Novel Separation System of Trivalent Actinides-combined Effects of Substituted Tris(2-pyridylmethyl)amine Ligand and Hydrophobic Counter-anion

Ishimori, Ken-ichiro; Watanabe, Masayuki; Kimura, Takaumi; Yaita, Tsuyoshi; Yamada, Takashi; Kataoka, Yumiko; Shinoda, Satoshi; Tsukube, Hiroshi

doi:10.1246/cl.2005.1112

Cited by 15 publications

(15 citation statements)

References 13 publications

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“…27,28 The stereoisomerism of f-block complexes influences their spectroscopic properties 29 and their Am/Eu selectivities. 30 Some stereoisomers exist for the S-donor and O-donor complexes based on the chelating effects of the ligands (Figure 3). The S-donor complex, [M(Me 2 PS 2 ) 3 ], has two geometrical isomers (Δ, Λ) that are crystallographically inequivalent, as observed in single crystal X-ray diffraction experiments ( Figure 3a).…”

Section: Calculationsmentioning

confidence: 99%

Roles of d- and f-orbital electrons in the complexation of Eu(III) and Am(III) ions with alkyldithiophosphinic acid and alkylphosphinic acid using scalar-relativistic DFT calculations

Kaneko

Watanabe

Miyashita

et al. 2017

Journal of Nuclear and Radiochemical Sciences

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Scalar-relativistic density functional calculations were applied to the complexation of Eu(III) and Am(III) ions with alkyldithiophosphinic acid (S-donor) and alkylphosphinic acid (O-donor) from the viewpoint of the bonding nature of valence orbitals of a metal ion. Two and four conformers for the S-donor and O-donor complexes, respectively, were optimized at the ZORA-BP86 level. The stabilization energies by complex formation between the metal ions and the ligands toward the hydrated metal ions were estimated at the ZORA-B2PLYP level; these calculations reproduced the experimental Am/Eu selectivities, where the S-donor ligand preferably coordinates to Am(III) ion rather than Eu(III) ion, whereas O-donor ligand selectively coordinates to Eu(III) ion rather than Am(III) ion. Electron population analyses based on the molecular orbitals indicated that the d-orbital electrons in both the Eu and Am complexes participate in bonding covalent interactions with donor atoms and have surprisingly similar contributions. This result suggests that the covalent interaction between the d-orbital electrons in the metal ion and the ligands may be due to the geometrical similarity of the molecular structures of the Eu and Am complexes. In contrast, the contributions of the f-orbital electrons in the metal ions were different in the Eu and Am complexes. In the case of the S-donor complexes, non-bonding and bonding contributions were observed for the Eu and Am complexes, respectively, and in the case of the O-donor complex, bonding and anti-bonding contributions were observed for the Eu and Am complexes, respectively. This result implies that the selectivities of Eu(III) and Am(III) ions were determined by the difference in the participation of their f-orbital electrons, not their d-orbital electrons, in covalent interactions.

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Section: Calculationsmentioning

confidence: 99%

Roles of d- and f-orbital electrons in the complexation of Eu(III) and Am(III) ions with alkyldithiophosphinic acid and alkylphosphinic acid using scalar-relativistic DFT calculations

Kaneko

Watanabe

Miyashita

et al. 2017

Journal of Nuclear and Radiochemical Sciences

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“…Since the early 1980s, considerable efforts have been devoted worldwide to develop efficient An(III)/Ln(III) separations by solvent extraction processes which rely upon the slightly higher affinity of trivalent actinides towards soft donor ligands containing sulphur-or nitrogen-bearing groups [13][14][15][16][17][18][19].…”

Section: Introductionmentioning

confidence: 99%

Development and demonstration of a new SANEX Partitioning Process for selective actinide(III)/lanthanide(III) separation using a mixture of CyMe₄BTBP and TODGA

