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

Journal Article · · Nature Communications
 [1];  [2];  [3];  [4];  [3];  [5];  [3];  [2];  [1]
  1. University of Edinburgh, Scotland (United Kingdom)
  2. University of Manchester (United Kingdom)
  3. University of Edinburgh, Scotland (United Kingdom); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
  4. European Commission Joint Research Centre, Karlsruhle (Germany)
  5. Harwell Science and Innovation Campus, Didcot (United Kingdom). Diamond Light Source
+ Show Author Affiliations
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.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
Engineering and Physical Sciences Research Council (EPSRC); European Commission; European Research Council (ERC); European Union’s Horizon 2020; Japan Society for the Promotion of Science (JSPS); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); University of Edinburgh
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1994342
Journal Information:
Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 13; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
chemical bonding
coordination chemistry