Derivatives of (2-carbamoyl ethyl)diphenylphosphine oxides: synthesis and extraction properties with respect to actinides and lanthanides

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A series of (2–carbamoyl ethyl)diphenylphosphine oxides (KFO) has been synthesized from commercially available reagents — diphenyl chlorophosphine and acrylamides. The influence of the number of ligand fragments of Ph2P(O)(CH2)2C(O), the nature of the oligoyl radical binding these fragments, as well as the presence of additional coordination centers in the KEFO molecule on the extraction properties of KEFO with respect to actinides and lanthanides was investigated. It was found that N,N′-methylene-bis[3-(diphenylphosphoryl) has the greatest efficiency in the extraction of actinidespropionamide] (III), in which two diphenylphosphorylpropionyl radicals are bound by a rigid HNCH2NH linker (the degree of extraction of U(VI) reaches ~73%, and Th(IV) — ~85%), while in the case of lanthanides, on the contrary, ligand V, containing the maximum amount of this kind of phosphoryl carbonyl radicals attached to a conformationally non-rigid nitrogenous heterocyclic matrix, as well as KEFO (II), containing an additional C=O group in an alkyl radical attached to a nitrogen atom, has significant advantages carbamoyl fragment (when using this compound, gadolinium extraction is close to 92%). The obtained data show that highly effective and selective extractants of both 4f and 5f elements can be created on the basis of (2-carbamoyl ethyl)diphenylphosphine oxide structure.

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Sobre autores

A. Safiulina

Bochvar High-Technology Research Institute of Inorganic Materials; Mendeleev University of Chemical Technology of Russia

Autor responsável pela correspondência
Email: AMSafiulina@bochvar.ru
Rússia, Moscow, 123098; Moscow, 125047

A. Lizunov

Bochvar High-Technology Research Institute of Inorganic Materials

Email: AMSafiulina@bochvar.ru
Rússia, Moscow, 123098

E. Goryunov

Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences

Email: AMSafiulina@bochvar.ru
Rússia, Moscow, 119334

G. Bodrin

Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences

Email: AMSafiulina@bochvar.ru
Rússia, Moscow, 119334

I. Goryunova

Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences

Email: AMSafiulina@bochvar.ru
Rússia, Moscow, 119334

T. Strelkova

Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences

Email: AMSafiulina@bochvar.ru
Rússia, Moscow, 119334

M. Grigor'ev

Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences

Email: AMSafiulina@bochvar.ru
Rússia, Moscow, 119071

V. Brel'

Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences

Email: AMSafiulina@bochvar.ru
Rússia, Moscow, 119334

I. Tananaev

Federal Research Center “Kola Scientific Center of the Russian Academy of Sciences”; Tananaev Institute of Chemistry and Technology of Rare Elements and Mineral Raw Materials, RAS

Email: AMSafiulina@bochvar.ru
Rússia, Apatity, 184209; Apatity, 184209

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2. Fig. 1. Dependence of the distribution coefficients of uranium(VI) on the concentration of nitric acid during extraction with 0.01 mol/L solutions of compounds I–V in chloroform with a content of 0.025 mmol/L uranium(VI) in the initial solution.

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3. Fig. 2. Logarithmic dependences of the distribution coefficients of U(VI) on the concentration of ligand CL during extraction with compounds II, III and IV from 1 mol/L HNO3 in CHCl3 (initial concentration of uranyl nitrate in the aqueous phase 0.025 mmol/L).

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4. Fig. 3. Dependence of the distribution coefficients of thorium(IV) on the concentration of nitric acid during extraction with 0.01 mol/L solutions of compounds I–V in chloroform with a content of 0.025 mmol/L thorium(IV) in the initial solution.

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5. Fig. 4. Logarithmic dependences of the distribution coefficients of Th(VI) on the concentration of ligand CL during extraction with compounds II and III from 1 mol/L HNO3 in CHCl3 (initial concentration of thorium nitrate in the aqueous phase 0.025 mmol/L).

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6. Fig. 5. Dependence of the distribution coefficients of La(III), Nd(III), Gd(III), Ho(III) and Yb(III) on the concentration of nitric acid during extraction with 0.01 mol/L solutions of ligands I (a), II (b) , III (c), IV (d) and V (e) in chloroform at a content of 0.025 mmol/L lanthanide in the initial solution.

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7. Fig. 6. Logarithmic dependences of the distribution coefficients of Gd(III) (a) and Nd(III) (b) on the concentration of ligand CL during extraction with compounds II and V from 1 mol/L HNO3 in CHCl3 (initial concentration of Ln(III) in the aqueous phase 0.025 mmol/l).

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8. Fig. 7. Distribution coefficients of f-elements during extraction with 0.01 mol/L solutions of CEPO I–V and CMPO in chloroform from 5 mol/L HNO3.

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9. Scheme

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