Modolo¹,

Wilden²,

Malmbeck³

et al. 2013

Radiochimica Acta

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SANEX / Minor actinides / Americium / Curium / Partitioning / TODGA / CyMe 4 BTBP Summary. Within the framework of the European collaborative project ACSEPT, a new SANEX partitioning process was developed at Forschungszentrum Jülich for the separation of the trivalent minor actinides americium, curium and californium from lanthanide fission products in spent nuclear fuels. The development is based on batch solvent extraction studies, singlecentrifugal contactor tests and on flow-sheet design by computer code calculations. The used solvent is composed of 6,6-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenzo-[1,2-4]trizazin-3-yl)-[2,2 ]-bipyridine (CyMe 4 BTBP) and N,N,N ,N-tetraoctyldiglycolamide (TODGA) dissolved in noctanol. A spiked continuous counter-current test was carried out in miniature centrifugal contactors with the aid of a 20stage flow-sheet consisting of 12 extraction, 4 scrubbing and 4 stripping stages. A product fraction containing more than 99.9% of the trivalent actinides Am(III), Cm(III) and Cf(III) was obtained. High product/feed decontamination factors > 1000 were achieved for these actinides. The trivalent lanthanides were directed to the raffinate of the process with the actinide (III) product stream being contaminated with less than 0.5 mass-% of the initial lanthanides.

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“…1), [8][9][10][11] which is a neutral hexadentate ligand with four pyridyl groups connected by ethylenediamine. Diglycolamide and nitrogen-donor type extractants have been under intense study concerning extraction and group separation of actinides and lanthanides in the field of nuclear industry, 12,13 and also offer considerable potential as extractants for mutual separation among lanthanide elements. We describe herein that DODGAA and TPEN have rather simple CHON-structures but provide unprecedentedly high separation performances for the individual lanthanide elements.…”

Section: Introductionmentioning

confidence: 99%

Extraction Behavior and Separation of Lanthanides with a Diglycol Amic Acid Derivative and a Nitrogen-donor Ligand

et al. 2007

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Novel Separation System of Trivalent Actinides-combined Effects of Substituted Tris(2-pyridylmethyl)amine Ligand and Hydrophobic Counter-anion

Cited by 15 publications

References 13 publications

Roles of d- and f-orbital electrons in the complexation of Eu(III) and Am(III) ions with alkyldithiophosphinic acid and alkylphosphinic acid using scalar-relativistic DFT calculations

Roles of d- and f-orbital electrons in the complexation of Eu(III) and Am(III) ions with alkyldithiophosphinic acid and alkylphosphinic acid using scalar-relativistic DFT calculations

Development and demonstration of a new SANEX Partitioning Process for selective actinide(III)/lanthanide(III) separation using a mixture of CyMe₄BTBP and TODGA

Extraction Behavior and Separation of Lanthanides with a Diglycol Amic Acid Derivative and a Nitrogen-donor Ligand

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Novel Separation System of Trivalent Actinides-combined Effects of Substituted Tris(2-pyridylmethyl)amine Ligand and Hydrophobic Counter-anion

Cited by 15 publications

References 13 publications

Roles of d- and f-orbital electrons in the complexation of Eu(III) and Am(III) ions with alkyldithiophosphinic acid and alkylphosphinic acid using scalar-relativistic DFT calculations

Roles of d- and f-orbital electrons in the complexation of Eu(III) and Am(III) ions with alkyldithiophosphinic acid and alkylphosphinic acid using scalar-relativistic DFT calculations

Development and demonstration of a new SANEX Partitioning Process for selective actinide(III)/lanthanide(III) separation using a mixture of CyMe4BTBP and TODGA

Extraction Behavior and Separation of Lanthanides with a Diglycol Amic Acid Derivative and a Nitrogen-donor Ligand

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Development and demonstration of a new SANEX Partitioning Process for selective actinide(III)/lanthanide(III) separation using a mixture of CyMe₄BTBP and TODGA