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Emergence of the structure-directing role of f-orbital overlap-driven covalency

Lookup NU author(s): Dr Erli Lu, Dr Stephen Liddle

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This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).

Abstract

© 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.

Publication metadata

Author(s): Lu E, Sajjad S, Berryman VEJ, Wooles AJ, Kaltsoyannis N, Liddle ST

Publication type: Article

Publication status: Published

Journal: Nature Communications

Year: 2019

Volume: 10

Issue: 1

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

URL: https://doi.org/10.1038/s41467-019-08553-y

DOI: 10.1038/s41467-019-08553-y

PubMed id: 30733443

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