Differential uranyl(v) oxo-group bonding between the uranium and metal cations from groups 1, 2, 4, and 12; a high energy resolution X-ray absorption, computational, and synthetic study

Zegke, Markus, Zhang, Xiaobin, Pidchenko, Ivan, Hlina, Johann A., Lord, Rianne M. ORCID: https://orcid.org/0000-0001-9981-129X, Purkis, Jamie, Nichol, Gary S., Magnani, Nicola, Schreckenbach, Georg, Vitova, Tonya, Love, Jason B. and Arnold, Polly L. (2019) Differential uranyl(v) oxo-group bonding between the uranium and metal cations from groups 1, 2, 4, and 12; a high energy resolution X-ray absorption, computational, and synthetic study. Chemical Science, 10. pp. 9740-9751. ISSN 2041-6520

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Abstract

The uranyl(VI) ‘Pacman’ complex [(UO2)(py)(H2L)] A (L = polypyrrolic Schiff-base macrocycle) is reduced by Cp2Ti(η2-Me3SiC[triple bond, length as m-dash]CSiMe3) and [Cp2TiCl]2 to oxo-titanated uranyl(V) complexes [(py)(Cp2TiIIIOUO)(py)(H2L)] 1 and [(ClCp2TiIVOUO)(py)(H2L)] 2. Combination of ZrII and ZrIV synthons with A yields the first ZrIV–uranyl(V) complex, [(ClCp2ZrOUO)(py)(H2L)] 3. Similarly, combinations of Ae0 and AeII synthons (Ae = alkaline earth) afford the mono-oxo metalated uranyl(V) complexes [(py)2(ClMgOUO)(py)(H2L)] 4, [(py)2(thf)2(ICaOUO)(py) (H2L)] 5; the zinc complexes [(py)2(XZnOUO)(py)(H2L)] (X = Cl 6, I 7) are formed in a similar manner. In contrast, the direct reactions of Rb or Cs metal with A generate the first mono-rubidiated and mono-caesiated uranyl(V) complexes; monomeric [(py)3(RbOUO)(py)(H2L)] 8 and hexameric [(MOUO)(py)(H2L)]6 (M = Rb 8b or Cs 9). In these uranyl(V) complexes, the pyrrole N–H atoms show strengthened hydrogen-bonding interactions with the endo-oxos, classified computationally as moderate-strength hydrogen bonds. Computational DFT MO (density functional theory molecular orbital) and EDA (energy decomposition analysis), uranium M4 edge HR-XANES (High Energy Resolution X-ray Absorption Near Edge Structure) and 3d4f RIXS (Resonant Inelastic X-ray Scattering) have been used (the latter two for the first time for uranyl(V) in 7 (ZnI)) to compare the covalent character in the UV–O and O–M bonds and show the 5f orbitals in uranyl(VI) complex A are unexpectedly more delocalised than in the uranyl(V) 7 (ZnI) complex. The Oexo–Zn bonds have a larger covalent contribution compared to the Mg–Oexo/Ca–Oexo bonds, and more covalency is found in the U–Oexo bond in 7 (ZnI), in agreement with the calculations.

Item Type:	Article
Faculty \ School:	Faculty of Science > School of Chemistry (former - to 2024)
UEA Research Groups:	Faculty of Science > Research Groups > Chemistry of Materials and Catalysis Faculty of Science > Research Groups > Chemistry of Life Processes Faculty of Science > Research Centres > Centre for Molecular and Structural Biochemistry
Related URLs:	https://doi.org/10.1039/C8SC05717F
Depositing User:	LivePure Connector
Date Deposited:	30 Jan 2020 04:15
Last Modified:	25 Sep 2024 14:28
URI:	https://ueaeprints.uea.ac.uk/id/eprint/73868
DOI:	10.1039/C8SC05717F

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