Isolation of a Star‐Shaped Uranium(V/VI) Cluster from the Anaerobic Photochemical Reduction of Uranyl(VI) - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Angewandte Chemie International Edition Année : 2016

Isolation of a Star‐Shaped Uranium(V/VI) Cluster from the Anaerobic Photochemical Reduction of Uranyl(VI)

Sarah White
  • Fonction : Auteur
Rosario Scopelliti
  • Fonction : Auteur
Marinella Mazzanti

Résumé

Abstract Actinide oxo clusters are an important class of compounds due to their impact on actinide migration in the environment. The photolytic reduction of uranyl(VI) has potential application in catalysis and spent nuclear fuel reprocessing, but the intermediate species involved in this reduction have not yet been elucidated. Here we show that the photolysis of partially hydrated uranyl(VI) in anaerobic conditions leads to the reduction of uranyl(VI), and to the incorporation of the resulting U V species into the stable mixed‐valent star‐shaped U VI /U V oxo cluster [U(UO 2 ) 5 (μ 3 ‐O) 5 (PhCOO) 5 (Py) 7 ] ( 1 ). This cluster is only the second example of a U VI /U V cluster and the first one associating uranyl groups to a non‐uranyl(V) center. The U V center in 1 is stable, while the reaction of uranyl(V) iodide with potassium benzoate leads to immediate disproportionation and formation of the U 12 IV U 4 V O 24 cluster {[K(Py) 2 ] 2 [K(Py)] 2 [U 16 O 24 (PhCOO) 24 (Py) 2 ]} ( 5 ).

Domaines

Chimie

Dates et versions

hal-04568625 , version 1 (05-05-2024)

Identifiants

Citer

Lucile Chatelain, Sarah White, Rosario Scopelliti, Marinella Mazzanti. Isolation of a Star‐Shaped Uranium(V/VI) Cluster from the Anaerobic Photochemical Reduction of Uranyl(VI). Angewandte Chemie International Edition, 2016, 55 (46), pp.14325-14329. ⟨10.1002/anie.201608754⟩. ⟨hal-04568625⟩
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