Complexation of Pu(IV) with TMDGA, TEDGA, and TODGA diglycolamide ligands was followed by vis-NIR spectroscopy. A crystal structure determination reveals that TMDGA forms a 1 : 3 homoleptic Pu(IV) complex with the nitrate anions forced into the outer coordination sphere.
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http://dx.doi.org/10.1039/c2cc34967a | DOI Listing |
Inorg Chem
August 2023
Department of Chemistry and Nuclear Science and Engineering Center, Colorado School of Mines, Golden, Colorado 80401, United States.
-tetramethyl diglycolamide (TMDGA), a methylated variant of the diglycolamide extractants being proposed as curium holdback reagents in advanced used nuclear fuel reprocessing technologies, has been crystallized with plutonium, a transuranic actinide that has multiple accessible oxidation states. Two plutonium TMDGA complexes, [Pu(TMDGA)][Pu(NO)] and[Pu(TMDGA)][Pu(NO)]·0.75MeOH, were crystallized through solvent diffusion of a reaction mixture containing plutonium(III) nitrate and TMDGA.
View Article and Find Full Text PDFInorg Chem
May 2023
Aix Marseille Université, CEA, CNRS, BIAM, UMR7265, IPM, Saint Paul-Lez-Durance 13108, France.
Inorg Chem
March 2022
CEA, DES, ISEC, DMRC, Univ Montpellier, Marcoule, 30207 Bagnols sur Cèze, France.
A new hexanuclear plutonium cluster has been stabilized in aqueous media with acetate ligands. To probe the formation of such a complex structure, visible-near infrared (vis-NIR) absorption spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) were combined. The presence of PuO(OH)(CHCOO) species in solution was first detected by vis-NIR and EXAFS spectroscopy.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2021
CEA, DES, ISEC, DMRC, Univ Montpellier, Marcoule, F-30207 Bagnols-sur-Ceze Cedex, France.
The strong influence of the structure of amide derivatives on their extraction properties has been demonstrated in several studies in the literature. To investigate and rationalize the influence of the nature and length of the monoamide alkyl chains on Pu(iv) extraction/complexation, a theoretical study was performed using the Density Functional Theory (DFT) method in the scalar relativistic framework. For that, the geometries for the inner/outer-sphere complexes and interaction energies of [Pu(NO3)4] and [Pu(NO3)6]2- with different ligands have been calculated.
View Article and Find Full Text PDFACS Earth Space Chem
November 2019
Research Centre for Radwaste Disposal and Williamson Research Centre for Molecular Environmental Science, School of Earth and Environmental Sciences, The University of Manchester, Manchester, M13 9PL, United Kingdom.
Understanding interactions between iron (oxyhydr)oxide nanoparticles and plutonium is essential to underpin technology to treat radioactive effluents, in cleanup of land contaminated with radionuclides, and to ensure the safe disposal of radioactive wastes. These interactions include a range of adsorption, precipitation, and incorporation processes. Here, we explore the mechanisms of plutonium sequestration during ferrihydrite precipitation from an acidic solution.
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