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Structural chemistry of fluoride complexes of uranyl

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Abstract

The crystal structures of uranyl fluoride complexes with alkali metal cations and ammonium, with protonated cations of organic bases, with divalent transition metal cations, and with mixed monovalent and divalent transition metal cations studied by the single-crystal X-ray diffraction method have been systematized and discussed. The crystal chemical features of the structures of the uranyl fluoride complexes were determined: the coordination polyhedron of the hexavalent uranium atom in the structures of the uranyl fluoride complexes has a pentagonal-bipyramidal structure; the oxygen atoms of the uranyl group are located on the vertical axis of the bipyramid, perpendicular to the equatorial plane in which five atoms of the coordinated ligands are located. With the exception of UO2F2 (uranium center CN 6), a pentagonal-bipyramidal configuration of the central atom polyhedron is realized in all the studied structures of the fluoride complexes of uranyl. Based on the performed studies on the structural chemistry of uranyl fluoride complexes, the regularity in the formation of this class of compounds was established. The dependence of the frequency of the asymmetric stretching vibration of the uranyl ion on the structure of the complex anion and on the formation of hydrogen bonds in the structures of the investigated uranyl fluoride complexes has been established.

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Acknowledgements

RD is grateful to Dr. A. A. Udovenko for the participation in the study of a number of the crystal structures of fluoride complexes of uranyl.

Funding

This work received financial support from the Slovenian Research Agency (research core funding No. P1–0045; Inorganic Chemistry and Technology).

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  1. Department of Inorganic Chemistry and Technology, Jožef Stefan Institute, Jamova Cesta 39, 1000, Ljubljana, Slovenia

    Ruven L. Davidovich & Evgeny A. Goreshnik

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  1. Ruven L. Davidovich
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  2. Evgeny A. Goreshnik
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RD and EG wrote the main manuscript text.

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Correspondence to Evgeny A. Goreshnik.

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Davidovich, R.L., Goreshnik, E.A. Structural chemistry of fluoride complexes of uranyl. Struct Chem 34, 265–284 (2023). https://doi.org/10.1007/s11224-022-02095-8

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