Interaction of 6,6′′-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-2,2′:6′,2′′-terpyridine (CyMe4-BTTP) with some trivalent ions such as lanthanide(iii) ions and americium(iii)

Lewis, Frank W.; Harwood, Laurence M.; Hudson, Michael J.; Drew, Michael G. B.; Modolo, Giuseppe; Sypuła, Michał; Desreux, Jean F.; Bouslimani, Nouri; Vidick, Geoffrey

doi:10.1039/b924988e

Cited by 34 publications

(35 citation statements)

References 51 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Interestingly, the extraction performance of the ligand is comparable to that of CyMe 4 -BTTP 60 9 ( Figure 6), which was capable of forming only 1:1 complexes in nitrate media. 27 …”

Section: Discussionmentioning

confidence: 99%

“…Once again the species distribution curve showed asymptotic behavior (see Figure 28 in the Supporting Information), suggesting incomplete complexation at the beginning of the titration. It is interesting to note that both 2 and CyMe 4 -BTTP 9, two ligands that share similar extraction structures of Yb(III) complexes can be determined unambiguously by an analysis of the paramagnetic shifts that it induces (which are essentially dipolar in nature), 32 this can only be applied to symmetrical complexes such as those formed by CyMe 4 -BTTP 9 27 or a related phenanthroline based bis-triazine 30 ligand. 10 Such an analysis on the Yb(III) complex of 2 is therefore not possible.…”

mentioning

confidence: 99%

“…The 1:1 stoichiometries of the lanthanide(III) nitrate complexes with ligand 9 are consistent with those found in the solid state and in liquid-liquid extraction of Eu(III) from nitric acid into octanol. 27 For La(III), the best interpretation points to 75 the formation of an exclusive 1:1 complex with 2 and a 1:2 complex with 9. The corresponding stability constants (log β) are given in Table 2.…”

mentioning

confidence: 99%

See 2 more Smart Citations

Complexation of lanthanides, actinides and transition metal cations with a 6-(1,2,4-triazin-3-yl)-2,2′:6′,2′′-terpyridine ligand: implications for actinide(iii)/lanthanide(iii) partitioning

et al. 2012

Self Cite

View full text Add to dashboard Cite

The quadridentate N-heterocyclic ligand 6- (5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-2,2′ : 6′,2′′-terpyridine (CyMe 4 -hemi-BTBP) has been synthesized and its interactions with Am(III), U(VI), Ln(III) and some transition metal cations have been evaluated by X-ray crystallographic analysis, Am(III)/Eu(III) solvent extraction experiments, UV absorption spectrophotometry, NMR studies and ESI-MS. Structures of 1 : 1 complexes with Eu(III), Ce(III) and the linear uranyl (UO 2 2+ ) ion were obtained by X-ray crystallographic analysis, and they showed similar coordination behavior to related BTBP complexes. In methanol, the stability constants of the Ln(III) complexes are slightly lower than those of the analogous quadridentate bis-triazine BTBP ligands, while the stability constant for the Yb(III) complex is higher. 1 H NMR titrations and ESI-MS with lanthanide nitrates showed that the ligand forms only 1 : 1 complexes with Eu(III), Ce(III) and Yb(III), while both 1 : 1 and 1 : 2 complexes were formed with La(III) and Y(III) in acetonitrile. A mixture of isomeric chiral 2 : 2 helical complexes was formed with Cu(I), with a slight preference (1.4 : 1) for a single directional isomer. In contrast, a 1 : 1 complex was observed with the larger Ag(I) ion. The ligand was unable to extract Am(III) or Eu(III) from nitric acid solutions into 1-octanol, except in the presence of a synergist at low acidity. The results show that the presence of two outer 1,2,4-triazine rings is required for the efficient extraction and separation of An(III) from Ln(III) by quadridentate N-donor ligands. † Electronic supplementary information (ESI) available: Procedures and characterization data for known compounds, Mercury plot of ligand 2 and its Eu, Ce and U complexes, NMR stack plots and species distribution curves, enlargements of mass peaks for La(III), Eu(III), Cu(I) and Ag(I) complexes of 2. CCDC 869233-869236. For ESI and crystallographic data in CIF or other electronic format see

show abstract

“…Interestingly, the extraction performance of the ligand is comparable to that of CyMe 4 -BTTP 60 9 ( Figure 6), which was capable of forming only 1:1 complexes in nitrate media. 27 …”

Section: Discussionmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

See 1 more Smart Citation

Complexation of lanthanides, actinides and transition metal cations with a 6-(1,2,4-triazin-3-yl)-2,2′:6′,2′′-terpyridine ligand: implications for actinide(iii)/lanthanide(iii) partitioning

et al. 2012

Self Cite

View full text Add to dashboard Cite

show abstract

“…We therefore synthesized a Pd(II) complex of BTBP 13 using a procedure reported by us previously [28] in order to characterize the type of species that could be involved in the extraction of Pd(II). The 1:1 and 1:2 complexes of related BTBPs with Ni(II) have been reported previously.…”

