IDEAS home Printed from https://ideas.repec.org/a/nat/natcom/v13y2022i1d10.1038_s41467-022-33459-7.html
   My bibliography  Save this article

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

Author

Listed:
  • 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
    as

    Download full text from publisher

    File URL: https://www.nature.com/articles/s41467-022-33459-7
    File Function: Abstract
    Download Restriction: no

    File URL: https://libkey.io/10.1038/s41467-022-33459-7?utm_source=ideas
    LibKey link: if access is restricted and if your library uses this service, LibKey will redirect you to where you can use your library subscription to access this item
    ---><---

    References listed on IDEAS

    as
    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.
    Full references (including those not matched with items on IDEAS)

    Most related items

    These are the items that most often cite the same works as this one and are cited by the same works as this one.
    1. Alyssa N. Gaiser & Cristian Celis-Barros & Frankie D. White & Maria J. Beltran-Leiva & Joseph M. Sperling & Sahan R. Salpage & Todd N. Poe & Daniela Gomez Martinez & Tian Jian & Nikki J. Wolford & Nat, 2021. "Creation of an unexpected plane of enhanced covalency in cerium(III) and berkelium(III) terpyridyl complexes," Nature Communications, Nature, vol. 12(1), pages 1-9, December.
    2. Brian N. Long & María J. Beltrán-Leiva & Cristian Celis-Barros & Joseph M. Sperling & Todd N. Poe & Ryan E. Baumbach & Cory J. Windorff & Thomas E. Albrecht-Schönzart, 2022. "Cyclopentadienyl coordination induces unexpected ionic Am−N bonding in an americium bipyridyl complex," Nature Communications, Nature, vol. 13(1), pages 1-7, December.
    3. Brian N. Long & María J. Beltrán-Leíva & Joseph M. Sperling & Todd N. Poe & Cristian Celis-Barros & Thomas E. Albrecht-Schönzart, 2023. "Altering the spectroscopy, electronic structure, and bonding of organometallic curium(III) upon coordination of 4,4′−bipyridine," Nature Communications, Nature, vol. 14(1), pages 1-9, December.

    More about this item

    Statistics

    Access and download statistics

    Corrections

    All material on this site has been provided by the respective publishers and authors. You can help correct errors and omissions. When requesting a correction, please mention this item's handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-33459-7. See general information about how to correct material in RePEc.

    If you have authored this item and are not yet registered with RePEc, we encourage you to do it here. This allows to link your profile to this item. It also allows you to accept potential citations to this item that we are uncertain about.

    If CitEc recognized a bibliographic reference but did not link an item in RePEc to it, you can help with this form .

    If you know of missing items citing this one, you can help us creating those links by adding the relevant references in the same way as above, for each refering item. If you are a registered author of this item, you may also want to check the "citations" tab in your RePEc Author Service profile, as there may be some citations waiting for confirmation.

    For technical questions regarding this item, or to correct its authors, title, abstract, bibliographic or download information, contact: Sonal Shukla or Springer Nature Abstracting and Indexing (email available below). General contact details of provider: http://www.nature.com .

    Please note that corrections may take a couple of weeks to filter through the various RePEc services.

    IDEAS is a RePEc service. RePEc uses bibliographic data supplied by the respective publishers.