Some selected aminophosphine oxides (AmPOs) and their corresponding La(iii) and Th(iv) complexes are synthesized and analyzed by FT-IR, 1H-NMR, 31P{1H}-NMR, elemental analysis and TGA data.

Selvakumar R

Department of Mathematics

School of Advanced Sciences

Vellore Campus

Akella Sivaramakrishna

Department of Chemistry

Pavankumar B.B

Goud E.V

Kumar S.K.A

Vijayakrishna K

Rao C.V.S.B

Sabharwal K.N

Jha P.C.

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

RSC Advances

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

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

New bisphosphoramides (having phenyl (EDAPOPh2) and ethoxy (EDADEP) substituents attached to phosphoryl groups bridged with ethylenediamine spacer) are synthesized and structurally characterized by spectroscopic techniques as well as elemental analysis. The molecular structure of EDAPOPh2was determined by single crystal X-ray diffraction technique. The interaction of these bisphosphoramides with calf thymus DNA (ct-DNA) is investigated using UV–Visible absorption and fluorescence spectral data as well as the DFT calculations. These studies reveal that EDAPOPh2and EDADEP interact with DNA in a partial intercalation mode. The intrinsic binding constants Kbof two different bisphosphoramides with ct-DNA were determined by fluorescence spectroscopy as 2.08 × 104and 3.86 × 104M−1respectively. The results indicated that the two compounds bind to ct-DNA with different binding affinities, i.e. EDAPOPh2&gt; EDADEP. The binding mechanism of these bisphosphoramides to ct-DNA is also discussed. © 2017

Inorganica Chimica Acta

Synthesis, structure and DNA interaction studies of bisphosphoramides: Theoretical and experimental insights

This review summarizes significant contributions reported on aminophosphine oxides (AmPOs), specifically those containing at least one amino group present as amino substituents on α- and β-carbons including direct P–N bond containing molecules. AmPOs have additional ‘N’ site(s), including highly basic ‘P=O’ groups, and these features make favor smooth and unexpected behavior. The most striking manifestations of flexibility of AmPOs are that they are exciting ligand systems for the coordination chemistry of actinides, and their involvement in catalytic organic reactions including enantioselective opening of meso-epoxides, addition of silyl enol ethers, allylation with allyltributylstannane, etc. The diverse properties of the AmPOs and their metal complexes demonstrate both the scope and complexity of these systems, depending on the basicity of phosphoryl group, and nature of the substituents on the pentavalent tetracoordinate phosphorus atom and metal. Two components key to understanding the challenges of actinide separations are detailed here, namely, previously described separation methods, and recent investigations into the fundamental coordination chemistry of actinides. Both are aimed at probing the critical features necessary for improved selectivity of separations. This review leads to the conclusion that, although many AmPOs have already been discovered and developed over the past century, many opportunities nevertheless exist for further developments towards new extraction processes and new catalytic materials by fine tuning the electronic and steric properties of substituents on the central phosphorus atom. © 2017, Springer International Publishing Switzerland.

Topics in Current Chemistry

Aminophosphine Oxides: A Platform for Diversified Functions

Dicyclohexylphosphinic acid (DcyHPA) and some of its metal complexes with lanthanides (La, Ce, Gd, Sm and Nd) and actinides (U and Th) were prepared and subsequently the structural composition was elucidated. The single crystal XRD data and theoretical analysis revealed that the ligand (DcyHPA) exists as a dimer in solid state. DcyHPA showed dual nature for the extraction of U(VI), Th(IV) and Am(III) from nitric acid medium i.e. at lower acidity, the ligand behaves as an acidic extractant and extracted the metal through cation exchange mechanism while solvation mechanism played a major role for extraction at higher acidity. Additionally, density functional theory (DFT) calculations were demonstrated to understand the electronic structure of thorium-DcyHPA metal complex formed during the extraction process. © 2016 Elsevier Ltd

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

Some aminophosphine oxides (AmPOs), (R1)(R2)(R 3)P=O [R1=R2=R3= HNCH 2CH=CH2; R1= R2=Ph, R 3=HNCH2CH=CH2; R1=R 2=R3=HNNMe2; R1=R2=Ph, R3=HNNMe2; R1=R2=R3= NC4H8O; R1= R2=Ph, R3= NC4H8O], have been synthesized. The coordination chemistry of these AmPOs is studied with La(III), Th(IV), and U(VI) salts. The products are characterized by various analytical and spectroscopic techniques, and the thermal properties of the ligands and their complexes examined. The TGA data for these compounds show different decomposition temperatures, as well as thermal stability of the metal complexes. Comparisons are made among different ligands on their selective complexing ability towards some chosen metal salts. Mulliken population analysis shows that the basicity of P=O of ligand increases with an increase in the number of P-bonded amino groups. © 2013 Taylor &amp; Francis.

Investigations on synthesis, thermolysis, and coordination chemistry of aminophosphine oxides

Arabian Journal of Chemistry

The production of rare earth elements group via tributyl phosphate extraction and precipitation stripping using oxalic acid

Dental Abstracts

Ch-ch-ch-changes

Journal of Organometallic Chemistry

Electronic aspects of the phosphine-oxide → phosphinous acid tautomerism and the assisting role of transition metal centers

Sax's Dangerous Properties of Industrial Materials

Bis(Dimethylamino)Dimethylstannane 993-74-8

Function of substituents in coordination behaviour, thermolysis and ligand crossover reactions of phosphine oxides

Journal	Data powered by TypesetRSC Advances
Publisher	Data powered by TypesetRoyal Society of Chemistry (RSC)
ISSN	20462069
Open Access	0