Structural chemistry of UO₂Cl₂ complexes with neutral donor ligands (review)

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Abstract

The crystal structures of UO2Cl2 complexes with neutral ligands, containing O, N, S and C donor atoms, studied by single-crystal X-ray diffraction analysis have been systematized and discussed. The crystal chemical features of the structure of mixed-ligand complexes UO2Cl2Ln were determined depending on the ratio of the number of Cl atoms to the number of donor atoms O, N, S and C of coordinated ligands in the compound. In the mixed-ligand complexes UO2Cl2Ln at the ratios 2Cl : O, 2Cl : 3O(N) and Cl : 4O, the coordination polyhedron of the hexavalent uranium atom in the structure has a pentagonal-bipyramidal structure. The oxygen atoms of the uranyl group are located on the vertical axis of the pentagonal bipyramid, perpendicular to the equatorial plane of the polyhedron, in which five atoms of coordinated ligands are located. At the ratio 2Cl : 2O (N, S, C) in mixed-ligand complexes UO2Cl2Ln uranium atoms form tetragonal bipyramidal polyhedra (distorted octahedra) with uranyl groups in the axial vertices, chlorine atoms and donor ligand atoms in the equatorial plane. In a small group of mixed-ligand compounds UO2Cl2Ln with a 2Cl : 4N ratio, hexagonal-bipyramidal polyhedra of U atoms with Cl and N atoms in the equatorial plane and a nonlinear group UO22+ (∠ O(1)=U=O(2) 161.81(11)–168.3(3)°) was established.

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Ruven L. Davidovich

Institute of Chemistry, FEB RAS

Author for correspondence.
Email: davidovich@ich.dvo.ru
ORCID iD: 0000-0002-8473-3580

Doctor of Sciences in Chemistry, Chief Researcher, Professor

Russian Federation, Vladivostok

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Supplementary files

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2. Fig. 1. The structure of the molecular complex [UO₂Cl₂(THF)₃] in the structure of UO₂Cl₂(THF)₃ [5]

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3. Fig. 2. The structure of the molecular complex [UO₂(Hgly)₂Cl₂] in the structure of UO₂(Hgly)₂Cl₂ [6]

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4. Fig. 3. The structure of the molecular complex [UO₂Cl₂(L₃)₂] (L₃ = (CH₂)₅NCON(i-Pr)₂) in the structure {UO₂Cl₂(Cl₂H₂₄N₂O₂)₂}[10]

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5. Fig. 4. Structure of cis-[UO₂Cl₂(Cy₃PNH)₂] (a) and trans-[UO₂Cl₂(Cy₃PNH)₂] (b) complexes in the structure of UO₂Cl₂(Cy₃PNH)₂·2CH₂Cl₂ [17]

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