Extraction of Scandium, Rare-Earth Elements, and Yttrium From Nitric Acid Solutions by Selected Diphosphine Dioxides

Туранов, А. Н.; Карандашев, В. К.; Kharitonov, A. V.; Yarkevich, A. N.; Safronova, Z. V.

doi:10.1080/07366290008934724

Cited by 37 publications

(7 citation statements)

References 14 publications

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“…This is apparently due to the fact that the size of the chelate ring in the extractable complex increases with an increase in the length of alkylene bridges linking the PO groups in the extractant molecule. Similar influence of the length of the alkylene bridge in the NBOPC molecule was noted previously in the extraction of Am(III) [17] and Ln(III) [18] with tetraphenylalkylenediphosphine dioxides and alkyl-substituted alkylenediphosphonic acids [19,20].…”

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confidence: 62%

Extraction Properties of Bis(diphenylphosphinylethyl)phosphinic Acid in Nitric Acid Solutions

2005

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Extraction of microamounts of U(VI), Th(IV), Sc(III), and Ln(III) from HNO 3 solutions with solutions of bis(diphenylphosphinylethyl)phosphinic acid in dichloroethane was studied. The stoichiometry of the extractable complexes was determined, and the effect of the inorganic anion and organic diluent on the extraction of rare-earth elements was examined. An increase in the number of phosphoryl groups in the extractant molecule and replacement of ethylene bridges between the phosphorus atoms by methylene bridges enhance the extraction of metal ions from nitric acid solutions.The interest in extraction properties of polyfunctional organophosphorus acids increased recently, because of the prospects for using these agents in radiochemical practice for the recovery of transplutonium, rare-earth (Ln), and other elements from nitric acid solutions [1]. It was shown that dibasic P, P`-di-(2-ethylhexyl)methylenediphosphonic acid [2, 3] and monobasic (diphenylphosphinylmethyl)phenylphosphinic [4] and bis(diphenylphosphinylmethyl)phosphinic (I) [5] acids exhibit extremely high extractive power toward Th(IV), U(VI), Am(III), and Ln(III) in nitric acid solutions. It was suggested that the high extractive power of acid I is due to the possibility of formation of six-membered chelate rings with metal ions, since the phosphoryl groups in this agent are linked with methylene bridges. In this connection, it is interesting to study how the length of the alkylene bridge between the P(O)OH and P(O) fragments and the number of phosphoryl groups in the extractant molecule affect its extractive power.To this end, we studied the extraction of U(VI), Th(IV), Sc(III), and Ln(III) from aqueous solutions of HNO 3 with solutions of bis(2-diphenylphosphinylethyl)phosphinic (II) and 2-phenylethyl-(2-diphenylphosphinylethyl)phosphinic (III) acids in dichloroethane. For comparison, we also studied the extraction with a neutral analog of II, pentaphenyldiethylenetriphosphine trioxide IV [6], and with diphenylphosphinic acid V.

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confidence: 62%

Extraction Properties of Bis(diphenylphosphinylethyl)phosphinic Acid in Nitric Acid Solutions

2005

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“…It should be noted that, in the extraction from 3 M HNO 3 , D Sc is lower than D Ln for La3Ho (Fig. 4), whereas in the extraction with TPMDPO scandium is extracted from aqueous solutions of similar composition more efficiently than REE [20]. With increasing C HNO 3 , b La/Sc decreases, and at C HNO 3 = 7 M Sc is extracted with a solution of L more efficiently than REE (Fig.…”

Section: Ion [Eqs (4) (5)]mentioning

confidence: 91%

Extraction Properties of Butyl Bis(dibutoxyphosphinylmethyl)phosphinate in Nitric Acid Solutions

2005

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The extraction of HNO 3 and microamounts of U(VI), Th(IV), Sc(III), REE(III), and Am(III) nitrates from HNO 3 solutions with solutions of butyl bis(dibutoxyphosphinylmethyl)phosphinate in organic diluents was studied. The stoichiometry of the extractable complexes was determined, and the apparent extraction constants were calculated. The capability of the extractant to recover the examined elements from nitric acid solutions grows with an increase in the number of phosphoryl groups in its molecule. The recovery of the metal ions into the organic phase becomes more efficient in going to more polar organic diluents.Neutral bidentate organophosphorus compounds, alkylenediphosphine dioxides and diaryl(dialkylcarbamoylmethyl)phosphine oxides (CMPOs), exhibit high extractive power toward trivalent transplutonium (TPE) and rare-earth (REE) elements [1310]. However, low solubility of tetraphenylmethylenediphosphine dioxide (TPMDPO) in organic diluents is its essential drawback, considerably decreasing the extraction capacity of TPMDPO and restricting the feasibility of its use for recovering TPE from high-level waste (HLW) from spent nuclear fuel reprocessing [4]. Replacement of phenyl substituents at the P atom in the TPMDPO molecule by alkyl and especially alkoxy groups makes the extractant more compatible with organic diluents but drastically decreases its extraction power [3]. In particular, dibutyl phenyl(ethyl)phosphinylmethylphosphonate is fully miscible with decane, but its extraction power toward Am(III) is lower than that of TPMDPO and even of monodentate dioctyl-(isoamyl)phosphine oxide [11]. Dialkyl methylphosphonates exhibit still lower extraction power; nevertheless, they recover Am(III) from nitric acid solutions with fairly high distribution factors [12,13]. In going from monodentate dialkyl methylphosphonates to bifunctional tetraalkyl methylenediphosphonates, the extraction power toward Am(III) and REE(III) considerably increases [14].It is interesting to examine the extraction power of compounds containing, along with phosphonate centers, also other donor fragments, in particular, phosphinate groups, and to reveal how the number of phosphoryl groups in molecules of polyphosphoryl compounds affects their extraction power. To this end, we examined regular trends in the distribution of HNO 3 , U(VI), Th(IV), Sc(III), Am(III), and REE(III) between aqueous HNO 3 and solutions of butyl bis(dibutoxyphosphinylmethyl)phosphinate (L) in organic diluents.

