Phosphoryl-containing Podands Research Articles

Effect of Ionic Liquid on the Extraction of Lanthanides(III) from Nitric Acid Solutions with Phosphoryl-Containing Podands

Effect of Ionic Liquid on the Extraction of Lanthanides(III) from Nitric Acid Solutions with Phosphoryl-Containing Podands

Effect of the Structure of Phosphoryl-Containing Podands on the Extraction of Actinides and Lanthanides(III) from Nitric Acid Solutions

Effect of the Structure of Phosphoryl-Containing Podands on the Extraction of Actinides and Lanthanides(III) from Nitric Acid Solutions

Design of Extractants for F-Block Elements in a Series of (2-(Diphenylphosphoryl)methoxyphenyl)diphenylphosphine Oxide Derivatives: Synthesis, Quantum-Chemical, and Extraction Studies.

With the aim to find new efficient extractants for recovery of f-block elements from processing wastes of different origin, we have compared a series of phosphoryl-containing podands, including (2-(diphenylphosphorylmethoxy)phenyl)diphenylphosphine oxide 1 and its analogues 5–7, where the ArP(O)Ph2 group of phosphine oxide type is replaced by phosphonic fragments. Quantum-chemical modelling of the structures of phosphoryl-containing podands 1 and 5–7 has been performed, which was later confirmed by the data of X-ray diffraction. The features of extraction of nitric acid, as well as U(VI), Th(IV), Nd(III), and Ho(III) with compounds 1 and 5–7 from nitric acid media into 1,2-dichloroethane have been studied. The compositions of extracted complexes have been determined.

Synergistic Solvent Extraction of Lanthanides(III) with Mixtures of 4-Benzoyl-3-Methyl-1-Phenyl-5-Pyrazolone and Phosphoryl-Containing Podands

The solvent extraction of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu from weak acidic chloride solutions into an organic phase containing 4-benzoyl-3-methyl-1-phenyl-5-pyrazolone (HP) and phosphoryl-containing podands (L) has been studied. A considerable synergistic effect was observed in the presence of neutral ligands L in the organic phase containing HP. The stoichiometry of the Ln(III) extracted species was determined by slope analysis and the equilibrium constants were calculated. It was found that the lanthanide(III) ions are extracted with mixtures of HP and neutral ligands in toluene from weak acidic solutions as LnLP3 complexes.

Extraction of Rare-Earth Elements(III) with Mixtures of 1-Phenyl-3-methyl-4-benzoyl-5-pyrazolone and Phosphoryl-Containing Podands

Extraction of rare-earth elements(III) ions from chloride solutions with mixtures of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone and phosphoryl-containing podands in organic solvents has been studied. The observed significant synergistic effect is associated with the formation of hydrophobic mixed-ligand complexes of rare-earth elements(III). The stoichiometry of the extracted complexes has been determined, and the extraction constants have been calculated. The influence of the phosphoryl-containing podand structure, the organic solvent nature, and the aqueous phase composition on the efficiency of the extraction of rare-earth element(III) ions into the organic phase has been considered.

Liquid- and Solid-Phase Extraction of Uranium(VI), Thorium(IV), and Rare Earth Elements(III) from Nitric Acid Solutions Using Acid-Type Phosphoryl-Containing Podands

A possibility to use acid-type phosphoryl-containing podands with diethylene glycol polyether chain, which differ in substituent at the phosphoryl group, as extractants for the recovery of U(VI), Th(IV), and rare earth elements(III) from nitric acid solutions has been studied. Features of the effect of HNO3 concentration on U(VI) and Th(IV) extraction with solutions of the phosphoryl-containing podands in dichloroethane has been revealed. Uranium(VI) is extracted as a normal intracomplex salt of dibasic acid UO2L3 with chelate coordination of both POO− groups to one cation. Thorium(IV) produces a complex as a normal intracomplex salt of composition Th(L3)2 where two bivalent anions of ligand acid are coordinated via all four POO− groups to Th(IV) cation. Sorption of U(VI), Th(IV), and REE(III) by impregnated sorbent based on LPS-500 polymer with 1,5-bis[2-(oxyethoxyphosphoryl-4-ethyl)phenoxy]-3-oxapentane from 0.052 and 3.52 mol/L HNO3 has been studied. It has been established that the obtained sorbent shows high selectivity in the separation of U(VI), Th(IV), and REE(III). The separation factor for uranium(VI) and europium(III) (βU/Eu) has been found to be 202 and ∼55000 upon sorption from 3.52 and 0.052 mol/L HNO3, respectively, at V/m = 500 mL/g. At thorium(IV) sorption from 3.52 and 0.052 mol/L HNO3, βTh/U = 66 and ∼5050, respectively.

