Investigations on synthesis, coordination behavior and actinide recovery of unexplored dicyclohexylphosphinic acid

Goud, E. Veerashekhar; Das, Dhrubajyoti; Sivaramakrishna, Akella; Vijayakrishna, Kari; Sabareesh, Varatharajan; Gopakumar, Gopinadhanpillai; Rao, C. V. S. Brahmmananda; Lone, Mohsin Y.; Jha, Prakash C.

doi:10.1016/j.poly.2016.07.013

Cited by 11 publications

(4 citation statements)

References 42 publications

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“…The resulting organic-soluble complexes formed are eventually extracted into the organic medium to complete the extraction process. Plentiful experimental evidence is available to support this mechanism, and most of them, by and large, are based on the equilibrium constant, solubility, and structural characterization of the complexes formed during extraction. − In addition to this, theoretical studies provided further insights into the metal–ligand interactions, − nature of bonding, , solvation, − and so on and furnished ample evidence to support the experimentally proposed extraction mechanism.…”

Section: Introductionmentioning

confidence: 98%

Insights into the Coordination Behavior of Methyl-Substituted Phosphinic Acids with Actinides

et al. 2022

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The electronic structure and complexation behavior of methylsubstituted phosphinic acids with U(VI) and Pu(IV) were explored by applying quantum chemical methods. In contrast to Ingold's classification, our results indicate that the methyl group is electron-withdrawing, reducing the phosphoryl group electron density in substituted phosphinic acids. The magnitude of the computed complexation energy values increases along with the series, PA → MPA → DMPA, and MP → MMP → MDMP, implying an increasing complexation tendency upon methyl group substitution for both U(VI) and Pu(IV) complexes. One of the nitrate groups in UO 2 (NO 3 ) 2 •2L complexes (L = PA, MPA, and DMPA) is in monodentate coordination mode due to the additional stability gained from O 2 N−O•••H hydrogen bonding interactions with the acidic H atoms of respective ligands. The calculation indicates marginally stronger metal−ligand interactions in Pu(IV) complexes compared to that in U(VI), which is supported by the computed complexation energies, M−O P bond lengths, ν(P�O), the extent of metal−ligand charge transfer, and properties of M−O P bond critical points. The energy landscape of substituted phosphinic acid ligands is further analyzed within the framework of the activation strain model to explain the energetic preference of certain conformers.

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Section: Introductionmentioning

confidence: 98%

Insights into the Coordination Behavior of Methyl-Substituted Phosphinic Acids with Actinides

et al. 2022

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“…This trend is reversed compared to that observed for molecular diluents. Unlike molecular diluents, where the liquid–liquid biphasic mass transfer of metal ions using the neutral ligand proceeds through a solvation mechanism involving neutral metal–ligand species, an ion exchange mechanism is proposed to be operative in the present case . However, further confirmation is required through detailed speciation.…”

Section: Resultsmentioning

confidence: 81%

Experimental and Theoretical Investigation on the Extractive Mass Transfer of Eu³⁺Ions Using Novel Amide Ligands in 1-Hexyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)imide

Ghosh,

Pandey,

Sengupta

et al. 2023

Inorg. Chem.

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Novel amide ligands in the ionic liquid (1-hexyl-3methylimidazolium bis(trifluoromethylsulfonyl)imide) were utilized for the liquid−liquid biphasic mass transfer of Eu 3+ ions from aqueous acidic waste solution. The cation exchange mechanism was found to be operative with the formation of [Eu(NO 3 ) 2 L 3 ] + species (L = 4-chloro-N-(1-methyl-1H-pyrazol-3-yl)picolinamide). However, the presence of an inner-sphere water molecule was revealed by density functional theory (DFT) calculations. The viscosity-induced slower kinetics was evidenced during mass transfer, which was improved by increasing temperature. The process was exothermic in nature. The improvement in the kinetics of extractive mass transfer at higher temperatures is evinced by a reduction in the distribution ratio value. The spontaneity of the reaction was evidenced through the negative Gibbs free energy value, whereas the process enhances the entropy of the system, probably by releasing water molecules at least partially during complexation. The structures of bare ligands and complexes have been optimized by using DFT calculations. A high value of complexation energy, solvation energy, and associated enthalpy and free energy change reveal the efficacy in binding Eu with O and N donor atoms. In addition, natural population analysis, atoms-in-molecules analysis, and energy decomposition analysis have been employed to explore the nature of bonding existing in Eu−O and Eu−N bonds.

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“…Th(NO 3 )(DEHP) 3 , 32 Th(NO 3 ) 2 (DEHP) 2 , 33 Th[H(DEHP) 2 ] 4 , 36 and Th(NO 3 ) 2 (DcyHPA) 2 (DcyHPA: dicyclohexylphosphinic acid). 37 Therefore, it is essential to determine the molar ratio of functional ligand to Th 4+ when organophosphorus monacid is applied as functional ligand to synthesize Th 4 -IIP.…”

Section: +mentioning

confidence: 99%

Synthesis and characterization of a new ion-imprinted polymer for the selective separation of thorium(iv) ions at high acidity

Liang

Chen

et al. 2017

RSC Adv.

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Investigations on synthesis, coordination behavior and actinide recovery of unexplored dicyclohexylphosphinic acid

Cited by 11 publications

References 42 publications

Insights into the Coordination Behavior of Methyl-Substituted Phosphinic Acids with Actinides

Insights into the Coordination Behavior of Methyl-Substituted Phosphinic Acids with Actinides

Experimental and Theoretical Investigation on the Extractive Mass Transfer of Eu³⁺Ions Using Novel Amide Ligands in 1-Hexyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)imide

Synthesis and characterization of a new ion-imprinted polymer for the selective separation of thorium(iv) ions at high acidity

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Investigations on synthesis, coordination behavior and actinide recovery of unexplored dicyclohexylphosphinic acid

Cited by 11 publications

References 42 publications

Insights into the Coordination Behavior of Methyl-Substituted Phosphinic Acids with Actinides

Insights into the Coordination Behavior of Methyl-Substituted Phosphinic Acids with Actinides

Experimental and Theoretical Investigation on the Extractive Mass Transfer of Eu3+Ions Using Novel Amide Ligands in 1-Hexyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)imide

Synthesis and characterization of a new ion-imprinted polymer for the selective separation of thorium(iv) ions at high acidity

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Experimental and Theoretical Investigation on the Extractive Mass Transfer of Eu³⁺Ions Using Novel Amide Ligands in 1-Hexyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)imide