Preorganization of N,O-hybrid phosphine oxide chelators for effective extraction of trivalent Am/Eu ions – a computational study

Abstract

N, O-hybrid phosphine oxide ligands with N-heterocyclic cores are the advanced extractants for extracting actinides over lanthanides. Yet, the challenging task in designing an efficient hybrid ligand is tracing the...

Kinetic features of solvent extraction by N,O-donor ligands of f-elements: a comparative study of diamides based on 1,10-phenanthroline and 2,2′-bipyridine

“…The anti-conformation of the pyridine rings agrees with the data of a large number of works, 11,23,77,78 where the slow extraction kinetics is explained by the necessity of the bipyridine fragment to switch into the binding syn -conformation. 72–76…”

“…The anti-conformation of the pyridine rings agrees with the data of a large number of works, 11,23,77,78 where the slow extraction kinetics is explained by the necessity of the bipyridine fragment to switch into the binding syn-conformation. [72][73][74][75][76] The examples of the binding conformations of similar phenanthroline N-,O-donor ligands, are shown in ref.…”

“…the difference between the energies of bonded and free forms of the ligand 71 ) for ligands with a mobile core, as they need to adopt a binding conformation for efficient complex formation. [72][73][74][75][76] The mutual rotation of the pyridyl rings determines a high pre-organization energy 11,23,77,78 and, consequently, slow extraction kinetics.…”

Why trans and not cis? – Molecular dynamics and DFT study on selective separation of dihaloethene isomers using perethylated pillar[5]arene

“…The covalent character of the host-guest interactions is calculated using the formula [orbital energy/ (electrostatic energy + orbital energy)] Â 100 as reported in the literature. 41,42 The covalency of the cis complex increases in the order DFE (36.42%) o DCE (41.22%) o DBE (42.35%) o DIE (43.07%) and that of the trans complex increases in the order DFE (34.38%) o DCE (39.11%) o DBE (42.75%) o DIE (44.58%). The electrostatic interaction and the orbital interaction for trans complexes increase from F to I. EDA gives promising information to prove that EP5 has a greater preference for selecting trans-DXEs.…”

Theoretical investigation on the ligands constructed from phenanthroline and five-membered N-heterocyclic rings for bonding and separation properties of Am(iii) and Eu(iii)

“…Furthermore, DFT method has been utilized to predict the separation properties of various N-containing ligands for lanthanides and actinides. [23][24][25][26] For instance, Kong 23 and collaborators employed DFT methodologies to investigate the separation performance of preorganized pyridylpyrazole-based ligands for Am(III)/Eu(III), indicating that enhancing the rigidity of the bridging framework rather than the side chains can improve the ligand's selectivity towards Am(III)/Eu(III). Huang et al 24 conducted theoretical studies on N,N,N 0 ,N 0 -tetrakis[(6-carboxypyridin-2-yl)methyl]ethylene-diamine (H 4 TPAEN) ligands and their derivatives for actinide separation.…”