Species distribution and coordination of uranyl chloro complexes in acetonitrile

Christoph Hennig; Kelly Servaes; Peter Nockemann; Kristof Van Hecke; Luc Van Meervelt; Johan Wouters; Linda Fluyt; Christiane Görller-Walrand; Rik Van Deun

doi:10.1021/ic7014435

Species distribution and coordination of uranyl chloro complexes in acetonitrile

Christoph Hennig, Kelly Servaes, Peter Nockemann, Kristof Van Hecke, Luc Van Meervelt, Johan Wouters, Linda Fluyt, Christiane Görller-Walrand, Rik Van Deun

Unit of theoretical and structural physico-chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

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-O_ax = 1.77 Å, U-O_H2O = 2.43 Å, U-N_MeCN = 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.

Original language	English
Pages (from-to)	2987-2993
Number of pages	7
Journal	Inorganic Chemistry
Volume	47
Issue number	8
DOIs	https://doi.org/10.1021/ic7014435
Publication status	Published - 21 Apr 2008

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10.1021/ic7014435

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@article{9a6d7d0cad2d4bf888375bcde4a83d43,

title = "Species distribution and coordination of uranyl chloro complexes in acetonitrile",

abstract = "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 {\AA}, U-OH2O = 2.43 {\AA}, U-NMeCN = 2.53 {\AA}, and U-Cl = 2.68 {\AA}. 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) {\AA}, b = 14.8441(5) {\AA}, c = 10.8521(5) {\AA}, 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.",

author = "Christoph Hennig and Kelly Servaes and Peter Nockemann and {Van Hecke}, Kristof and {Van Meervelt}, Luc and Johan Wouters and Linda Fluyt and Christiane G{\"o}rller-Walrand and {Van Deun}, Rik",

year = "2008",

month = apr,

day = "21",

doi = "10.1021/ic7014435",

language = "English",

volume = "47",

pages = "2987--2993",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "8",

}

TY - JOUR

T1 - Species distribution and coordination of uranyl chloro complexes in acetonitrile

AU - Hennig, Christoph

AU - Servaes, Kelly

AU - Nockemann, Peter

AU - Van Hecke, Kristof

AU - Van Meervelt, Luc

AU - Wouters, Johan

AU - Fluyt, Linda

AU - Görller-Walrand, Christiane

AU - Van Deun, Rik

PY - 2008/4/21

Y1 - 2008/4/21

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=43149094678&partnerID=8YFLogxK

U2 - 10.1021/ic7014435

DO - 10.1021/ic7014435

M3 - Article

AN - SCOPUS:43149094678

SN - 0020-1669

VL - 47

SP - 2987

EP - 2993

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 8

ER -

Species distribution and coordination of uranyl chloro complexes in acetonitrile

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CCDC 679899: Experimental Crystal Structure Determination

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Species distribution and coordination of uranyl chloro complexes in acetonitrile

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CCDC 679899: Experimental Crystal Structure Determination

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