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.

Akella Sivaramakrishna

Department of Chemistry

School of Advanced Sciences

Vellore Campus

Veerashekhar Goud E

Pavan Kumar B.B

Shruthi Y

Paul A

Vijayakrishna K

Brahmananda Rao C.V.S

Sabharwal K.N

Clayton H.S.

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

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

Journal of Coordination Chemistry

To delineate the effect of P–C bond of phosphorous esters on the extraction of actinides, diverse organophosphorus esters (trihexyl phosphonate (THP), dihexylhexyl phosphonate (DHHP), hexyldihexyl phosphinate (HDHP) and trihexylphosphine oxide (THPO)) were synthesized and spectroscopically characterized. The physical properties such as density, viscosity are reported in subsequent sections. The extraction behaviour of the ligands were evaluated for U(VI), Th(IV) and Am(III), as well as acid uptake as a function of nitric acid ranging from 0.01–6 M. Distribution ratios for U(VI), Th(IV) and Am(III) indicate a large difference in solvent strength among these compounds. Replacement of P–O–C group by P–C group i.e. introduction of electron donating group greatly increases the solvent strength. The P=O stretching frequency can be correlated with the solvent strength of these compounds, and the conclusions are further supported by density functional theory calculations. © 2018 Elsevier B.V.

Journal of Molecular Liquids

Trihexyl phosphate to trihexyl phosphine oxide: Diverse effect on extraction behavior 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.

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

Polyhedron

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

Physical Review B

Erratum: Accurate and simple analytic representation of the electron-gas correlation energy [Phys. Rev. B 45, 13244 (1992)]

Purification of Laboratory Chemicals

Purification of Organic Chemicals

Complexation studies of Cm(III), Am(III), and Eu(III) with linear and cyclic carboxylates and polyaminocarboxylates

Journal of Rare Earths

Preparation of lanthanum sulfide nanoparticles by thermal decomposition of lanthanum complex

Synthesis and characterization of new imidophosphanes and phosphine oxides containing 3,3,4,4-tetramethylsuccinimidyl group

Journal	Journal of Coordination Chemistry
Publisher	Informa UK Limited
ISSN	0095-8972
Open Access	0