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Exploring the Subtle Effect of Aliphatic Ring Size on Minor Actinide‐Extraction Properties and Metal Ion Speciation in Bis‐1,2,4‐Triazine Ligands
The synthesis and evaluation of three novel bis‐1,2,4‐triazine ligands containing five‐membered aliphatic rings are reported. Compared to the more hydrophobic ligands 1–3 containing six‐membered aliphatic rings, the distribution ratios for relevant f‐block metal ions were approximately one order of...
Autores principales: | , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2019
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7027750/ https://www.ncbi.nlm.nih.gov/pubmed/31489718 http://dx.doi.org/10.1002/chem.201903685 |
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author | Zaytsev, Andrey V. Bulmer, Rachel Kozhevnikov, Valery N. Sims, Mark Modolo, Giuseppe Wilden, Andreas Waddell, Paul G. Geist, Andreas Panak, Petra J. Wessling, Patrik Lewis, Frank W. |
author_facet | Zaytsev, Andrey V. Bulmer, Rachel Kozhevnikov, Valery N. Sims, Mark Modolo, Giuseppe Wilden, Andreas Waddell, Paul G. Geist, Andreas Panak, Petra J. Wessling, Patrik Lewis, Frank W. |
author_sort | Zaytsev, Andrey V. |
collection | PubMed |
description | The synthesis and evaluation of three novel bis‐1,2,4‐triazine ligands containing five‐membered aliphatic rings are reported. Compared to the more hydrophobic ligands 1–3 containing six‐membered aliphatic rings, the distribution ratios for relevant f‐block metal ions were approximately one order of magnitude lower in each case. Ligand 10 showed an efficient, selective and rapid separation of Am(III) and Cm(III) from nitric acid. The speciation of the ligands with trivalent f‐block metal ions was probed using NMR titrations and competition experiments, time‐resolved laser fluorescence spectroscopy and X‐ray crystallography. While the tetradentate ligands 8 and 10 formed Ln(III) complexes of the same stoichiometry as their more hydrophobic analogues 2 and 3, significant differences in speciation were observed between the two classes of ligand, with a lower percentage of the extracted 1:2 complexes being formed for ligands 8 and 10. The structures of the solid state 1:1 and 1:2 complexes formed by 8 and 10 with Y(III), Lu(III) and Pr(III) are very similar to those formed by 2 and 3 with Ln(III). Ligand 10 forms Cm(III) and Eu(III) 1:2 complexes that are thermodynamically less stable than those formed by ligand 3, suggesting that less hydrophobic ligands form less stable An(III) complexes. Thus, it has been shown for the first time how tuning the cyclic aliphatic part of these ligands leads to subtle changes in their metal ion speciation, complex stability and metal extraction affinity. |
format | Online Article Text |
id | pubmed-7027750 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-70277502020-02-24 Exploring the Subtle Effect of Aliphatic Ring Size on Minor Actinide‐Extraction Properties and Metal Ion Speciation in Bis‐1,2,4‐Triazine Ligands Zaytsev, Andrey V. Bulmer, Rachel Kozhevnikov, Valery N. Sims, Mark Modolo, Giuseppe Wilden, Andreas Waddell, Paul G. Geist, Andreas Panak, Petra J. Wessling, Patrik Lewis, Frank W. Chemistry Full Papers The synthesis and evaluation of three novel bis‐1,2,4‐triazine ligands containing five‐membered aliphatic rings are reported. Compared to the more hydrophobic ligands 1–3 containing six‐membered aliphatic rings, the distribution ratios for relevant f‐block metal ions were approximately one order of magnitude lower in each case. Ligand 10 showed an efficient, selective and rapid separation of Am(III) and Cm(III) from nitric acid. The speciation of the ligands with trivalent f‐block metal ions was probed using NMR titrations and competition experiments, time‐resolved laser fluorescence spectroscopy and X‐ray crystallography. While the tetradentate ligands 8 and 10 formed Ln(III) complexes of the same stoichiometry as their more hydrophobic analogues 2 and 3, significant differences in speciation were observed between the two classes of ligand, with a lower percentage of the extracted 1:2 complexes being formed for ligands 8 and 10. The structures of the solid state 1:1 and 1:2 complexes formed by 8 and 10 with Y(III), Lu(III) and Pr(III) are very similar to those formed by 2 and 3 with Ln(III). Ligand 10 forms Cm(III) and Eu(III) 1:2 complexes that are thermodynamically less stable than those formed by ligand 3, suggesting that less hydrophobic ligands form less stable An(III) complexes. Thus, it has been shown for the first time how tuning the cyclic aliphatic part of these ligands leads to subtle changes in their metal ion speciation, complex stability and metal extraction affinity. John Wiley and Sons Inc. 2019-10-30 2020-01-07 /pmc/articles/PMC7027750/ /pubmed/31489718 http://dx.doi.org/10.1002/chem.201903685 Text en © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Full Papers Zaytsev, Andrey V. Bulmer, Rachel Kozhevnikov, Valery N. Sims, Mark Modolo, Giuseppe Wilden, Andreas Waddell, Paul G. Geist, Andreas Panak, Petra J. Wessling, Patrik Lewis, Frank W. Exploring the Subtle Effect of Aliphatic Ring Size on Minor Actinide‐Extraction Properties and Metal Ion Speciation in Bis‐1,2,4‐Triazine Ligands |
title | Exploring the Subtle Effect of Aliphatic Ring Size on Minor Actinide‐Extraction Properties and Metal Ion Speciation in Bis‐1,2,4‐Triazine Ligands |
title_full | Exploring the Subtle Effect of Aliphatic Ring Size on Minor Actinide‐Extraction Properties and Metal Ion Speciation in Bis‐1,2,4‐Triazine Ligands |
title_fullStr | Exploring the Subtle Effect of Aliphatic Ring Size on Minor Actinide‐Extraction Properties and Metal Ion Speciation in Bis‐1,2,4‐Triazine Ligands |
title_full_unstemmed | Exploring the Subtle Effect of Aliphatic Ring Size on Minor Actinide‐Extraction Properties and Metal Ion Speciation in Bis‐1,2,4‐Triazine Ligands |
title_short | Exploring the Subtle Effect of Aliphatic Ring Size on Minor Actinide‐Extraction Properties and Metal Ion Speciation in Bis‐1,2,4‐Triazine Ligands |
title_sort | exploring the subtle effect of aliphatic ring size on minor actinide‐extraction properties and metal ion speciation in bis‐1,2,4‐triazine ligands |
topic | Full Papers |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7027750/ https://www.ncbi.nlm.nih.gov/pubmed/31489718 http://dx.doi.org/10.1002/chem.201903685 |
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