters of the solvent extraction process were determined and the influence of the synergistic agent on the extraction process was discussed. Additionally, the synergistic increase and separation factors were determined. The equilibrated organic phases were analyzed using <sup>1</sup>H NMR spectroscopy to elucidate the synergism in an extraction mechanism. The role of the ionic diluent in complexation processes and selectivity was investigated with the employment of the two synergistic agents for various metal s-, p-, d- and f-cations in the periodic table, with almost 22 metal ions.https://www.mdpi.com/1420-3049/30/4/786lanthanoidssynergistic extraction4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one1,10-phenanthroline2,2′-bipyridineNMR
spellingShingle Maria Atanassova
Nina Todorova
Svetlana Simova
Synergistic Solvent Extraction of Lanthanoids with Traditional Ligands (4-Acylpyrazolone and Bidentate Nitrogen Bases) in a Nontraditional Diluent Confirmed by Slope Analysis and NMR
Molecules
lanthanoids
synergistic extraction
4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one
1,10-phenanthroline
2,2′-bipyridine
NMR
title Synergistic Solvent Extraction of Lanthanoids with Traditional Ligands (4-Acylpyrazolone and Bidentate Nitrogen Bases) in a Nontraditional Diluent Confirmed by Slope Analysis and NMR
title_full Synergistic Solvent Extraction of Lanthanoids with Traditional Ligands (4-Acylpyrazolone and Bidentate Nitrogen Bases) in a Nontraditional Diluent Confirmed by Slope Analysis and NMR
title_fullStr Synergistic Solvent Extraction of Lanthanoids with Traditional Ligands (4-Acylpyrazolone and Bidentate Nitrogen Bases) in a Nontraditional Diluent Confirmed by Slope Analysis and NMR
title_full_unstemmed Synergistic Solvent Extraction of Lanthanoids with Traditional Ligands (4-Acylpyrazolone and Bidentate Nitrogen Bases) in a Nontraditional Diluent Confirmed by Slope Analysis and NMR
title_short Synergistic Solvent Extraction of Lanthanoids with Traditional Ligands (4-Acylpyrazolone and Bidentate Nitrogen Bases) in a Nontraditional Diluent Confirmed by Slope Analysis and NMR
title_sort synergistic solvent extraction of lanthanoids with traditional ligands 4 acylpyrazolone and bidentate nitrogen bases in a nontraditional diluent confirmed by slope analysis and nmr
topic lanthanoids
synergistic extraction
4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one
1,10-phenanthroline
2,2′-bipyridine
NMR
url https://www.mdpi.com/1420-3049/30/4/786
work_keys_str_mv AT mariaatanassova synergisticsolventextractionoflanthanoidswithtraditionalligands4acylpyrazoloneandbidentatenitrogenbasesinanontraditionaldiluentconfirmedbyslopeanalysisandnmr
AT ninatodorova synergisticsolventextractionoflanthanoidswithtraditionalligands4acylpyrazoloneandbidentatenitrogenbasesinanontraditionaldiluentconfirmedbyslopeanalysisandnmr
AT svetlanasimova synergisticsolventextractionoflanthanoidswithtraditionalligands4acylpyrazoloneandbidentatenitrogenbasesinanontraditionaldiluentconfirmedbyslopeanalysisandnmr