1,5-Bis[2-(Dioxyphosphoryl)-4-ethylphenoxy]-3-oxapentane and Its Analogs: Acidity and Complexation in Aqueous Media Containing Copper(II) Cation

Dissociation and complexation with Cu(II) cation is studied for phosphoryl-containing podands (tetrabasic 1,5-bis[2-(dioxyphosphoryl)-4-ethylphenoxy]acidic-type-3-oxapentane (H4LP) and dibasic 1,5-bis[2-(oxyethoxyphosphoryl)-4-ethylphenoxy]-pentane (H2LP)) and their carbonyl analog (polyether dibasic acid 1,5-bis[2-(oxycarbonylphenoxy)]oxapentane (H2LC) in water in the presence of 5% dimethylformamide potentiometrically, spectrophotometrically, and conductometrically. Phosphoryl podands exhibit good complexing properties and can selectively bind metal cations. The dissociation constants are determined and the distribution diagram of ionized species of the compounds under study depending on pH is plotted. The molar ratio between the metal and podand in all complexes is found to be 1 : 1. The stability constants of complexes with Cu2+ cation are calculated. The most stable copper(II) complexes are formed with the tetrabasic podand.

1,5-bis[2-(dioxyphosphoryl)-4-ethylphenoxy]-3-oxapentane and its Analogs as Promising Organic Ligands for Copper(II) Binding s

The dissociation and complexation ability toward Cu(II) of acidic type phosphoryl-containing podands – tetrabasic 1,5-bis[2-(dioxyphosphoryl)-4-ethylphenoxy]-3-oxapentane (L1), dibasic – 1,5-bis[2-(ethoxyhydroxyphosphoryl)-4-ethylphenoxy]-pentane (L2) and also of their carboxylic analogue dibasic 1,5-bis[2-(oxycarbonylphenoxy)]-3-oxapentane (L3) were investigated by spectrophotometric, conductometric and potentiometric methods in water in the presence 5% of dimethyl formamide. Spectrophotometric and conductometric titration data provided evidence for formation of 1:1 (M:L) complexes. The dissociation constants were determined and species distribution diagrams for studied acids were obtained by potentiometric method. These data are of interest for the design of binary extragents and medicinal drugs based on the studied ligands. The stability constants of Cu(II) 1:1 (M:L) complexes were estimated. Analysis of the titration curves suggests that deprotonation forms of the studied ligands react with Cu2+. Substitution of carboxylic groups in acyclic polyesters by phosphonic results in increased stability of the copper(II) complexes

Phosphoryl-containing acidic podands as extractants for recovery of f-elements

aOJSC Uralchem Joint Chemical Company, 10 Presnenskaya nab., 123317 Moscow, Russian Federation. Fax: +7 (495) 721 8585. Е mail: alfiya.safiulina@uralchem.com bA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 119991 Moscow, Russian Federation. Fax: +7 (499) 135 6549. E mail: matveeva@ineos.ac.ru cOJSC Leading Research Institute of Chemical Technology, 33 Kashirskoe sh., 115409 Moscow, Russian Federation dNational Research Nuclear Institute MIFI, 31 Kashirskoe sh., 115409 Moscow, Russian Federation eA. N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 4/31 Leninsky prosp., 119071 Moscow, Russian Federation. Fax: +7 (495) 952 5308 fInstitute of Physiologically Active Substances, Russian Academy of Sciences, 1 Severnyi proezd, 142432 Chernogolovka, Moscow Region, Russian Federation

Phosphoryl-containing acidic podands as extractants for recovery of f-elements

Bidistilled water was used for the preparation of mixed solvents:methanol—water (7 : 1 vol/vol) and DCE saturated with water(0.20%). 1,2Dichloroethane saturated with water was obtainedby the extraction of equal volumes of water and DCE for 20 minfollowed by phase separation using centrifugation.The apparent molecular weight of particles (associates)

Extractive and sorption preconcentration of rhenium(VII) with the use of phosphoryl-containing podands

Interphase distribution of micro amounts of ReO 4 − between aqueous solutions of mineral acids and solutions of phosphoryl-containing mono-, di-, and tripodands, derived from 1-(methoxydiphenylphosphoryl)-2-diphenylphosphorylbenzene in dichloroethane was studied. The stoichiometry of extracted complexes was determined, the effect of HNO3, HCl, and H2SO4 concentration in aqueous phase and the nature of organic solvent on the efficiency of transition of ions into organic phase was considered. The growth of the number of phosphoryl groups in podand molecule enhances its extraction ability toward Re(VII). The possibility of selective recovery and preconcentration of Re(VII) with complexing sorbent obtained by noncovalent binding of phosphoryl-containing podand on the surface of macroporous polymer Amberlite XAD7HP was shown.

