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Strongly coupled binuclear uranium–oxo complexes from uranyl oxo rearrangement and reductive silylation

Nature Chemistry volume 4, pages 221–227 (2012)Cite this article

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Abstract

The most common motif in uranium chemistry is the d0f0 uranyl ion [UO2]2+ in which the oxo groups are rigorously linear and inert. Alternative geometries, such as the cis-uranyl, have been identified theoretically and implicated in oxo-atom transfer reactions that are relevant to environmental speciation and nuclear waste remediation. Single electron reduction is now known to impart greater oxo-group reactivity, but with retention of the linear OUO motif, and reactions of the oxo groups to form new covalent bonds remain rare. Here, we describe the synthesis, structure, reactivity and magnetic properties of a binuclear uranium–oxo complex. Formed through a combination of reduction and oxo-silylation and migration from a trans to a cis position, the new butterfly-shaped Si–OUO2UO–Si molecule shows remarkably strong UV–UV coupling and chemical inertness, suggesting that this rearranged uranium oxo motif might exist for other actinide species in the environment, and have relevance to the aggregation of actinide oxide clusters.

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Figure 1: The new butterfly-shaped binuclear UV complexes are formed from the addition of excess uranyl amide salts to the wedge-shaped uranyl macrocyclic complex as a result of oxo-silylation and oxo-migration from a trans to a cis position.
Figure 2: Solid-state structure of the binuclear silylated uranium oxo complex [(Me3SiOUO)2(L)] 2a.
Figure 3: Molecular orbitals of primary σ and π character in the unrestricted singlet state of 2a.
Figure 4: Solid-state magnetic behaviour of 2a between 2 and 300 K.
Figure 5: Reactions between uranyl silylamides and H4L to afford butterfly-uranyl complexes 2 and 3 and probable structures of the constituent parts of 3.

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Acknowledgements

P.L.A. and J.B.L. acknowledge support from the Engineering and Physical Sciences Research Council EPSRC (UK), EaStCHEM and the University of Edinburgh. G.S. acknowledges financial support from the Natural Sciences and Engineering Research Council of Canada (NSERC).

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Author notes

  1. Polly L. Arnold and Jason B. Love: These authors contributed equally to this work

Authors and Affiliations

  1. EaStCHEM School of Chemistry, University of Edinburgh, Edinburgh, EH9 3JJ, UK

    Polly L. Arnold, Guy M. Jones & Jason B. Love

  2. Department of Chemistry, University of Manitoba, Winnipeg, Manitoba, R3T 2N2, Canada

    Samuel O. Odoh & Georg Schreckenbach

  3. Chemical Sciences Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Stop 70A1150, California, 94720-8175, Berkeley, USA

    Nicola Magnani

  4. European Commission, Joint Research Centre, Institute for Transuranium Elements, Postfach 2340, D-76125, Karlsruhe, Germany

    Nicola Magnani

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Contributions

G.M.J. synthesized and characterized the compounds. P.L.A. and J.B.L. generated and managed the project, helped characterize the complexes, analysed the data and wrote the manuscript. G.S. and S.O.O. carried out and interpreted the computational analyses of bonding. N.M. performed the ligand-field and magnetic superexchange calculations.

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Correspondence to Polly L. Arnold or Jason B. Love.

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Supplementary information

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Supplementary information (PDF 2828 kb)

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Crystallographic data for [UO2{N(SiMe2Ph)2}2(py)2] (CIF 14 kb)

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Crystallographic data for compound 2a (CIF 46 kb)

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Crystallographic data for compound 2b (CIF 45 kb)

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Crystallographic data for compound 4 (CIF 48 kb)

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Arnold, P., Jones, G., Odoh, S. et al. Strongly coupled binuclear uranium–oxo complexes from uranyl oxo rearrangement and reductive silylation. Nature Chem 4, 221–227 (2012). https://doi.org/10.1038/nchem.1270

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