Facile Reductive Silylation of UO22+ to Uranium(IV) Chloride

Kiernicki, John J.; Zeller, Matthias; Bart, Suzanne C.

doi:10.1002/anie.201609838

Title: Facile Reductive Silylation of UO₂²⁺ to Uranium(IV) Chloride

Journal Article · Mon Dec 19 00:00:00 EST 2016 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201609838· OSTI ID:1533090

Kiernicki, John J. ^[1]; Zeller, Matthias ^[2]; Bart, Suzanne C. ^[1]

Purdue Univ., West Lafayette, IN (United States)
Purdue Univ., West Lafayette, IN (United States) ; Youngstown State Univ., OH (United States)

General reductive silylation of the UO₂²⁺ cation occurs readily in a one-pot, two-step stoichiometric reaction at room temperature to form uranium(IV) siloxides. Addition of two equivalents of an alkylating reagent to UO₂X₂(L)₂ (X=Cl, Br, I, OTf; L=triphenylphosphine oxide, 2,2'-bipyridyl) followed by two equivalents of a silyl (pseudo)halide, R₃Si-X (R=aryl, alkyl, H; X=Cl, Br, I, OTf, SPh), cleanly affords (R₃SiO)₂UX₂(L)₂ in high yields. Support is included for the key step in the process, reduction of UVI to UV. This procedure is applicable to a wide range of commercially available uranyl salts, silyl halides, and alkylating reagents. Under this protocol, one equivalent of SiCl₄or two equivalents of Me₂SiCl₂ results in direct conversion of the uranyl to uranium(IV) tetrachloride. Full spectroscopic and structural characterization of the siloxide products is reported.

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Research Organization:: Purdue Univ., West Lafayette, IN (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0008479

OSTI ID:: 1533090

Journal Information:: Angewandte Chemie (International Edition), Vol. 56, Issue 4; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 23 works

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Axially Symmetric U−O−Ln- and U−O−U-Containing Molecules from the Control of Uranyl Reduction with Simple f-Block Halides Arnold, Polly L.; Cowie, Bradley E.; Suvova, Markéta Angewandte Chemie International Edition, Vol. 56, Issue 36 https://doi.org/10.1002/anie.201705197	journal	August 2017
Three Mechanisms in One Material: Uranium Capture by a Polyoxometalate-Organic Framework through Combined Complexation, Chemical Reduction, and Photocatalytic Reduction Zhang, Hailong; Liu, Wei; Li, Ao Angewandte Chemie International Edition, Vol. 58, Issue 45 https://doi.org/10.1002/anie.201909718	journal	September 2019
Ligand‐Supported Facile Conversion of Uranyl(VI) into Uranium(IV) in Organic and Aqueous Media Faizova, Radmila; Fadaei‐Tirani, Farzaneh; Bernier‐Latmani, Rizlan Angewandte Chemie International Edition, Vol. 59, Issue 17 https://doi.org/10.1002/anie.201916334	journal	February 2020
Monomeric thorium chalcogenolates with bipyridine and terpyridine ligands Ringgold, Marissa; Wu, Wen; Stuber, Matthew Dalton Transactions, Vol. 47, Issue 41 https://doi.org/10.1039/c8dt02543f	journal	January 2018
Axially Symmetric U−O−Ln- and U−O−U-Containing Molecules from the Control of Uranyl Reduction with Simple f-Block Halides Arnold, Polly L.; Cowie, Bradley E.; Suvova, Markéta Angewandte Chemie, Vol. 129, Issue 36 https://doi.org/10.1002/ange.201705197	journal	August 2017
Three Mechanisms in One Material: Uranium Capture by a Polyoxometalate–Organic Framework through Combined Complexation, Chemical Reduction, and Photocatalytic Reduction Zhang, Hailong; Liu, Wei; Li, Ao Angewandte Chemie, Vol. 131, Issue 45 https://doi.org/10.1002/ange.201909718	journal	September 2019
Ligand‐Supported Facile Conversion of Uranyl(VI) into Uranium(IV) in Organic and Aqueous Media Faizova, Radmila; Fadaei‐Tirani, Farzaneh; Bernier‐Latmani, Rizlan Angewandte Chemie, Vol. 132, Issue 17 https://doi.org/10.1002/ange.201916334	journal	April 2020

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Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
Chemistry
alkylation
oxo complexes
reduction
reductive silylation
uranium

CCDC 1479888: Experimental Crystal Structure Determination Kiernicki, John J.; Zeller, Matthias; Bart, Suzanne C. https://doi.org/10.5517/ccdc.csd.cc1lnybj The current record is supplemented by this dataset	dataset	January 2017
CCDC 1479889: Experimental Crystal Structure Determination Kiernicki, John J.; Zeller, Matthias; Bart, Suzanne C. https://doi.org/10.5517/ccdc.csd.cc1lnyck The current record is supplemented by this dataset	dataset	January 2017
CCDC 1479890: Experimental Crystal Structure Determination Kiernicki, John J.; Zeller, Matthias; Bart, Suzanne C. https://doi.org/10.5517/ccdc.csd.cc1lnydl The current record is supplemented by this dataset	dataset	January 2017
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CCDC 1479892: Experimental Crystal Structure Determination Kiernicki, John J.; Zeller, Matthias; Bart, Suzanne C. https://doi.org/10.5517/ccdc.csd.cc1lnygn The current record is supplemented by this dataset	dataset	January 2017
CCDC 1502199: Experimental Crystal Structure Determination Kiernicki, John J.; Zeller, Matthias; Bart, Suzanne C. https://doi.org/10.5517/ccdc.csd.cc1mf518 The current record is supplemented by this dataset	dataset	January 2017
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Title: Facile Reductive Silylation of UO22+ to Uranium(IV) Chloride

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