Synergistic Solvent Extraction of Lanthanides(III) with Mixtures of 4-benzoyl-3-methyl-1-phenylpyrazol-5-one and Some Novel Carbamoyl- and Phosphorylmethoxymethylphosphine Oxides

The solvent extraction of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y from weak acidic hydrochloric acid solutions into an organic phase containing 4-benzoyl-3-methyl-1-phenylpyrazol-5-one (HP) and neutral tridentate organophosphorus ligands R2P(O)CH2OCH2C(O)NBu2 R = Bu (I), R = Ph (II) and R2P(O)CH2OCH2P(O)R12 R = R1 = Bu (III); R = Bu, R1 = Ph (IV); R = R1 = Ph(V) has been studied. A considerable synergistic effect was observed in the presence of HP in the organic phase containing tetraoctyldiglycolamide (TODGA) and neutral organophosphorus ligands I - V. A successive replacement of C(O)NAlk2 groups in the diglycolamide extractant molecule by P(O)Ph2 groups leads to an increase in the extraction efficiency of Ln(III) ions when toluene was used as diluent. Phosphoryl-containing podand I possess a higher extraction efficiency towards Ln(III) ions than TODGA. The extraction equilibrium was investigated and the equilibrium constants were calculated. It was found that the lanthanide(III) ions are extracted as LnLP3 and LnL2P3 complexes with mixtures of HP and I in toluene from weak acidic solutions.

Extraction of REEs(III), U(VI), and Th(IV) with acidic phosphoryl-containing podands from nitric acid solutions

The extraction of microamounts of REEs(III), U(VI), and Th(IV) from HNO3 solutions with solutions of acidic phosphoryl-containing podands in 1,2-dichloroethane was studied. The stoichiometry of the extractable complexes was determined. The influence of the extractant structure and aqueous phase composition on the efficiency and selectivity of the recovery of REEs(III), U(VI), and Th(IV) into the organic phase was considered.

Extraction of rare earth elements with 1-(diphenylphosphorylmethoxy)-2-diphenylphosphoryl-4-ethylbenzene with the use of 1,1,7-trihydrododecafluoroheptanol as a solvent

Extraction of rare earth elements from nitric acid solutions in a 1,1,7-trihydrododecafluoroheptanol-water system with the use of phosphoryl-containing podand 1-(diphenylphosphorylmethoxy)-2-diphenylphosphoryl-4-ethylbenzene (L) was studied. The content of metals in organic phase was shown to be negligible at nitric acid concentration lower 1 mol/L. Distribution ratio sharply increases with nitric acid concentration from 1 mol/L and reaches 5.5 for the yttrium subgroup elements at HNO3 concentration of 6 mol/L. The rare earth elements of the yttrium subgroup were found to be extracted much better than the rare earth elements of the cerium subgroup under the same conditions, the distribution ratios in both subgroups smoothly rise with atomic number of element. It was shown using the shift of extraction equilibrium that the M: L ratio in extracted complexes is 1: 2 irrespective of the nature of rare earth element. The structure of complex {Yb[η2-(O,O′)-L]2(η2-O2NO)2}(O2NOHNO3), whose single crystals were isolated from extraction solution, was established by X-ray diffraction study. The system can be used for the isolation and separation of rare earth elements.

ChemInform Abstract: Modeling of Ion Complexation and Extraction Using Substructural Molecular Fragments.

A substructural molecular fragment (SMF) method has been developed to model the relationships between the structure of organic molecules and their thermodynamic parameters of complexation or extraction. The method is based on the splitting of a molecule into fragments, and on calculations of their contributions to a given property. It uses two types of fragments: atom/bond sequences and “augmented atoms” (atoms with their nearest neighbors). The SMF approach is tested on physical properties of C2−C9 alkanes (boiling point, molar volume, molar refraction, heat of vaporization, surface tension, melting point, critical temperature, and critical pressures) and on octanol/water partition coefficients. Then, it is applied to the assessment of (i) complexation stability constants of alkali cations with crown ethers and phosphoryl-containing podands, and of β-cyclodextrins with mono- and 1,4-disubstituted benzenes, and (ii) solvent extraction constants for the complexes of uranyl cation by phosphoryl-containing ...

