title: Isolation of a Star-Shaped Uranium(V/VI) Cluster from the Anaerobic Photochemical Reduction of Uranyl(VI).
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 UVspecies into the stable mixed-valent star-shaped UVI/UVoxo cluster [U(UO2)5(μ3-O)5(PhCOO)5(Py)7] (1). This cluster is only the second example of a UVI/UVcluster and the first one associating uranyl groups to a non-uranyl(V) center. The UVcenter in 1 is stable, while the reaction of uranyl(V) iodide with potassium benzoate leads to immediate disproportionation and formation of the U12IVU4VO24cluster {[K(Py)2]2[K(Py)]2[U16O24(PhCOO)24(Py)2]} (5).
authors.affiliation: Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-, 1015, Lausanne, Switzerland.
authors.forename: Lucile
authors.initials: L
authors.lastname: Chatelain
authors.affiliation: Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-, 1015, Lausanne, Switzerland.
authors.forename: Sarah
authors.initials: S
authors.lastname: White
authors.affiliation: Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-, 1015, Lausanne, Switzerland.
authors.forename: Rosario
authors.initials: R
authors.lastname: Scopelliti
authors.affiliation: Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-, 1015, Lausanne, Switzerland. marinella.mazzanti@epfl.ch.
authors.forename: Marinella
authors.identifier: 0000-0002-3427-008X
authors.initials: M
authors.lastname: Mazzanti
keywords: actinides; cluster compounds; pentavalent uranyl; uranium; uranyl compounds