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“…Furthermore, they can serve as useful precursors in the synthesis of a variety of synthetically elaborated bifunctional adducts by the ready addtion of several nucleophiles to the double bond 5. Bisphosphine oxides are used as organoextractions in hydrometallurgy,6 and are key intermediates for the preparation of various valuable phosphine ligands7 in homogeneous catalysis, organocatalysts for the allylation of N ‐acylhydrazones8 and stereoselective direct aldol reactions of trifluoroethyl thioestesters 9…”

Section: Methodsmentioning

confidence: 99%

Nickel(II)‐Magnesium‐Catalyzed Cross‐Coupling of 1,1‐Dibromo‐1‐alkenes with Diphenylphosphine Oxide: One‐Pot Synthesis of (E)‐1‐Alkenylphosphine Oxides or Bisphosphine Oxides

et al. 2013

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A novel nickel(II)-magnesium-mediated cross-coupling of diphenylphosphine oxide with a variety of 1,1-dibromo-1-alkenes has been developed, which provides a powerful and general methodology for the stereoselective synthesis of various (E)-1-alkenylphosphine oxides or bisphosphine oxides, with operational simplicity of the procedure, good to high yields and broad substrate applicability. Mechanistic studies reveal that the reaction might involve a Hirao reduction, cross-coupling and Michael addition.Transition metal-catalyzed carbon-phosphorus bond formation by cross-coupling reactions has attracted increasing attention in the last two decades due to its wide applicability in biological, pharmaceutical, material and catalytic sciences. [1] Alkenylphosphine oxides and bisphosphine oxides are important classes of phosphorus-containing, extremely valuable compounds in organic chemistry. For example, alkenylphosphine oxides are endowed with a wide-range of biological activities, [2] outstanding flame-retardant properties [3] and eminent metal-complexing abilities as ligands. [4] Furthermore, they can serve as useful precursors in the synthesis of a variety of synthetically elaborated bifunctional adducts by the ready addtion of several nucleophiles to the double bond. [5] Bisphos-phine oxides are used as organoextractions in hydrometallurgy, [6] and are key intermediates for the preparation of various valuable phosphine ligands [7] in homogeneous catalysis, organocatalysts for the allylation of N-acylhydrazones [8] and stereoselective direct aldol reactions of trifluoroethyl thioestesters. [9] Recently, a few transition metal-catalyzed methods for the preparation of alkenylphosphine oxides have continuously emerged including the Pd-catalyzed cross-coupling of alkenyl halides with phosphine oxides, [10] olefin cross-metathesis, [11] Cu-catalyzed decarboxylative coupling, [12] cleavage of silylepoxides [13] or stannyloxiranes [14] with lithium diphenylphosphide, hydrophosphination of terminal alkynes with diphosphines and hydrosilanes in the presence of oxygen, [15] Rh-catalyzed reaction of 1-alkynylphosphines with water, [16] in situ reactions of functionalized mono-A C H T U N G T R E N N U N G ylides with carbonyl compounds [17] and transition metal-catalyzed addition of P(O)H compounds to alk-A C H T U N G T R E N N U N G ynes. [18,20] Bisphosphine oxides can be prepared by several methods such as the Pd- [18f,19] or Rh-catalyzed [20] double hydrophosphinylation of alkynes, substitution reactions of 1,2-dichloride complex, [21] double nucleophilic addition of secondary phosphine oxides to methylacetylene, [22] Kolbe electrolytic coupling reactions of phosphinoyl-acetic or propanoic acids [23] and catalytic olefin cross-or homo-metathesis. [11,24] However, these traditional procedures suffer from relatively strict reaction conditions, low selectivity, poor substrate scope or unsatisfactory yield, and there is still a strong need for developing more convenient and efficient approaches to alkenylphosphine oxides and b...

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Extraction of Scandium, Rare-Earth Elements, and Yttrium From Nitric Acid Solutions by Selected Diphosphine Dioxides

Cited by 37 publications

References 14 publications

Extraction Properties of Bis(diphenylphosphinylethyl)phosphinic Acid in Nitric Acid Solutions

Extraction Properties of Bis(diphenylphosphinylethyl)phosphinic Acid in Nitric Acid Solutions

Extraction Properties of Butyl Bis(dibutoxyphosphinylmethyl)phosphinate in Nitric Acid Solutions

Nickel(II)‐Magnesium‐Catalyzed Cross‐Coupling of 1,1‐Dibromo‐1‐alkenes with Diphenylphosphine Oxide: One‐Pot Synthesis of (E)‐1‐Alkenylphosphine Oxides or Bisphosphine Oxides

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