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

Abstract

The stabilization of uranyl(V) (UO2+) by Fe(II) in natural systems remains an open question in uranium chemistry. Stabilization of UVO2+ 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).

Supplementary files

Article information

Article type
Edge Article
Submitted
19 Jun 2022
Accepted
03 Aug 2022
First published
05 Aug 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2022, Accepted Manuscript

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

T. Vitova, R. Faizova, J. I. Amaro Estrada, L. Maron, T. Prüßmann, T. Neill, A. Beck, B. Schacherl, F. Fadaei Tirani and M. Mazzanti, Chem. Sci., 2022, Accepted Manuscript , DOI: 10.1039/D2SC03416F

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