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Species distribution and coordination of uranyl chloro complexes in acetonitrile

(2008) INORGANIC CHEMISTRY. 47(8). p.2987-2993
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Abstract
The complex formation of the uranyl ion, UO22+, with chloride ions in acetonitrile has been investigated by factor analysis of UV-vis absorption and U L-3 edge EXAFS (extended X-ray absorption fine structure) spectra. As a function of increasing [Cl-]/[UO22+] ratio, the five monomeric species [UO2(H2O)(5)](2+), [UO2Cl(H2O)(2)(MeCN)(2)](+), [UO2Cl2(H2O)(MeCN)(2)], [UO2Cl3(MeCN)(2)](-), and [UO2Cl4](2-) have been observed. The distances determined in the first coordination sphere are: U-O-ax = 1.77 angstrom, U-O-H2O = 2.43 angstrom, U-N-MeCN = 2.53 angstrom, and U-Cl = 2.68 angstrom. A crystalline material has been obtained from the intermediate solution with the [Cl-]/[UO22+] ratio of similar to 2, where [UO2Cl2(H2O)(MeCN)(2)] is the dominating species. The crystal structure analysis of this material revealed a tetrameric complex, [(UO2)(4)(mu(2)-Cl)(4)(mu(3)-O)(2)(H2O)(2)(CH3CN)(4)]center dot(CH3CN). The crystal data are: monoclinic, space group P2(1)/n, a 10.6388(5) angstrom, b = 14.8441(5) angstrom, c = 10.8521(5) angstrom, beta = 109.164(5)degrees, 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 mu(3)-O atom in the tetramer.
Keywords
EXAFS, ION, AQUEOUS-SOLUTION, CRYSTAL-STRUCTURE, HYDROXIDE COMPLEXES, ELECTRONIC-STRUCTURE, ABSORPTION FINE-STRUCTURE, SPECTRA, SPECTROSCOPY, URANIUM(VI)

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Chicago
Hennig, Christoph, Kelly Servaes, Peter Nockemann, Kristof Van Hecke, Luc Van Meervelt, Johan Wouters, Linda Fluyt, Christiane Görller-Walrand, and Rik Van Deun. 2008. “Species Distribution and Coordination of Uranyl Chloro Complexes in Acetonitrile.” Inorganic Chemistry 47 (8): 2987–2993.
APA
Hennig, Christoph, Servaes, K., Nockemann, P., Van Hecke, K., Van Meervelt, L., Wouters, J., Fluyt, L., et al. (2008). Species distribution and coordination of uranyl chloro complexes in acetonitrile. INORGANIC CHEMISTRY, 47(8), 2987–2993.
Vancouver
1.
Hennig C, Servaes K, Nockemann P, Van Hecke K, Van Meervelt L, Wouters J, et al. Species distribution and coordination of uranyl chloro complexes in acetonitrile. INORGANIC CHEMISTRY. 2008;47(8):2987–93.
MLA
Hennig, Christoph, Kelly Servaes, Peter Nockemann, et al. “Species Distribution and Coordination of Uranyl Chloro Complexes in Acetonitrile.” INORGANIC CHEMISTRY 47.8 (2008): 2987–2993. Print.
@article{1190071,
  abstract     = {The complex formation of the uranyl ion, UO22+, with chloride ions in acetonitrile has been investigated by factor analysis of UV-vis absorption and U L-3 edge EXAFS (extended X-ray absorption fine structure) spectra. As a function of increasing [Cl-]/[UO22+] ratio, the five monomeric species [UO2(H2O)(5)](2+), [UO2Cl(H2O)(2)(MeCN)(2)](+), [UO2Cl2(H2O)(MeCN)(2)], [UO2Cl3(MeCN)(2)](-), and [UO2Cl4](2-) have been observed. The distances determined in the first coordination sphere are: U-O-ax = 1.77 angstrom, U-O-H2O = 2.43 angstrom, U-N-MeCN = 2.53 angstrom, and U-Cl = 2.68 angstrom. A crystalline material has been obtained from the intermediate solution with the [Cl-]/[UO22+] ratio of similar to 2, where [UO2Cl2(H2O)(MeCN)(2)] is the dominating species. The crystal structure analysis of this material revealed a tetrameric complex, [(UO2)(4)(mu(2)-Cl)(4)(mu(3)-O)(2)(H2O)(2)(CH3CN)(4)]center dot(CH3CN). The crystal data are: monoclinic, space group P2(1)/n, a 10.6388(5) angstrom, b = 14.8441(5) angstrom, c = 10.8521(5) angstrom, beta = 109.164(5)degrees, 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 mu(3)-O atom in the tetramer.},
  author       = {Hennig, Christoph and Servaes, Kelly and Nockemann, Peter and Van Hecke, Kristof and Van Meervelt, Luc and Wouters, Johan and Fluyt, Linda and G{\"o}rller-Walrand, Christiane and Van Deun, Rik},
  issn         = {0020-1669},
  journal      = {INORGANIC CHEMISTRY},
  keyword      = {EXAFS,ION,AQUEOUS-SOLUTION,CRYSTAL-STRUCTURE,HYDROXIDE COMPLEXES,ELECTRONIC-STRUCTURE,ABSORPTION FINE-STRUCTURE,SPECTRA,SPECTROSCOPY,URANIUM(VI)},
  language     = {eng},
  number       = {8},
  pages        = {2987--2993},
  title        = {Species distribution and coordination of uranyl chloro complexes in acetonitrile},
  url          = {http://dx.doi.org/10.1021/0014435},
  volume       = {47},
  year         = {2008},
}

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