New polar fluorinated diluents for diamide extractants

Alyapyshev, M. Yu.; Бабаин, В. А.; Eliseev, I. I.; Kenf, E.; Ткаченко, Л. И.

doi:10.1007/s10967-016-4907-1

Cited by 23 publications

(11 citation statements)

References 20 publications

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“…It was a matter of practical interest to measure the solubility of diamides 3a-h in solvent "F-3" (3-nitrobenzotriuoride), which is widely used for its high solvation ability towards actinide complexes and its ability to reveal the best extraction properties of N-heterocyclic diamides. 31,32 Expectedly, the solubility increases in the rows 3a-3c and 3f-3g with increase of lipophilicity (Table 1).…”

Section: Resultsmentioning

confidence: 95%

The impact of alicyclic substituents on the extraction ability of new family of 1,10-phenanthroline-2,9-diamides

et al. 2020

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Section: Resultsmentioning

confidence: 95%

The impact of alicyclic substituents on the extraction ability of new family of 1,10-phenanthroline-2,9-diamides

et al. 2020

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“…We chose methanitrobenzotrifluoride (F-3) as the solvent for the extraction experiments. Our choice was based on the previously demonstrated high capacity of extraction systems based on it for f -elements. , We quantitatively measured the solubility of the ligands in the F-3 solvent, which we used for extraction tests (Table ). Having higher LogP values, L1 and L3 are much more soluble in F-3.…”

Section: Resultsmentioning

confidence: 99%

Structural Insight into Complexation Ability and Coordination of Uranyl Nitrate by 1,10-Phenanthroline-2,9-diamides

et al. 2021

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Reprocessing of spent nuclear fuel (SNF) is an important task in a frame of ecology and rational use of natural resources. Uranium, as the main component of SNF (>95%), can be recovered for further use as fresh nuclear fuel. To minimize an amount of solid radioactive waste generated during SNF reprocessing, new extractants are under investigation. Diamides of 1,10-phenanthroline-2,9-dicarboxylic acid are perspective tetradentate N-donor ligands that form strong complexes with f-elements, which are soluble in polar organic solvents. As an example of three ligands of this class, we conducted a comparative study and showed how the substituent in the amide functional group affects the extraction ability toward uranyl nitrate from nitric acid media. We have performed a careful study (NMR, FT-IR, XRD, RMC-EXAFS) of the structures of synthesized complexes of new ligands with uranyl nitrate and used quantum mechanical calculations to explain the discovered regularities through.

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“…We used m -nitrobenzotrifluoride, a common solvent in the extraction of diamides and N-heterocyclic compounds . From a practical point of view, it is advantageous because it involves a low risk of fires and explosions and has high phase stability. − The selected range of nitric acid concentrations was determined by the content of nitric acid in the HLW. Because of the different ligand solubilities, the working concentrations were chosen as follows: 0.01 mol/L for bipyridine-based ligands and 0.002 mol/L for phenanthroline-based ligands.…”

Section: Resultsmentioning

confidence: 99%

Way to Enforce Selectivity via Steric Hindrance: Improvement of Am(III)/Eu(III) Solvent Extraction by Loaded Diphosphonic Acid Esters

et al. 2021

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Hybrid donor extractants are a promising class of compounds for the separation of trivalent actinides and lanthanides. Here, we investigated a series of sterically loaded diphosphonate ligands based on bipyridine (BiPy-PO-iPr and BiPy-PO-cHex) and phenanthroline (Phen-PO-iPr and Phen-PO-cHex). We studied their complex formation with nitrates of trivalent f-elements in solvent extraction systems (Am and Eu) and homogeneous acetonitrile solutions (Nd, Eu, and Lu). Phenanthroline extractants demonstrated the highest efficiency and selectivity [SF(Am/Eu) up to 14] toward Am(III) extraction from nitric acid solutions among all of the studied diphosphonates of N-heterocycles. The binding constants established by UV–vis titration also indicated stronger binding of sterically impaired diphosphonates compared to the primary substituted diphosphonates. NMR titration and slope analysis during solvent extraction showed the formation of 2:1 complexes at high concentrations (>10–3 mol/L) for phenanthroline-based ligands. According to UV–vis titrations at low concentrations (10–5–10–6 mol/L), the phenanthroline-based ligands formed 1:1 complexes. Bipyridine-based ligands formed 1:1 complexes regardless of the ligand concentration. Luminescence titrations revealed that the quantum yields of the complexes with Eu(III) were 81 ± 8% (BiPy-PO-iPr) and 93 ± 9% (Phen-PO-iPr). Single crystals of the structures [Lu(μ2,κ4-(iPrO)2P(O)Phen(O)2(OiPr))(NO3)2]2 and Eu(Phen-PO-iPr)(NO3)3 were obtained by chemical synthesis with the Phen-PO-iPr ligand. X-ray diffraction studies revealed a closer contact of the f-element with the aromatic N atoms in the case of sterically loaded PO ligands compared with sterically deficient ligands. Density functional theory calculations allowed us to rationalize the observed selectivity trends in terms of the bond length, Mayer bond order, and preorganization energy.

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New polar fluorinated diluents for diamide extractants

Cited by 23 publications

References 20 publications

The impact of alicyclic substituents on the extraction ability of new family of 1,10-phenanthroline-2,9-diamides

The impact of alicyclic substituents on the extraction ability of new family of 1,10-phenanthroline-2,9-diamides

Structural Insight into Complexation Ability and Coordination of Uranyl Nitrate by 1,10-Phenanthroline-2,9-diamides

Way to Enforce Selectivity via Steric Hindrance: Improvement of Am(III)/Eu(III) Solvent Extraction by Loaded Diphosphonic Acid Esters

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