title: Two Dihydroxo-Bridged Plutonium(IV) Nitrate Dimers and Their Relevance to Trends in Tetravalent Ion Hydrolysis and Condensation.
abstract: We report the room temperature synthesis and structural characterization of a μ2-hydroxo-bridged Pu(IV) dimer obtained from an acidic nitric acid solution. The discrete Pu2(OH)2(NO3)6(H2O)4 moiety crystallized with two distinct crystal structures, [Pu2(OH)2(NO3)6(H2O)4]2·11H2O (1) and Pu2(OH)2(NO3)6(H2O)4·2H2O (2), which differ primarily in the number of incorporated water molecules. High-energy X-ray scattering (HEXS) data obtained from the mother liquor showed evidence of a correlation at 3.7(1) Å but only after concentration of the stock solution. This distance is consistent with the dihydroxo-bridged distance of 3.799(1) Å seen in the solid-state structure as well as with the known Pu-Pu distance in PuO2. The structural characterization of a dihydroxo-bridged Pu moiety is discussed in terms of its relevance to the underlying mechanisms of tetravalent metal-ion condensation.
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory , 9700 South Cass Avenue, Argonne, Illinois 60439, United States.
authors.forename: Karah E
authors.initials: KE
authors.lastname: Knope
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory , 9700 South Cass Avenue, Argonne, Illinois 60439, United States.
authors.forename: S
authors.initials: S
authors.lastname: Skanthakumar
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory , 9700 South Cass Avenue, Argonne, Illinois 60439, United States.
authors.forename: L
authors.initials: L
authors.lastname: Soderholm