Neptunium(V) Isothiocyanate Complexes with 4′-Aryl-Substituted 2,2′:6′,2″-Terpyridines and N , N -Dimethylacetamide as Molecular Ligands
2021; American Chemical Society; Volume: 60; Issue: 3 Linguagem: Inglês
10.1021/acs.inorgchem.0c03315
ISSN1520-510X
AutoresА. М. Федосеев, Mikhail S. Grigoriev, I. A. Charushnikova, Н.А. Буданцева, Nadezhda M. Stanetskaya, Vladimir S. Tyurin,
Tópico(s)Nuclear Materials and Properties
ResumoNew complexes of neptunyl(V) isothiocyanate with 4′-aryl-substituted 2,2′:6′,2″-terpyridines (Terpy) and N,N-dimethylacetamide (DMA) were obtained: [(NpO2)(4′-Ph-Terpy)(DMA)(NCS)]·DMA, [(NpO2)(4′-(4-(CF3)C6H4)-Terpy)(DMA)(NCS)]·2H2O·DMA, [(NpO2)(4′-(3-BrC6H4)-Terpy)(DMA)(NCS)]·DMA, and [(NpO2)(4′-(2-(COOH)C6H4)-Terpy)(DMA)(NCS)]·DMA. The structures of the compounds were determined with X-ray diffraction analysis. The neptunium coordination polyhedra were found to be pentagonal bipyramids with O atoms of the NpO2 groups in the apical positions and the equatorial planes formed by three N atoms of the terpyridine ligand, a N atom of the isothiocyanate anion, and an O atom of DMA. The influence of the substituents of the Ar group on the crystal structure is discussed. The IR spectra contain well-resolved bands of characteristic vibrations of all groups in the complex. The electronic absorption spectra are typical for neptunium(V) complexes and contain an intense narrow absorption band belonging to an f–f transition with a maximum of 988 nm and several long-wave satellites of lower intensity. The substituted terpyridines were shown to be efficient for the extraction of various valence forms of neptunium from the isothiocyanate solutions.
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