KIT | KIT-Bibliothek | Impressum | Datenschutz

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 1; Hlina, Johann A.; Lord, Rianne M.; Purkis, Jamie; Nichol, Gary S.; Magnani, Nicola; Schreckenbach, Georg; Vitova, Tonya ORCID iD icon 1; Love, Jason B.; Arnold, Polly L.
1 Institut für Nukleare Entsorgung (INE), Karlsruher Institut für Technologie (KIT)

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)(Cp₂$Ti^{III}$OUO)(py)(H₂L)] 1 and [(ClCp₂$Ti^{IV}$OUO)(py)(H₂L)] 2. Combination of $Zr^{II}$ and $Zr^{IV}$ synthons with A yields the first $Zr^{IV}$–uranyl(V) complex, [(ClCp₂ZrOUO)(py)(H₂L)] 3. Similarly, combinations of $Ae^{0}$ and $Ae^{II}$ 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 $U^{V}$–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. ... mehr


Verlagsausgabe §
DOI: 10.5445/IR/1000099854
Veröffentlicht am 29.04.2022
Originalveröffentlichung
DOI: 10.1039/C8SC05717F
Scopus
Zitationen: 22
Web of Science
Zitationen: 22
Dimensions
Zitationen: 27
Zugehörige Institution(en) am KIT Institut für Nukleare Entsorgung (INE)
Publikationstyp Zeitschriftenaufsatz
Publikationsjahr 2019
Sprache Englisch
Identifikator ISSN: 2041-6520, 2041-6539
KITopen-ID: 1000099854
HGF-Programm 32.01.04 (POF III, LK 01) Entw.u.Anpassung v.Speziationsmethoden
Weitere HGF-Programme 54.11.11 (POF IV, LK 01) Accelerator Operation, Research and Development
Erschienen in Chemical science
Verlag Royal Society of Chemistry (RSC)
Band 10
Heft 42
Seiten 9740–9751
Vorab online veröffentlicht am 06.09.2019
Nachgewiesen in Web of Science
Dimensions
Scopus
KIT – Die Forschungsuniversität in der Helmholtz-Gemeinschaft
KITopen Landing Page