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Unusual complexation behaviors of R-BTPs with water molecule and Pd(ii) caused by electronic modulation of substituents on BTP backbone: new insights into palladium separation under the framework of minor actinides’ partitioning.
- Source :
-
New Journal of Chemistry . 6/21/2019, Vol. 43 Issue 23, p9052-9065. 14p. - Publication Year :
- 2019
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Abstract
- 2,6-Bis(5,6-dialkyl-1,2,4-triazin-3-yl)-pyridine (R-BTP) is one of the most promising classes of soft N-donor ligands for minor trivalent actinide (such as Am(iii) and Cm(iii)) separation but its complexation behavior with interfering element Pd(ii) is still unknown. The effect of substituents (R-) on the modulation of R-BTP's complexation with Pd(ii) was studied by single crystal diffractometry, 1H NMR spectroscopy, ESI-MS, and density functional theory (DFT) calculation methods. The formation of both 1 : 1 and 2 : 1 complexes of R-BTP with Pd(ii) were firstly identified, and their electronic and geometric structures were determined. It has been found that the modification of the R-BTP skeleton with substituents (R-) changing from methyl (C1) to s-butyl (C4) leads to two different coordination models with water. The structures of 2 : 1 R-BTP/Pd(ii) complexes were determined to be unusually paramagnetic, distorted six-coordinate compounds. However, the 1 : 1 species was found to have a typical square-planar geometry. The extraction properties of four R-BTPs for Pd(ii) and other fission or corrosion products were studied. This work can help to further understand the complexation behavior of Pd(ii) with R-BTP, which provides theoretical insights into the partitioning of minor actinides and Pd(ii) from high level active waste (HLW) using R-BTP type ligands. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 11440546
- Volume :
- 43
- Issue :
- 23
- Database :
- Academic Search Index
- Journal :
- New Journal of Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 136898106
- Full Text :
- https://doi.org/10.1039/c9nj00343f