Crystal structure of complexes of pentavalent neptunium with 1,8-bis[2-(diphenylphosphinylmethyl)]phenoxy-3,6-dioxaoctane (L) and hexavalent actinides (U, Np, Pu) with 1,8-bis[2-(diphenylphosphinyl)]phenoxy-3,6-dioxaoctane (L1)

Complexes of pentaand hexavalent actinides with phosphoryl-containing podands incorporating a triethylene glycol fragment and 2-(diphenylphosphinyl)phenyl (L1) or 2-(diphenylphosphinylmethyl)phenyl (L) end groups were synthesized and structurally characterized. The complexes can be described by the following formulas: [NpO2L(C2H5OH)(NO3)] (I) for pentavalent neptunium and [AnO2(L1)2](OH)2 · nH2O (II), where An is U (IIa), Np (IIb), and Pu (IIc), for the isostructural compounds of hexavalent actinides. In I, L is a bidentate bridging ligand. The Np5+ coordination polyhedron is a pentagonal bipyramid. The bipyramid equatorial plane is formed by the oxygen atoms of two podands L, the bidentate nitrate ion, and the ethanol OH group. The oxygen atoms of the phosphoryl groups of the podand are involved in the coordination environment of two NpO2+ cations where they connect the electrically neutral neptunoyl nitrate fragments to infinite chains along the [100] direction, which are in turn connected into ribbons by strong hydrogen bonds. The crystal of II consists of the complex cations [AnO2(L1)2]2+, hydroxyl ions, and water molecules of crystallization. The environment of AnO22+ is formed by four ligands L1 whose oxygen atoms form a tetragonal-bipyramidal coordination environment. Each of the two crystallographically independent ligands L1 is connected to two AnO2+ cations. This gives positively charged layers of actinyl cations perpendicular to the [010] direction connected by molecular ligands. The layers contain channels accommodating hydroxyl ions and crystallization water molecules.

The extraction of noble metals by macrocyclic compounds

This is analytical article devoted to the extraction of noble metals by acyclic analogs of crown ethers (podands) covering the period from 1980 to 2007. Most attention is given to the extraction of noble metals by phosphoryl-containing podands from hydrochloric acid solutions. The efficiency of extraction depends mostly on the number and nature of donor centers in a reagent molecule. It is shown that the use of podands as noble metal extractants does not help to solve the problem of selective separation of noble metals from complex solutions.

Computer-aided design of new metal binders

Summary Chemoinformatics approaches open new opportunities for computer-aided design of new efficient metal binders. Here, we demonstrate performances of ISIDA and COMET software tools to predict stability constants (log K) of the metal ion/organic ligand complexes in solution and to design in silico new molecules possessing desirable properties. The predictive models for log K of lanthanides complexation in water have been developed. Some new uranyl binders based on monoamides and on phosphoryl-containing podands were suggested theoretically, then synthesized and tested experimentally. Reasonable agreement between experimental uranyl distribution coefficients and theoretically predicted values has been observed.

Extraction of U(VI), Th(IV), and rare-earth elements from nitric acid solutions with phosphoryl-and carbonyl-containing podands

The distribution of HNO3 and microamounts of nitrates of U(VI), Th(IV), La, Ce, Pr, Nd, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y between aqueous solutions of HNO3 and solutions of N,N′-dimethyl-N,N′-diphenyl-3-oxapentanediamide (I) and 1,3-bis(diphenylphosphinoyl)-2-oxapropane (II) in organic diluents was studied. The stoichiometry of the extractable complexes was determined, and the effect exerted by the extractant structure and by the organic diluent on the efficiency of recovery of rare-earth elements (REE) into the organic phase was examined. In nitric acid solutions, carbonyl-containing podand I surpasses in the extraction ability phosphoryl-containing podand II. The possibility of using a macroporous polymeric sorbent impregnated with compound I for recovering REE from nitric acid solutions was demonstrated.

“In Silico” Design of New Uranyl Extractants Based on Phosphoryl‐Containing Podands: QSPR Studies, Generation and Screening of Virtual Combinatorial Library, and Experimental Tests.

This paper is devoted to computer-aided design of new extractants of the uranyl cation involving three main steps: (i) a QSPR study, (ii) generation and screening of a virtual combinatorial library, and (iii) synthesis of several predicted compounds and their experimental extraction studies. First, we performed a QSPR modeling of the distribution coefficient (logD) of uranyl extracted by phosphoryl-containing podands from water to 1,2-dichloroethane. Two different approaches were used: one based on classical structural and physicochemical descriptors (implemented in the CODESSA PRO program) and another one based on fragment descriptors (implemented in the TRAIL program). Three statistically significant models obtained with TRAIL involve as descriptors either sequences of atoms and bonds or atoms with their close environment (augmented atoms). The best models of CODESSA PRO include its own molecular descriptors as well as fragment descriptors obtained with TRAIL. At the second step, a virtual combinatori...