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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, ISSN: 2041-6539, Vol: 10, Issue: 42, Page: 9740-9751
2019
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Article Description

The uranyl(vi) 'Pacman' complex [(UO)(py)(HL)] A (L = polypyrrolic Schiff-base macrocycle) is reduced by CpTi(η-MeSiCCSiMe) and [CpTiCl] to oxo-titanated uranyl(v) complexes [(py)(CpTiOUO)(py)(HL)] 1 and [(ClCpTiOUO)(py)(HL)] 2. Combination of Zr and Zr synthons with A yields the first Zr-uranyl(v) complex, [(ClCpZrOUO)(py)(HL)] 3. Similarly, combinations of Ae and Ae synthons (Ae = alkaline earth) afford the mono-oxo metalated uranyl(v) complexes [(py)(ClMgOUO)(py)(HL)] 4, [(py)(thf)(ICaOUO)(py) (HL)] 5; the zinc complexes [(py)(XZnOUO)(py)(HL)] (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)(RbOUO)(py)(HL)] 8 and hexameric [(MOUO)(py)(HL)] (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 M 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 U-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 O-Zn bonds have a larger covalent contribution compared to the Mg-O/Ca-O bonds, and more covalency is found in the U-O bond in 7 (ZnI), in agreement with the calculations.

Bibliographic Details

Zegke, Markus; Zhang, Xiaobin; Pidchenko, Ivan; Hlina, Johann A; Lord, Rianne M; Purkis, Jamie; Nichol, Gary S; Magnani, Nicola; Schreckenbach, Georg; Vitova, Tonya; Love, Jason B; Arnold, Polly L

Royal Society of Chemistry (RSC)

Chemistry

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