Alkyl and cyclic substituted aminophosphonates (AmPs) were synthesized and characterized with various spectroscopic techniques. The molecular structures of diphenyl phenyl aminophosphonate (DPhPhAmP) and diphenyl cyclohexyl aminophosphonate (DPhCyAmP) were elucidated based on the single crystal XRD analysis. Extraction behavior of these synthesized AmPs were investigated with some actinides [U(VI), Th(IV), and Am(III)] and also studied their acid uptake as a function of nitric acid concentration. Here we have compared the extraction behavior of aminophosphonates (AmPs) towards actinides as a function of alkyl, cyclic and alicyclic substituents. © 2018 Elsevier B.V.

Akella Sivaramakrishna

Department of Chemistry

School of Advanced Sciences

Vellore Campus

Das D

Brahmmananda Rao C.V.S

Sivaraman N

Vijayakrishna K.

Vellore Institute of Technology (VIT) is a private university located in&nbsp;Tamil Nadu, India. Founded in 1984, as Vellore Engineering College, the institution offers 20 undergraduate, 34 postgraduate, four integrated and four research programs. It has campuses in Vellore, Amravati, Bhopal and Chennai.

VIT is one of the top ranked private universities in India according to NIRF, THE and QS Rankings.&nbsp;Govt. of India has recognized&nbsp;VIT, Vellore as an&nbsp;Institution of Eminence. This has allowed VIT to take independent quality initiatives and move up in world ranking.

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VIT University

Inorganica Chimica Acta

A novel phosphoramidate-functionalized polymeric resin was synthesized by anchoring diethyl (3-(1H-imidazol-1-yl)propyl)phosphoramidate group with chloromethylated polystyrene divinylbenzene resin. The grafted resin was characterized using elemental analysis, Fourier transform infrared, solid-state 31P NMR energy-dispersive X-ray spectroscopies, and thermogravimetric analysis. The surface morphology of the functionalized resin was investigated using scanning electron microscopy and the surface area was measured with Brunauer–Emmett–Teller analysis. Sorption affinities of the functionalized resin towards actinides such as Th(IV) and U(VI) were determined under various concentrations of nitric acid solution (0.01–6 mol L−1). Desorption of the actinides from the loaded resin was performed using a solution of 0.01 mol L−1 nitric acid. Reusability of the grafted resin was studied over various successive cycles and the stability of the functional groups on the synthesized resin was monitored using various analytical techniques. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry

Polymer International

Phosphoramidate-functionalized Merrifield resin: synthesis and application in actinide separation

Carbamoylmethyl phosphine oxide (CMPO) derivatives are well known ligands in the separation and extraction of trivalent lanthanides and actinides from nuclear waste. The substituents of CMPO play major role in their selectivity and extractability. We report the synthesis and characterization of diphenylmorpholine carbamoylmethyl phosphine oxide (DPMCMPO) (L1) and diphenyl-N,N-diethyl carbamoylmethyl phosphine oxide (DPDECMPO) (L2) using various spectroscopic techniques, such as FT-IR, 1H, 13C, and 31P NMR. The molecular structure of DPMCMPO is confirmed by single crystal XRD analysis. The present study aims to understand the influence of substituents on ‘N’ atom of L1 (morpholine based DPMCMPO) and L2 (diethyl substituted DPDECMPO) ligands for the extraction of some selected actinide ions such as Th(IV), U(VI) and Am(III). The geometry and electronic structure of these ligands and their respective complexes with Th(NO3)4 and UO2(NO3)2 are further explored using density functional theory (DFT) calculations. The employed ligands (L1 and L2) show greater distribution values for Th(IV) over U(VI), due to strong “ligand-Th” complexation ability as suggested by DFT calculations. © 2017 Elsevier Ltd

Polyhedron

Diphenylmorpholine CMPO: Synthesis, coordination behavior and extraction studies of actinides

Tri-n-butyl phosphate (TBP) is most extensively used extractant in the nuclear fuel cycle. The present work investigates the effect of substituents and their role in the basicity of organophosphorus extractant on the uptake of actinides. In this connection, we have synthesized six different analogues of TBP by altering one of its butoxy group. The synthesized TBP derivatives were well characterized and evaluated for their solvent extraction behavior towards U(VI), Th(IV), Pu(IV) and Am(III), as well as acid uptake as a function of nitric acid ranging from 0.01 to 6 M and the data provides the comparison of their extraction behavior with that of 30% (1.1 M) tri-n-butyl phosphate under identical conditions. It was observed that distribution coefficient values strongly depend on the nature and size of the substituents. The presence of electron donating groups enhances the uptake of the actinides and the distribution coefficient values were significantly larger as compared to that of TBP. In addition, the effect of sodium nitrate on the extraction of uranium and enthalpy of extraction were also studied and revealed that the extraction process was exothermic. © 2017 Elsevier B.V.

Extraction of actinides by Tri-n-butyl phosphate derivatives: Effect of substituents

Extraction behavior of some selected actinides like U(VI), Th(IV), and Am(III) was investigated with three different H-phosphine oxides, viz. diphenyl hydrogen phosphine oxide (DPhPO), dihexyl hydrogen phosphine oxide (DHePO) and diphenyl phosphite (DPP). The H-phosphine oxides exhibited a dual nature towards the extraction of actinides where the ligand not only extracts the metals by cation exchange but also by coordination with the phosphoryl group at lower and higher acidic concentrations, respectively. Among all ligands employed, DPhPO showed highest extraction with actinides with a substituent dependent trend as follows: DPhPO &gt; DHePO &gt; DPP. This trend emphasizes the importance of substituents around the phosphine oxide towards their extraction of actinides. The coordination behavior of DPhPO was studied by investigating its corresponding complexes with Th(NO3)4 and UO2(NO3)2. The metal complexes of these actinides were characterized using FT-IR, 1H and 31P NMR spectroscopic techniques. Density Functional Theory (DFT) calculations were also performed to understand the electronic and geometric structure of the ligand and the corresponding metal complexes. © 2017 Informa UK Limited, trading as Taylor &amp; Francis Group.

Journal of Coordination Chemistry

Extraction and coordination behavior of diphenyl hydrogen phosphine oxide towards actinides

AbstractThree different alicyclic substituents H-phosphonates, namely, dicyclopentyl H-phosphonate, dicyclohexyl H-phosphonate and dimenthyl H-phosphonate were synthesized and used for liquid–liquid extraction of actinide elements (U, Am and Th) and lanthanide (Gd) in

Journal	Data powered by TypesetInorganica Chimica Acta
Publisher	Data powered by TypesetElsevier BV
ISSN	0020-1693
Open Access	0