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The mechanism of Fe induced bond stability of uranyl( v )

Vitova, Tonya ORCID iD icon 1; Faizova, Radmila; Amaro-Estrada, Jorge I.; Maron, Laurent ; Pruessmann, Tim ORCID iD icon 1; Neill, Thomas 1; Beck, Aaron 1; Schacherl, Bianca ORCID iD icon 1; Tirani, Farzaneh Fadaei; Mazzanti, Marinella
1 Institut für Nukleare Entsorgung (INE), Karlsruher Institut für Technologie (KIT)

Abstract:

The stabilization of uranyl(V) (UO21+) by Fe(II) in natural systems remains an open question in uranium chemistry. Stabilization of UVO21+ by Fe(II) against disproportionation was also demonstrated in molecular complexes. However, the relation between the Fe(II) induced stability and the change of the bonding properties have not been elucidated up to date. We demonstrate that U(V) – oaxial bond covalency decreases upon binding to Fe(II) inducing redirection of electron density from the U(V) – oaxial bond towards the U(V) – equatorial bonds thereby increasing bond covalency. Our results indicate that such increased covalent interaction of U(V) with the equatorial ligands resulting from iron binding lead to higher stability of uranyl(V). For the first time a combination of U M4,5 high energy resolution X-ray absorption near edge structure (HR-XANES) and valence band resonant inelastic X-ray scattering (VB-RIXS) and ab initio multireference CASSCF and DFT based computations were applied to establish the electronic structure of iron-bound uranyl(V).


Verlagsausgabe §
DOI: 10.5445/IR/1000150346
Veröffentlicht am 05.09.2022
Originalveröffentlichung
DOI: 10.1039/D2SC03416F
Scopus
Zitationen: 10
Web of Science
Zitationen: 9
Dimensions
Zitationen: 10
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Nukleare Entsorgung (INE)
Publikationstyp Zeitschriftenaufsatz
Publikationsjahr 2022
Sprache Englisch
Identifikator ISSN: 2041-6520, 2041-6539
KITopen-ID: 1000150346
HGF-Programm 32.11.01 (POF IV, LK 01) Nuclear Waste Disposal
Erschienen in Chemical Science
Verlag Royal Society of Chemistry (RSC)
Band 13
Heft 37
Seiten 11038-11047
Projektinformation THE ACTINIDE BOND (EU, H2020, 101003292)
Vorab online veröffentlicht am 05.08.2022
Nachgewiesen in Web of Science
Dimensions
Scopus
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