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).

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Abstract

<jats:title>Abstract</jats:title><jats:p>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 <jats:sup>15</jats:sup>N nuclear magnetic resonance spectroscopy, and find an exceptional nitride chemical shift and chemical shift anisotropy. This redefines the <jats:sup>15</jats:sup>N 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 <jats:sup>15</jats:sup>N chemical shift-bond order correlations, and reframe our understanding of actinide chemical bonding to guide future studies.</jats:p>

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: 18 Jan 2023 20:56
DOI: 10.1038/s41467-021-25863-2
Related URLs:
URI: https://livrepository.liverpool.ac.uk/id/eprint/3158375