RESUMEN
A broad range of 1,10-phenanthroline substrates was efficiently C-H functionalised, providing rapid, gram-scale access to substituted heteroaromatic cores of broad utility. Furthermore, this C-H functionalisation pathway was extended to the synthesis of previously inaccessible, ultra-soluble, 2,9-bis-triazinyl-1,10-phenanthroline (BTPhen) ligands for advanced nuclear fuel cycles.
RESUMEN
The first hydrophilic, 1,10-phenanthroline derived ligands consisting of only C, H, O and N atoms for the selective extraction of Am(iii) from spent nuclear fuel are reported herein. One of these 2,9-bis-triazolyl-1,10-phenanthroline (BTrzPhen) ligands combined with a non-selective extracting agent, was found to exhibit process-suitable selectivity for Am(iii) over Eu(iii) and Cm(iii), providing a clear step forward.
RESUMEN
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 (CyMe4-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.