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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

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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.

Graphical abstract: 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

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Publication details

The article was received on 20 Jan 2019, accepted on 07 May 2019 and first published on 08 May 2019


Article type: Paper
DOI: 10.1039/C9NJ00343F
New J. Chem., 2019, Advance Article

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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

    L. Xu, A. Zhang, N. Pu, Y. Lu, H. Yang, Z. Liu and Y. Ji, New J. Chem., 2019, Advance Article , DOI: 10.1039/C9NJ00343F

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