Elena V. Sharova

Extraction of Lanthanides(III) from HClO4 Solutions with Bis(diphenylphosphorylmethylcarbamoyl)alkanes

Abstract Novel polyfunctional neutral organophosphorus compounds, namely bis(diphenylphosphoryl-methylcarbamoyl)alkanes of general formula [Ph2P(O)CH2C(O)NH]2(CH2)n (I-III; n = 3, 5, 8), were synthesized and studied as extractants for La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y from perchloric acid solutions. The influence of both of HClO4 concentration in the aqueous phase and that of the extractant in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes has been determined. Bis(diphenylphosphorylmethylcarbamoyl)alkanes II and III possess a higher extraction efficiency towards Ln(III) than their monoanalogue Ph2P(O)CH2C(O)NHC9H19. The potentialities of polymeric resin impregnated with bis(diphenylphosphorylmethylcarbamoyl)pentane II for the preconcentration of lanthanides(III) from perchloric acid solutions are demonstrated.

Bis(carbamoylmethylphosphine oxide) ligands fixed on the arene core via 1,2,3-triazole linkers: novel effective extractants for palladium, lanthanides and actinides

Novel polydentate neutral organophosphorus ligands containing two diphenyl-(diethylcarbamoylmethyl)phosphine oxide moieties fixed on the arene platform via methylene-1,2,3-triazole linkers (Ar-CMPO) were synthesized by the method of “click” chemistry and studied as an extractant for Pd(II), U(VI), Th(IV) and lanthanide(III) ions from HNO3 solutions. The influence of aqueous and organic phases on the extraction efficiency was elucidated and the stoichiometry of the complexes extracted was determined. The introduction of a 1,2,3-triazole fragment into the methylene bridge of a CMPO molecule resulted in a considerable increase in the efficiency of Pd(II) extraction. This modification of a CMPO molecule does not essentially change the extraction efficiency towards U(VI) and Ln(III) but drastically decreases the Th(IV) extraction and changes the order in the extractability of U(VI) and Th(IV) from HNO3 solutions. Bis-CMPO ligands containing two 1,2,3-triazole moieties (Ar-CMPO) were found to possess a higher extraction efficiency towards Pd(II), U(VI), Th(IV) and lanthanide(III) ions than their mono analog 2-(diphenylphosphoryl)-N,N-diethyl-3-(1-phenyl-1H-1,2,3-triazol-4-yl)propanamide.

Extraction of Lanthanides(III), U(VI), and Th(IV) from Nitric Acid Solutions with 1,5-N,N'-Bis[(diphenylphosphoryl)acetylamino]pentanes

Novel polyfunctional neutral organophosphorus ligands, namely 1,5-N,N-bis[(diphenylphosphoryl)acetyl(alkyl)amino]pentanes [Ph2P(O)CH2C(O)NR]2(CH2)5 (Ia, R = C6H13; Ib, R = CH3), were studied as extractants for Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, and U from nitric acid solutions. The effect of both HNO3 concentration in the aqueous phase and that of the extractant in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes was determined by the slope analysis method. Compared with the related bisaminopentane [Ph2P(O)CH2C(O)NH]2(CH2)5 (Ic), the replacement of hydrogen atoms at the amide nitrogens by alkyl radicals (compounds Ia,b) leads to an increase of metal ions extraction. Bis-CMPO ligands Ia-c were found to possess higher extraction efficiency towards U(VI), Th(IV), and Ln(III) than their monophosphorylated analogue Ph2P(O)CH2C(O)N(C4H9)2.

Extraction of U(VI), Th(IV), and Lanthanides(III) from Nitric Acid Solutions with CMPO-Functionalized Ionic Liquid in Molecular Diluents

The extraction of microquantities of U(VI), Th(IV), and lanthanides(III) from nitric acid solutions with CMPO-functionalized ionic liquid 1-[3[[(diphenylphosphinyl)acetyl]amino]propyl]-3-tetradecyl-1H-imidazol-3-ium hexafluorophosphate, CMPO-FIL(I) in molecular organic diluents has been studied. The effect of HNO3 concentration in the aqueous phase and that of extractant concentration in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes was determined. CMPO-FIL(I) demonstrates greater extraction ability towards Ln(III) than its neutral CMPO analog, diphenylphosphorylacetic acid N-nonylamide. This inner synergistic effect increases with a decreasing organic diluent polarity. The partition of CMPO-FIL(I) between the equilibrium organic and aqueous phases is the dominant factor governing the extractability of Ln(III) ions in the extraction system.

