Published 2012 | Version v1
Book

Hindered rotation in a novel 1,2,4-triazinyl phenanthroline (T-Phen) ligand leading to improved separation of Am3+ and Eu3+ vis-a-vis 1,2,4-triazinyl bipyridine (T-Bipy): synthesis and computational validation of the experimental results

  • 1. Bioorganic Division, Bhabha Atomic Research Centre, Mumbai (India)
  • 2. Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai (India)

Description

A novel nitrogen donor ligand having more pre-organized structure, 1,2,4-triazinyl phenanthroline (T-phen), was synthesized and evaluated for lanthanide - actinide separation. The extraction and selectivity for Am3+ over Eu3+ was found to be improved with T-phen as compared to the analogous 1,2,4-triazinyl bipyridine bipy, which was explained by analyzing their conformational energies and energy differences between the frontier orbitals (highest occupied molecular orbital (HOMO) and lowest unoccupied molecular (LUMO) with the help of ab initio molecular orbital calculations. Higher covalence in Am3+ complexes compared to the Eu3+ complexes were indicated by more shared electrons between Am3+ and bonded 'N' atoms, shorter 'Am-N' bonds and higher overlap between the orbitals of Am3+ and ligands in the frontier orbitals complexes in case of both the ligands. The separation factor values with T-phen and T-bipy are given at varying pH values. The results suggest more efficient separation with T-phen as compared to T-bipy which is attributed to hindered rotation of the former ligand

Additional details

Publishing Information

Publisher
Bhabha Atomic Research Centre
Imprint Place
Mumbai (India)
Imprint Title
Proceedings of DAE-BRNS biennial symposium on emerging trends in separation science and technology
Imprint Pagination
274 p.
Journal Page Range
p. 36

Conference

Title
5. DAE-BRNS biennial symposium on emerging trends in separation science and technology
Acronym
SESTEC-2012
Dates
27 Feb - 1 Mar 2012
Place
Mumbai (India)

INIS

Country of Publication
India
Country of Input or Organization
India
INIS RN
44017228
Subject category
S37: INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY;
Resource subtype / Literary indicator
Conference
Quality check status
Yes
Descriptors DEI
AMERICIUM; EUROPIUM; LIGANDS; NITRIC ACID; PH VALUE; TBP;
Descriptors DEC
ACTINIDES; BUTYL PHOSPHATES; ELEMENTS; ESTERS; HYDROGEN COMPOUNDS; INORGANIC ACIDS; INORGANIC COMPOUNDS; METALS; NITROGEN COMPOUNDS; ORGANIC COMPOUNDS; ORGANIC PHOSPHORUS COMPOUNDS; OXYGEN COMPOUNDS; PHOSPHORIC ACID ESTERS; RARE EARTHS; TRANSPLUTONIUM ELEMENTS; TRANSURANIUM ELEMENTS;

Optional Information

Lead record
bv63d-v1n50
Notes
2 figs.