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    Thermally Stable Uranium Dinitrogen Complex with Siloxide Supporting Ligands
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    EaStCHEM School of Chemistry, University of Edinburgh, Joseph Black Building, The King’s Buildings, Edinburgh, EH9 3JJ, U.K.
    *E-mail: [email protected]
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    Organometallics

    Cite this: Organometallics 2013, 32, 15, 4214–4222
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    https://doi.org/10.1021/om4003957
    Published July 12, 2013
    Copyright © 2013 American Chemical Society
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    Abstract

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    A new dinitrogen adduct of a homoleptic uranium tris(siloxide) complex, [U{OSi(Mes)3}3]2(μ-η2:η2-N2), is reported. Synthesis of the 15N-labeled isotopomer and Raman spectroscopy confirm the reductive activation of N2 to a (N2)2– dianion. The 15N NMR shift of the 15N2-labeled isotopomer is also reported. Crystallographic characterization shows a side-on (N2)2– coordinated in either an eclipsed or staggered conformation in different crystals. The U–N2–U complex is stable to vacuum and shows high thermal stability, retaining the formally reduced dinitrogen at 100 °C. The parent three-coordinate uranium(III) [U{OSi(Mes)3}3] could not be isolated in our hands, with N2-free syntheses affording only uranium(IV) compounds. The rational synthesis and full characterization of two such U(IV) byproducts, [U{OSi(Mes)3}{N(SiMe3)2}3] and [U{OSi(Mes)3}4], is also reported.

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    Additional spectroscopic data and full crystallographic data (cif format). This material is available free of charge via the Internet at http://pubs.acs.org. Codes for access to the full crystallographic data through the CCDC are in Table 1.

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    This article is cited by 54 publications.

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    Organometallics

    Cite this: Organometallics 2013, 32, 15, 4214–4222
    Click to copy citationCitation copied!
    https://doi.org/10.1021/om4003957
    Published July 12, 2013
    Copyright © 2013 American Chemical Society
    Request reuse permissions

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