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.