Determination of structural parameters of uranyl ions complexed with organic acids using EXAFS

Two compounds of known crystal structure, sodium triacetatodioxouranium(VI), Na[UO 2(CH 3COO) 3], and dibenzoatodioxouranium(VI), UO 2[C 6H 5(COO)] 2, were studied by uranium L III-edge extended X-ray absorption fine structure, EXAFS, spectroscopy to differentiate between bidentate and monodentate c...

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Published inJournal of alloys and compounds Vol. 271; pp. 123 - 127
Main Authors Denecke, M.A, Reich, T, Bubner, M, Pompe, S, Heise, K.H, Nitsche, H, Allen, P.G, Bucher, J.J, Edelstein, N.M, Shuh, D.K
Format Journal Article
LanguageEnglish
Published United States Elsevier B.V 12.06.1998
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Abstract Two compounds of known crystal structure, sodium triacetatodioxouranium(VI), Na[UO 2(CH 3COO) 3], and dibenzoatodioxouranium(VI), UO 2[C 6H 5(COO)] 2, were studied by uranium L III-edge extended X-ray absorption fine structure, EXAFS, spectroscopy to differentiate between bidentate and monodentate coordination of carboxylate ions on the basis of the uranium–equatorial oxygen, O eq, bond lengths. Bidentate coordination can be verified by detecting carboxyl carbon atoms and the neighboring distal carbon atom of the organic rest. In contrast, EXAFS spectra for monodentate carboxylate complexes show no evidence of carbon atoms beyond the O eq coordination shell. The mode of coordination was determined by EXAFS analysis for solid uranyl complexes with humic, methoxybenzoic, and salicylic acids. A correlation between the U L III-edge X-ray absorption near-edge structure, XANES, and the U–O eq bond distance according to the relationship Δ E· R(O eq) 2=constant was observed. For the samples studied, the constant was determined to be 197±8 eV Å 2.
AbstractList Two compounds of known crystal structure, sodium triacetatodioxouranium(VI), Na[UO 2(CH 3COO) 3], and dibenzoatodioxouranium(VI), UO 2[C 6H 5(COO)] 2, were studied by uranium L III-edge extended X-ray absorption fine structure, EXAFS, spectroscopy to differentiate between bidentate and monodentate coordination of carboxylate ions on the basis of the uranium–equatorial oxygen, O eq, bond lengths. Bidentate coordination can be verified by detecting carboxyl carbon atoms and the neighboring distal carbon atom of the organic rest. In contrast, EXAFS spectra for monodentate carboxylate complexes show no evidence of carbon atoms beyond the O eq coordination shell. The mode of coordination was determined by EXAFS analysis for solid uranyl complexes with humic, methoxybenzoic, and salicylic acids. A correlation between the U L III-edge X-ray absorption near-edge structure, XANES, and the U–O eq bond distance according to the relationship Δ E· R(O eq) 2=constant was observed. For the samples studied, the constant was determined to be 197±8 eV Å 2.
Author Reich, T
Nitsche, H
Allen, P.G
Shuh, D.K
Bubner, M
Pompe, S
Heise, K.H
Denecke, M.A
Edelstein, N.M
Bucher, J.J
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Copyright 1998 Elsevier Science S.A.
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Keywords Bidentate coordination
Monodentate coordination
Extended X-ray absorption fine structure spectroscopy
Carboxylate ions
Dibenzoatodioxouranium(VI)
Sodium triacetatodioxouranium(VI)
Language English
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USDOE Director, Office of Science. Office of Basic Energy Studies. Division of Chemical Sciences (US)
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SSID ssj0001931
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Snippet Two compounds of known crystal structure, sodium triacetatodioxouranium(VI), Na[UO 2(CH 3COO) 3], and dibenzoatodioxouranium(VI), UO 2[C 6H 5(COO)] 2, were...
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elsevier
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Publisher
StartPage 123
SubjectTerms ABSORPTION SPECTROSCOPY
Bidentate coordination
Carboxylate ions
Dibenzoatodioxouranium(VI)
Extended X-ray absorption fine structure spectroscopy
MOLECULAR STRUCTURE
Monodentate coordination
ORGANIC ACIDS
RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
Sodium triacetatodioxouranium(VI)
URANYL COMPLEXES
X-RAY SPECTROSCOPY
Title Determination of structural parameters of uranyl ions complexed with organic acids using EXAFS
URI https://dx.doi.org/10.1016/S0925-8388(98)00038-3
https://www.osti.gov/biblio/771676
Volume 271
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