Design, synthesis and evaluation of carbamoylmethylphosphine sulfide (CMPS)-based chelates for separation of lanthanides and actinides

Matloka, Kornelia; Sah, Ajay K.; Srinivasan, Priya D.; Scott, Michael J.

doi:10.1016/j.crci.2007.02.006

Cited by 10 publications

(3 citation statements)

References 27 publications

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“…90 Conversion of phosphine oxide into the corresponding phosphine sulfide (CMPS, Chart 13) caused a drop in the extraction and selectivity for An over Ln(III). 91 Extension or removal of the methylene bridge caused a decrease in D values, whereas its alkylation increased the solubility and selectivity, albeit reducing the extraction capacity. [87][88][89] The alkyl chains hindered the formation of the chelate complex by limiting the conformational mobility around the central carbon atom.…”

Section: Cmposmentioning

confidence: 99%

Ligands for f-element extraction used in the nuclear fuel cycle

2017

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Liquid-liquid extraction is the major technique being applied for the partitioning of f-elements from nuclear waste. In this review, the recent developments in ligand design, optimization and extraction properties are summarised for the main classes of extractants (organophosphorus ligands, diamides and N-heterocycles), with a focus on the separation of actinides and lanthanides. Structural modifications, pre-organisation and different solvent systems, as key factors for the fine-tuning of the extraction properties, are discussed. From this review, it appears that small modifications of the structure of the ligand, the pre-organising platform or the solvent can have significant impact on the extraction (and separation) of metal ions. Interest in the combinations of ligands for the extraction processes is growing, since they provide improvements over individual ligands. Similarly, unconventional approaches are being pursued to develop more efficient and greener processes.

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Section: Cmposmentioning

confidence: 99%

Ligands for f-element extraction used in the nuclear fuel cycle

2017

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“…These observations, as well as general coordination chemistry principles and molecular mechanics (MM) computational analyses with other donor ligand systems,suggest that improved extraction performance might be realized by preorganization of two or more CMPO or CMP fragments on a central lipophilic platform. Indeed, several groups have explored attachment of CMPO fragments to C 3 -symmetric alkyl, − 1,3,5-trialkyl benzene, C 3 -symmetric amine, upper and lower rim-substituted calixarene, and resorcinarene platforms. In each case, the platform attachment linkage involves the amide N-atom of the CMPO fragment.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Lanthanide Coordination Chemistry, and Liquid–Liquid Extraction Performance of CMPO-Decorated Pyridine and Pyridine N-Oxide Platforms

et al. 2013

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Syntheses for a set of new ligands containing one or two carbamoylmethylphosphine oxide (CMPO) fragments appended to pyridine and pyridine N-oxide platforms are described. Molecular mechanics analyses for gas phase lanthanide-ligand interactions for the pyridine N-oxides indicate that the trifunctional NOPOCO molecules, 2-{[Ph2P(O)][C(O)NEt2]C(H)}C5H4NO (7) and 2-{[Ph2P(O)][C(O)NEt2]CHCH2}C5H4NO (8), and pentafunctional NOPOP'O'COC'O' molecules, 2,6-{[Ph2P(O)][C(O)NEt2]C(H)}2C5H3NO (9) and 2,6-{[Ph2P(O)][C(O)NEt2]CHCH2}2C5H3NO (10), should be able to adopt, with minimal strain, tridentate and pentadentate chelate structures, respectively. As a test of these predictions, selected lanthanide coordination chemistry of the N-oxide derivatives was explored. Crystal structure analyses reveal the formation of a tridentate NOPOCO chelate structure for a 1:1 Pr(III) complex containing 7 while 8 adopts a mixed bidentate/bridging monodentate POCO/NO binding mode with Pr(III). Tridentate and tetradentate chelate structures are obtained for several 1:1 complexes of 9 while a pentadentate chelate structure is observed with 10. Emission spectroscopy for one complex, [Eu(9)(NO3)3], in methanol, shows that the Eu(III) ion resides in a low-symmetry site. Lifetime measurements for methanol and deuterated methanol solutions indicate the presence of four methanol molecules in the inner coordination sphere of the metal ion, in addition to the ligand, with the nitrate anions most likely dissociated. The solvent extraction performance of 7-10 in 1,2-dichloroethane for Eu(III) and Am(III) in nitric acid solutions was analyzed and compared with the performance of 2,6-bis(di-n-octylphosphinoylmethyl)pyridine N-oxide (TONOPOP'O') and n-octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (OPhDiBCMPO) measured under identical conditions.

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“…90 Conversion of phosphine oxide into the corresponding phosphine sulfide (CMPS, Chart 2.14) caused a drop in the extraction and selectivity for An over Ln(III). 91 Extension or removal of the methylene bridge caused a decrease in D values, whereas its alkylation increased the solubility and Chart 2.14 selectivity, albeit reducing the extraction capacity. [87][88][89] The alkyl chains hindered the formation of the chelate complex by limiting the conformational mobility around the central carbon atom.…”

Section: Sfu(vi)/am(iii)mentioning

confidence: 97%

Alkylation and pre-organisation of diglycolamide ligands on flexible platforms for nuclear waste treatment

Leoncini

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Design, synthesis and evaluation of carbamoylmethylphosphine sulfide (CMPS)-based chelates for separation of lanthanides and actinides

Cited by 10 publications

References 27 publications

Ligands for f-element extraction used in the nuclear fuel cycle

Ligands for f-element extraction used in the nuclear fuel cycle

Synthesis, Lanthanide Coordination Chemistry, and Liquid–Liquid Extraction Performance of CMPO-Decorated Pyridine and Pyridine N-Oxide Platforms

Alkylation and pre-organisation of diglycolamide ligands on flexible platforms for nuclear waste treatment

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