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Covalent bond shortening and distortion induced by pressurization of thorium, uranium, and neptunium tetrakis aryloxides

Author

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  • Jacob J. Shephard

    (The University of Edinburgh)

  • Victoria E. J. Berryman

    (The University of Manchester)

  • Tatsumi Ochiai

    (The University of Edinburgh
    Lawrence Berkeley National Laboratory, University of California, Berkeley)

  • Olaf Walter

    (European Commission Joint Research Centre)

  • Amy N. Price

    (The University of Edinburgh
    Lawrence Berkeley National Laboratory, University of California, Berkeley)

  • Mark R. Warren

    (Diamond Light Source, Harwell Science and Innovation Campus)

  • Polly L. Arnold

    (The University of Edinburgh
    Lawrence Berkeley National Laboratory, University of California, Berkeley)

  • Nikolas Kaltsoyannis

    (The University of Manchester)

  • Simon Parsons

    (The University of Edinburgh)

Abstract

Covalency involving the 5f orbitals is regularly invoked to explain the reactivity, structure and spectroscopic properties of the actinides, but the ionic versus covalent nature of metal-ligand bonding in actinide complexes remains controversial. The tetrakis 2,6-di-tert-butylphenoxide complexes of Th, U and Np form an isostructural series of crystal structures containing approximately tetrahedral MO4 cores. We show that up to 3 GPa the Th and U crystal structures show negative linear compressibility as the OMO angles distort. At 3 GPa the angles snap back to their original values, reverting to a tetrahedral geometry with an abrupt shortening of the M-O distances by up to 0.1 Å. The Np complex shows similar but smaller effects, transforming above 2.4 GPa. Electronic structure calculations associate the M-O bond shortening with a change in covalency resulting from increased contributions to the M-O bonding by the metal 6d and 5f orbitals, the combination promoting MO4 flexibility at little cost in energy.

Suggested Citation

  • Jacob J. Shephard & Victoria E. J. Berryman & Tatsumi Ochiai & Olaf Walter & Amy N. Price & Mark R. Warren & Polly L. Arnold & Nikolas Kaltsoyannis & Simon Parsons, 2022. "Covalent bond shortening and distortion induced by pressurization of thorium, uranium, and neptunium tetrakis aryloxides," Nature Communications, Nature, vol. 13(1), pages 1-7, December.
    • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-33459-7
    DOI: 10.1038/s41467-022-33459-7
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    References listed on IDEAS

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    1. Nicola Casati & Annette Kleppe & Andrew P. Jephcoat & Piero Macchi, 2016. "Putting pressure on aromaticity along with in situ experimental electron density of a molecular crystal," Nature Communications, Nature, vol. 7(1), pages 1-8, April.
    2. Joseph M. Sperling & Evan J. Warzecha & Cristian Celis-Barros & Dumitru-Claudiu Sergentu & Xiaoyu Wang & Bonnie E. Klamm & Cory J. Windorff & Alyssa N. Gaiser & Frankie D. White & Drake A. Beery & Ale, 2020. "Compression of curium pyrrolidine-dithiocarbamate enhances covalency," Nature, Nature, vol. 583(7816), pages 396-399, July.
    3. Amy N. Price & Victoria Berryman & Tatsumi Ochiai & Jacob J. Shephard & Simon Parsons & Nikolas Kaltsoyannis & Polly L. Arnold, 2022. "Contrasting behaviour under pressure reveals the reasons for pyramidalization in tris(amido)uranium(III) and tris(arylthiolate) uranium(III) molecules," Nature Communications, Nature, vol. 13(1), pages 1-6, December.
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