Tripodal chelates bearing three diglycolamide units precisely arranged on a triphenoxymethane platform were synthesized to mimic the preferred tricapped trigonal prismatic geometry favored by lanthanides with oxygen donor ligands, and the ligand binds heavier lanthanides very efficiently in acidic media.
Structural modifications of carbamoylmethylphosphine oxide (CPMO)-functionalized triphenoxymethane platforms are described, and the influence of these changes on the ability of the ligand to extract actinides from simulated acidic nuclear waste streams has been evaluated. The ligand system has been shown to have excellent binding efficiency and a selectivity for An(IV) in comparison to the a simple monomeric CMPO ligand under analogous conditions. Both the extraction efficiency and selectivity are strongly dependent on the flexibility and electronic properties of the ligating units in the triphenoxymethane construct. The Tb(III) and Bi(III) nitrate complexes of tris-CMPO derivatives have been isolated, and their structures were elucidated by NMR, ESI FT-ICR MS, and X-ray analysis, providing information on the interactions between metal ions and the tris-CMPO molecules.
C 3 -symmetric triphenoxymethane platforms were substituted with carbamoylmethylphosphine sulfide arms and these tris-CMPS compounds were evaluated as extractants for f-element metal ions from 1 M nitric acid solution. Their properties were compared to the carbamoylmethylphosphine oxide derivatives on the same triphenoxymethane platform (tris-CMPO). The terbium complex of tris-CMPS was crystallized and examined via X-ray structural analysis to provide valuable insight into the binding properties of the soft tripodal chelate.
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