Section: Ligand Synthesismentioning

confidence: 99%

Synthesis and Evaluation of Lipophilic BTBP Ligands for An/Ln Separation in Nuclear Waste Treatment: The Effect of Alkyl Substitution on Extraction Properties and Implications for Ligand Design

et al. 2012

Self Cite

View full text Add to dashboard Cite

Northumbria University has developed Northumbria Research Link (NRL) to enable users to access the University's research output. Copyright © and moral rights for items on NRL are retained by the individual author(s) and/or other copyright owners. Single copies of full items can be reproduced, displayed or performed, and given to third parties in any format or medium for personal research or study, educational, or not-for-profit purposes without prior permission or charge, provided the authors, title and full bibliographic details are given, as well as a hyperlink and/or URL to the original metadata page. The content must not be changed in any way. Full items must not be sold commercially in any format or medium without formal permission of the copyright holder. The full policy is available online: http://nrl.northumbria.ac.uk/policies.html This document may differ from the final, published version of the research and has been made available online in accordance with publisher policies. To read and/or cite from the published version of the research, please visit the publisher's website (a subscription may be required.) Karel Stamberg, [b] Ana Núñez, [c] Hitos Galán [c] and Amparo G. Espartero [c] Keywords: Ligands / Actinides / Lanthanides / Nuclear waste / Extraction Submitted to the European Journal of Organic ChemistryFour new 6,6'-bis(1,2,4-triazin-3-yl)-2,2'-bipyridine (BTBP) ligands containing either additional alkyl groups on the pyridine rings, or 7-membered aliphatic rings attached to the triazine rings, have been synthesized, and the effects of additional alkyl substitution in the 4-and 4'-positions of the pyridine rings on their extraction properties with Ln(III) and An(III) cations in simulated nuclear waste solutions were studied. The speciation of ligand 13 with some trivalent lanthanide nitrates was elucidated by 1 H NMR titrations and electrospray-ionization mass spectrometry. Whereas ligand 13 formed both 1:1 and 1:2 complexes with La(III) and Y(III), only 1:2 complexes were observed with Eu(III) and Ce(III).Quite unexpectedly, both alkyl-substituted ligands 12 and 13 showed lower solubilities in certain diluents than the nonsubstituted ligand CyMe 4 -BTBP. Compared to CyMe 4 -BTBP, alkyl-substitution was found to decrease the rates of metal ion extraction of the BTBPs in both 1-octanol and cyclohexanone. A highly efficient (D Am > 10) and selective (SF Am/Eu > 90) extraction was observed for BTBPs 12 and 13 in cyclohexanone, and for BTBP 13 in 1-octanol in the presence of a phase-transfer agent. The implications of these results for the design of improved extractants for radioactive waste treatment are discussed. IntroductionOne of the major goals in the treatment of nuclear waste arising from the PUREX process is the selective removal of the radiotoxic minor actinides (Am and Cm) from the lanthanides in a solvent extraction process, known as the SANEX process.[1] Once removed, the oxides of these elements may be converted by high-energy neutrons (transmutation) into less radiotoxic or no...

show abstract

“…Although mildly selective (SF Am/Eu £12), the ligand was essentially unable to extract Am(III) or Eu(III) from HNO 3 into octan-1-ol in the absence of a synergist (D Am <0.04), making it less efficient than the tetradentate ligand CyMe 4 -BTBP (107) by about two orders of magnitude. 112 In a nitrate medium, only the 1:1 complexes with Ln(III) were observed by NMR spectroscopy and mass spectrometry, whereas the more-hydrophobic 1:2 complexes were formed in a perchlorate medium. This indicated that nitrate ions competed with ligand 109 for coordination sites on the metal, resulting in the lesshydrophobic 1:1 complexes that were not easily extracted.…”

Section: Scheme 8 Synthesis Of 66¢-bis(124-triazin-3-yl)-22¢-bipymentioning

confidence: 97%

Development of Highly Selective Ligands for Separations of Actinides from Lanthanides in the Nuclear Fuel Cycle

Lewis¹,

Hudson²,

Harwood³

2011

Synlett

View full text Add to dashboard Cite

This account summarizes recent work by us and others on the development of ligands for the separation of actinides from lanthanides contained in nuclear waste streams in the context of a future European strategy for nuclear waste management. The current status of actinide/lanthanide separations worldwide is briefly discussed, and the synthesis, development, and testing of different classes of heterocyclic soft N-and S-donor ligands in Europe over the last 20 years is presented. This work has led to the current benchmark ligand that displays many of the desirable qualities for industrial use. The improvement of radiolytic stability through ligand design is also discussed.

show abstract

Interaction of 6,6′′-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-2,2′:6′,2′′-terpyridine (CyMe4-BTTP) with some trivalent ions such as lanthanide(iii) ions and americium(iii)

Cited by 34 publications

References 51 publications

Complexation of lanthanides, actinides and transition metal cations with a 6-(1,2,4-triazin-3-yl)-2,2′:6′,2′′-terpyridine ligand: implications for actinide(iii)/lanthanide(iii) partitioning

Complexation of lanthanides, actinides and transition metal cations with a 6-(1,2,4-triazin-3-yl)-2,2′:6′,2′′-terpyridine ligand: implications for actinide(iii)/lanthanide(iii) partitioning

Synthesis and Evaluation of Lipophilic BTBP Ligands for An/Ln Separation in Nuclear Waste Treatment: The Effect of Alkyl Substitution on Extraction Properties and Implications for Ligand Design

Development of Highly Selective Ligands for Separations of Actinides from Lanthanides in the Nuclear Fuel Cycle

Contact Info

Product

Resources

About