Exceptional uranium(VI)-nitride triple bond covalency from ¹⁵N nuclear magnetic resonance spectroscopy and quantum chemical analysis.

Du, Jingzhen ORCID: 0000-0003-4037-9281, Seed, John A ORCID: 0000-0002-3751-0325, Berryman, Victoria EJ ORCID: 0000-0003-0200-4788, Kaltsoyannis, Nikolas, Adams, Ralph W ORCID: 0000-0001-8009-5334, Lee, Daniel ORCID: 0000-0002-1015-0980 and Liddle, Stephen T ORCID: 0000-0001-9911-8778 (2021) Exceptional uranium(VI)-nitride triple bond covalency from ¹⁵N nuclear magnetic resonance spectroscopy and quantum chemical analysis. Nature communications, 12 (1). 5649-.

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Abstract

Determining the nature and extent of covalency of early actinide chemical bonding is a fundamentally important challenge. Recently, X-ray absorption, electron paramagnetic, and nuclear magnetic resonance spectroscopic studies have probed actinide-ligand covalency, largely confirming the paradigm of early actinide bonding varying from ionic to polarised-covalent, with this range sitting on the continuum between ionic lanthanide and more covalent d transition metal analogues. Here, we report measurement of the covalency of a terminal uranium(VI)-nitride by ¹⁵N nuclear magnetic resonance spectroscopy, and find an exceptional nitride chemical shift and chemical shift anisotropy. This redefines the ¹⁵N nuclear magnetic resonance spectroscopy parameter space, and experimentally confirms a prior computational prediction that the uranium(VI)-nitride triple bond is not only highly covalent, but, more so than d transition metal analogues. These results enable construction of general, predictive metal-ligand ¹⁵N chemical shift-bond order correlations, and reframe our understanding of actinide chemical bonding to guide future studies.

Item Type:	Article
Divisions:	Faculty of Science and Engineering > School of Physical Sciences
Depositing User:	Symplectic Admin
Date Deposited:	13 Jul 2022 10:27
Last Modified:	15 Mar 2024 20:47
DOI:	10.1038/s41467-021-25863-2
Related URLs:	Author Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3158375