Lookup NU author(s): Dr Erli Lu,
Dr Stephen Liddle
This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).
© 2019, The Author(s). FEUDAL (f’s essentially unaffected, d’s accommodate ligands) is a longstanding bonding model in actinide chemistry, in which metal-ligand binding uses 6d-orbitals, with the 5f remaining non-bonding. The inverse-trans-influence (ITI) is a case where the model may break down, and it has been suggested that ionic and covalent effects work synergistically in the ITI. Here, we report an experimentally grounded computational study that quantitatively explores the ITI, and in particular the structure-directing role of f-orbital covalency. Strong donor ligands generate a cis-ligand-directing electrostatic potential (ESP) at the metal centre. When f-orbital participation, via overlap-driven covalency, becomes dominant via short actinide-element distances, this ionic ESP effect is overcome, favouring a trans-ligand-directed geometry. This study contradicts the accepted ITI paradigm in that here ionic and covalent effects work against each other, and suggests a clearly non-FEUDAL, structure-directing role for the f-orbitals.
Author(s): Lu E, Sajjad S, Berryman VEJ, Wooles AJ, Kaltsoyannis N, Liddle ST
Publication type: Article
Publication status: Published
Journal: Nature Communications
Print publication date: 01/12/2019
Online publication date: 07/02/2019
Acceptance date: 15/01/2019
Date deposited: 02/10/2019
ISSN (electronic): 2041-1723
Publisher: Nature Publishing Group
PubMed id: 30733443
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