Effect of Diluents on The Synergistic Solvent Extraction and Separation of Trivalent Lanthanoids With 4-Benzoyl-3-Phenyl-5-Isoxazolone and tert-Butylcalix[4]Arene Tetrakis(N,N-Dimethyl Acetamide) and Structural Study of Gd(III) Solid Complex By IR and NMR

Abstract

The solvent extraction of 14 lanthanoid(III) ions from a chloride medium with acidic chelating extractant 4-benzoyl-3-phenyl-5-isoxazolone (HPBI) and tert-butylcalix[4]arene tetrakis(N,N-dimethylacetamide) (S) as a synergistic agent in C6H6 has been studied. In all cases, Ln(III) ions were extracted as Ln(PBI)3·S species. Positive values of the synergistic coefficients show that all lanthanoids were extracted synergistically upon the addition of compound S to the chelating extractant. The values of the equilibrium constant and the separation factors were calculated. The synergistic solvent extraction of five selected lanthanoid ions (La3+, Nd3+, Eu3+, Ho3+, and Lu3+) with a mixture of HPBI and S from a perchlorate medium in other diluents such as CHCl3, C2H4Cl2, and CCl4 has been studied too. It was found that the values of the equilibrium constant increased in the order CHCl3 < C2H4Cl2 < CCl4. The effect of the diluents on the metal extraction and separation has been discussed. A solid complex of Gd(III) with HPBI and S was synthesized. The composition of the complex was determined as Gd(PBI)3·S using elemental analysis, IR, and 1H NMR data.

Comparing extraction, synergism and separation of lanthanoids using acidic and neutral compounds in chloroform and one ionic liquid: is the latter always “better”?

“…As part of our systematic work on the synergistic solvent extraction of lanthanoids, [1][2][3][4][5][6][7][8] we performed comparative studies aiming at (i) improving the extraction ability of b-diketone compounds by increasing their acidity, (ii) studying the dependence of the extraction properties on the number of the ligating groups on a calixarene scaffold and nally, (iii) understanding the role of the solvent for extraction, separation and synergism by comparing a traditional molecular solvent, chloroform, and one ionic liquid, namely 1-methyl-3-butylimidazolium bis(triuoromethanesulfonyl)imide, there-aer denoted as [C 1 C 4 im][Tf 2 N]. It is our opinion that the wellassessed strategy based on the individual independent improvements of the extractants used in a synergistic system, which has proven to be quite efficient in molecular solvents, [1][2][3][4][5][6][7][8] may nd some limitations in ionic liquids (ILs). Ionic liquids are studied for an increasing number of applications in various aspects of chemistry and of course liquid-liquid extraction of rare earths and other metals.…”

Synergistic Efficiency of 2-[(1-Aza-15-crown-5)-1-ylmethyl)]-4-(phenyldiazenyl)-naphthalen-1-ol in the Liquid Extraction of Light Lanthanoid(III) Ions with 4-Benzoyl-3-phenyl-5-isoxazolone: The Role of Aza-Crown and Azo-Dye Fragments on the Extraction Ability

“…32 It could be supposed that the complexes containing two PDN1A15C5 molecules are sandwich type complexes having one PDN1A15C5 or BA15C5 moiety on either side of the metal chelate. A similar suggestion has been made earlier by Mathur and Khopkar 33 for the complexes obtained in the synergistic extraction of some actinoids and Eu(III) with acylpyrazolone and benzo-15-crown-5.…”

Extraction Ability of 4-Benzoyl-3-phenyl-5-isoxazolone towards 4f-Ions into Ionic and Molecular Media

“…Atanassova et al have already demonstrated that the extraction of Ln ions using the strongly coordinating compound HPBI in a set of molecular diluents proceeds through a proton-exchange reaction, forming neutral tris complexes. [23][24][25][26][27] The extraction mechanism and the extraction constant of the neutral tris complexes (Kex,3) were represented by the following equations:…”

“…(11) from slope analysis (data not shown in the figures). [23][24][25][26][27] In addition, the values of log Kex,3 for La 3+ , Eu 3+ , and Lu 3+ in the chloroform system were determined to be -1.34 ± 0.10, 0.85 ± 0.11, and 0.73 ± 0.10 by a linear leastsquares fitting of the plots, respectively. Electroneutrality is an essential principle, as only neutral complexes may enter the hydrophobic molecular layer.…”

“…1,2-dichloroethane), including combinations with a wide variety of ligands, like crown ethers, 23 p-tert-butylcalix [4]arenes, 24,25 alkylammonium salts 26 including Aliquat 336 in its perchlorate form too. 27 Strong acidity due to the electron delocalization induced by the isoxazolone moiety makes 4-acyl-5-isoxazolones an interesting class of analogs to β-diketones with potential application at strong acidic media for developing a separation process for both lanthanoids and actinoids.…”