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6-(6-methyl-1,2,4,5-tetrazine-3-yl)-2,2′-bipyridine: a N-donor ligand for the separation of lanthanides(III) and actinides(III)

Here, we report the synthesis of the 6-(6-methyl-1,2,4,5-tetrazine-3-yl)-2,2′-bipyridine (MTB) ligand that has been developed for lanthanide/actinide separation. A multimethod study of the complexation of MTB with trivalent actinide and lanthanide ions is presented. Single-crystal X-ray diffraction...

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Main Authors: Greif, Gerlinde (Author) , Sauerwein, Fynn S. (Author) , Weßling, Patrik (Author) , Duckworth, Tamara M. (Author) , Patzschke, Michael (Author) , Gericke, Robert (Author) , Sittel, Thomas (Author) , März, Juliane (Author) , Wilden, Andreas (Author) , Modolo, Giuseppe (Author) , Panak, Petra (Author) , Roesky, Peter W. (Author)
Format: Article (Journal)
Language:English
Published: August 19, 2024
In: Inorganic chemistry
Year: 2024, Volume: 63, Issue: 33, Pages: 15259-15269
ISSN:1520-510X
DOI:10.1021/acs.inorgchem.4c01793
Online Access:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/acs.inorgchem.4c01793
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Author Notes:Gerlinde Greif, Fynn S. Sauerwein, Patrik Weßling, Tamara M. Duckworth, Michael Patzschke, Robert Gericke, Thomas Sittel, Juliane März, Andreas Wilden, Giuseppe Modolo, Petra J. Panak, and Peter W. Roesky
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Summary:Here, we report the synthesis of the 6-(6-methyl-1,2,4,5-tetrazine-3-yl)-2,2′-bipyridine (MTB) ligand that has been developed for lanthanide/actinide separation. A multimethod study of the complexation of MTB with trivalent actinide and lanthanide ions is presented. Single-crystal X-ray diffraction measurements reveal the formation of [Ce(MTB)2(NO3)3], [Pr(MTB)(NO3)3H2O], and [Ln(MTB)(NO3)3MeCN] (Ln = Nd, Sm, Eu, Gd). In addition, the complexation of Cm(III) with MTB in solution was studied by time-resolved laser fluorescence spectroscopy. The results show the formation of [Cm(MTB)1-3]3+ complexes, which occur in two different isomers. Quantum chemical calculations reveal an energy difference between these isomers of 12 kJ mol-1, clarifying the initial observations made by time-resolved laser fluorescence spectroscopy (TRLFS). Furthermore, quantum theory of atoms in molecules (QTAIM) analysis of the Cm(III) and Ln(III) complexes was performed, indicating a stronger covalent contribution in the Cm-N interaction compared to the respective Ln-N interaction. These findings align well with extraction data showing a preferred extraction of Am and Cm over lanthanides (e.g., max. SFAm/Eu = 8.3) at nitric acid concentrations <0.1 mol L-1 HNO3.
Item Description:Veröffentlicht: 5. August 2024
Gesehen am 12.05.2025
Physical Description:Online Resource
ISSN:1520-510X
DOI:10.1021/acs.inorgchem.4c01793

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