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

Jacob J. Shephard, Victoria E. J. Berryman, Tatsumi Ochiai, Olaf Walter, Amy N. Price, Mark R. Warren, Polly L. Arnold (), Nikolas Kaltsoyannis () and Simon Parsons ()
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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
Olaf Walter: European Commission Joint Research Centre
Amy N. Price: The University of Edinburgh
Mark R. Warren: Diamond Light Source, Harwell Science and Innovation Campus
Polly L. Arnold: The University of Edinburgh
Nikolas Kaltsoyannis: The University of Manchester
Simon Parsons: The University of Edinburgh

Nature Communications, 2022, vol. 13, issue 1, 1-7

Abstract: 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.

Date: 2022
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DOI: 10.1038/s41467-022-33459-7

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