Extraction Properties of 1,2,3-Triazole Modified Carbamoylmethylphosphine Oxide in Nitric Acid Media

A novel polyfunctional neutral organophosphorus compound, 2-(diphenylphosphoryl)-N,N-diethyl-3-(1-phenyl-1H-1,2,3-triazol-4-yl)propanamide (I), was synthesized and studied as an extractant for Pd(II), Ln(III), U(VI), and Th(IV) from HNO3 solutions. The influence of aqueous and organic phases on the extraction efficiency was elucidated and stoichiometry of the complexes extracted was determined. The introduction of a 1,2,3-triazole fragment into the methylene bridge of diphenyl(diethylcarbamoylmethyl)phosphine oxide resulted in a considerable increase of the efficiency of Pd(II) extraction. The potentialities of carbon nanotubes impregnated with compound I for the preconcentration of Pd(II) from nitric acid solutions are demonstrated. The introduction of a 1,2,3-triazole fragment into the methylene bridge of a CMPO molecule does not essentially change the extraction efficiency of compound I towards U(VI) and Ln(III) but drastically decreases the Th(IV) extraction and change the order in the extractactability of U(VI) and Th(IV) with this compound from HNO3 solutions.

Effective Modular Assembling of Novel Ligands Starting from (Thio)Phosphorylated Anilines

Abstract A series of novel oligodentate ligands has been designed by the modular assembly of ortho-(thio)phosphorylated anilines with a range of commercially available carbonyl compounds. The new ligands readily form complexes with a series of metal ions (Pd(II), Cu(II), Ni(II), and Re(I)) both in neutral and deprotonated forms, providing OO, SN, ONO, SNO, SNS, SNN, and ONN donor sets. The structure and composition of the resulting complexes depend on the nature and mutual disposition of the donating groups as well as on the reaction conditions. GRAPHICAL ABSTRACT

Extraction Properties of P(O)-Modified N-Aryl-Carbamoylmethylphosphine Oxides in Nitric Acid Media

Novel polyfunctional neutral organophosphorus compounds, P(O)-modified N-aryl- carbamoylmethylphosphine oxides, Ph2P(O)CH2C(O)NH-(o-C6H4)(CH2)n-P(O)Ph2 and Ph2P(O)CH2C(O)NH-(m-C6H4)(CH2)n-P(O)Ph2 (n = 1,2), were synthesized and studied as extractants for U(VI), Th(IV) and Ln(III) from HNO3 solutions. The influence of aqueous and organic phases on the extraction efficiency was elucidated and stoichiometry of the complexes extracted was determined. Introduction of an additional phosphoryl group into the phenyl substitutent at the nitrogen atom of diphenyl(N-phenylcarbamoylmethyl)phosphine oxide resulted in an increase of the efficiency of U(VI), Th(IV), Ln(III), and Re(VII) extraction.

Advantages of Organophosphorus Synthesis in Ionic Liquids: “Green” Approaches to Useful Phosphorus-Substituted Building Blocks

Novel examples concerning the application of ionic liquids as a promoting reaction media in organophosphorus chemistry are discussed. Imidazolium ionic liquids were found to accelerate the Michaelis-Arbuzov reaction allowing to perform it under very mild conditions. Both phosphonium and imidazolium ILs give the possibility to perform easily direct amidation of phosphoryl acetic acids by various amines. Nucleophilic displacement reactionin a series of bromoalkylphosphonates was carried out in quantitative yield to afford azidoalkylphosphonates using the [bmim][PF6]/H2O system.

Synthesis of camphecene derivatives using click chemistry methodology and study of their antiviral activity

A series of seventeen tetrazole derivatives of 1,7,7-trimethyl-[2.2.1]bicycloheptane were synthesized using click chemistry methodology and characterized by spectral data. Studies of cytotoxicity and in vitro antiviral activity against influenza virus A/Puerto Rico/8/34 (H1N1) in MDCK cells of the compounds obtained were performed. The structure-activity relationship analysis suggests that to possess virus-inhibiting activity, the compounds of this group should bear oxygen atom with a short linker (C2-C4), either as a hydroxyl group (18, 19, 29), keto-group (21) or as a part of a heterocycle (24). These compounds demonstrated low cytotoxicity along with high anti-viral activity.

Bis(carbamoylmethylphosphine oxide) ligands fixed on the arene core via 1,2,3-triazole linkers: Novel effective extractants for palladium, lanthanides and actinides

GRAPHICAL ABSTRACT ABSTRACT Novel polydentate neutral organophosphorus ligands containing two diphenyl-(diethylcarbamoyl-methyl)phosphine oxide moieties fixed on the arene platform via methylene-1,2,3-triazole linkers (Ar-CMPO) were synthesized by the method of click chemistry and studied as an extractant for Pd(II), U(VI), Th(IV), and lanthanides(III) ions from HNO3 solutions.