Résumé
The complex formation of the uranyl ion, UO2 2+, with chloride ions in acetonitrile has been investigated by factor analysis of UV-vis absorption and U L3 edge EXAFS (extended X-ray absorption fine structure) spectra. As a function of increasing [Cl-]/[UO 2 2+] ratio, the five monomeric species [UO 2(H2O)5]2+, [UO2Cl(H 2O)2(MeCN)2]+, [UO 2Cl2(H2O)(MeCN)2], [UO 2Cl3(MeCN)2]-, and [UO 2Cl4]2- have been observed. The distances determined in the first coordination sphere are: U-Oax = 1.77 Å, U-OH2O = 2.43 Å, U-NMeCN = 2.53 Å, and U-Cl = 2.68 Å. A crystalline material has been obtained from the intermediate solution with the [Cl-]/[UO2 2+] ratio of ∼2, where [UO2Cl2(H2O)(MeCN) 2] is the dominating species. The crystal structure analysis of this material revealed a tetrameric complex, [(UO2) 4(μ2-Cl)4(μ3-O) 2(H2O)2(CH3CN)4] ·(CH3CN). The crystal data are: monoclinic, space group P21/n, a = 10.6388(5) Å, b = 14.8441(5) Å, c = 10.8521(5) Å, β = 109.164(5)°, and Z = 2. The U(VI) coordination of the solution species [UO2Cl2(H2O)(MeCN) 2] changes during the crystallization by replacing one MeCN molecule with a bridging μ3-O atom in the tetramer.
langue originale | Anglais |
---|---|
Pages (de - à) | 2987-2993 |
Nombre de pages | 7 |
journal | Inorganic Chemistry |
Volume | 47 |
Numéro de publication | 8 |
Les DOIs | |
Etat de la publication | Publié - 21 avr. 2008 |
Empreinte digitale
Examiner les sujets de recherche de « Species distribution and coordination of uranyl chloro complexes in acetonitrile ». Ensemble, ils forment une empreinte digitale unique.Ensembles de données
-
CCDC 679899: Experimental Crystal Structure Determination
Fluyt, L. (Contributeur), Gorller-Walrand, C. (Contributeur), Hennig, C. (Contributeur), Nockemann, P. (Contributeur), Servaes, K. (Contributeur), Van Deun, R. (Contributeur), Van Hecke, K. (Contributeur), Van Meervelt, L. (Contributeur) & Wouters, J. (Contributeur), Cambridge Crystallographic Data Centre, 1 janv. 2008
DOI: 10.5517/ccqth77, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccqth77&sid=DataCite
Ensemble de données