1. Exploring electronic effects on the partitioning of actinides(iii) from lanthanides(iii) using functionalised bis-triazinyl phenanthroline ligands.
- Author
-
Edwards, Alyn C., Wagner, Christoph, Geist, Andreas, Burton, Neil A., Sharrad, Clint A., Adams, Ralph W., Pritchard, Robin G., Panak, Petra J., Whitehead, Roger C., and Harwood, Laurence M.
- Subjects
ACTINIDE elements ,RARE earth metals ,EXTRACTION (Chemistry) - Abstract
The first examples of 4,7-disubstituted 2,9-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzo-triazin-3-yl)-1,10-phenanthroline (CyMe
4 -BTPhen) ligands are reported herein. Evaluating the kinetics, selectivity and stoichiometry of actinide(iii) and lanthanide(iii) radiotracer extractions has provided a mechanistic insight into the extraction process. For the first time, it has been demonstrated that metal ion extraction kinetics can be modulated by backbone functionalisation and a promising new CHON compliant candidate ligand with enhanced metal ion extraction kinetics has been identified. The effects of 4,7-functionalisation on the equilibrium metal ion distribution ratios are far more pronounced than those of 5,6-functionalisation. The complexation of Cm(iii) with two of the functionalised ligands was investigated by TRLFS and, at equilibrium, species of 1 : 2 [M : L] stoichiometry were observed exclusively. A direct correlation between the ELUMO –EHOMO energy gap and metal ion extraction potential is reported, with DFT studies reaffirming experimental findings. [ABSTRACT FROM AUTHOR]- Published
- 2016
- Full Text
- View/download PDF