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Contrasting behaviour under pressure reveals the reasons for pyramidalization in tris(amido)uranium(III) and tris(arylthiolate) uranium(III) molecules
A range of reasons has been suggested for why many low-coordinate complexes across the periodic table exhibit a geometry that is bent, rather a higher symmetry that would best separate the ligands. The dominating reason or reasons are still debated. Here we show that two pyramidal UX(3) molecules, i...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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Nature Publishing Group UK
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9262880/ https://www.ncbi.nlm.nih.gov/pubmed/35798750 http://dx.doi.org/10.1038/s41467-022-31550-7 |
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author | Price, Amy N. Berryman, Victoria Ochiai, Tatsumi Shephard, Jacob J. Parsons, Simon Kaltsoyannis, Nikolas Arnold, Polly L. |
author_facet | Price, Amy N. Berryman, Victoria Ochiai, Tatsumi Shephard, Jacob J. Parsons, Simon Kaltsoyannis, Nikolas Arnold, Polly L. |
author_sort | Price, Amy N. |
collection | PubMed |
description | A range of reasons has been suggested for why many low-coordinate complexes across the periodic table exhibit a geometry that is bent, rather a higher symmetry that would best separate the ligands. The dominating reason or reasons are still debated. Here we show that two pyramidal UX(3) molecules, in which X is a bulky anionic ligand, show opposite behaviour upon pressurisation in the solid state. UN″(3) (UN3, N″ = N(SiMe(3))(2)) increases in pyramidalization between ambient pressure and 4.08 GPa, while U(SAr)(3) (US3, SAr = S-C(6)H(2)-(t)Bu(3)−2,4,6) undergoes pressure-induced planarization. This capacity for planarization enables the use of X-ray structural and computational analyses to explore the four hypotheses normally put forward for this pyramidalization. The pyramidality of UN3, which increases with pressure, is favoured by increased dipole and reduction in molecular volume, the two factors outweighing the slight increase in metal-ligand agostic interactions that would be formed if it was planar. The ambient pressure pyramidal geometry of US3 is favoured by the induced dipole moment and agostic bond formation but these are weaker drivers than in UN3; the pressure-induced planarization of US3 is promoted by the lower molecular volume of US3 when it is planar compared to when it is pyramidal. |
format | Online Article Text |
id | pubmed-9262880 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-92628802022-07-09 Contrasting behaviour under pressure reveals the reasons for pyramidalization in tris(amido)uranium(III) and tris(arylthiolate) uranium(III) molecules Price, Amy N. Berryman, Victoria Ochiai, Tatsumi Shephard, Jacob J. Parsons, Simon Kaltsoyannis, Nikolas Arnold, Polly L. Nat Commun Article A range of reasons has been suggested for why many low-coordinate complexes across the periodic table exhibit a geometry that is bent, rather a higher symmetry that would best separate the ligands. The dominating reason or reasons are still debated. Here we show that two pyramidal UX(3) molecules, in which X is a bulky anionic ligand, show opposite behaviour upon pressurisation in the solid state. UN″(3) (UN3, N″ = N(SiMe(3))(2)) increases in pyramidalization between ambient pressure and 4.08 GPa, while U(SAr)(3) (US3, SAr = S-C(6)H(2)-(t)Bu(3)−2,4,6) undergoes pressure-induced planarization. This capacity for planarization enables the use of X-ray structural and computational analyses to explore the four hypotheses normally put forward for this pyramidalization. The pyramidality of UN3, which increases with pressure, is favoured by increased dipole and reduction in molecular volume, the two factors outweighing the slight increase in metal-ligand agostic interactions that would be formed if it was planar. The ambient pressure pyramidal geometry of US3 is favoured by the induced dipole moment and agostic bond formation but these are weaker drivers than in UN3; the pressure-induced planarization of US3 is promoted by the lower molecular volume of US3 when it is planar compared to when it is pyramidal. Nature Publishing Group UK 2022-07-07 /pmc/articles/PMC9262880/ /pubmed/35798750 http://dx.doi.org/10.1038/s41467-022-31550-7 Text en © The Author(s) 2022 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) . |
spellingShingle | Article Price, Amy N. Berryman, Victoria Ochiai, Tatsumi Shephard, Jacob J. Parsons, Simon Kaltsoyannis, Nikolas Arnold, Polly L. Contrasting behaviour under pressure reveals the reasons for pyramidalization in tris(amido)uranium(III) and tris(arylthiolate) uranium(III) molecules |
title | Contrasting behaviour under pressure reveals the reasons for pyramidalization in tris(amido)uranium(III) and tris(arylthiolate) uranium(III) molecules |
title_full | Contrasting behaviour under pressure reveals the reasons for pyramidalization in tris(amido)uranium(III) and tris(arylthiolate) uranium(III) molecules |
title_fullStr | Contrasting behaviour under pressure reveals the reasons for pyramidalization in tris(amido)uranium(III) and tris(arylthiolate) uranium(III) molecules |
title_full_unstemmed | Contrasting behaviour under pressure reveals the reasons for pyramidalization in tris(amido)uranium(III) and tris(arylthiolate) uranium(III) molecules |
title_short | Contrasting behaviour under pressure reveals the reasons for pyramidalization in tris(amido)uranium(III) and tris(arylthiolate) uranium(III) molecules |
title_sort | contrasting behaviour under pressure reveals the reasons for pyramidalization in tris(amido)uranium(iii) and tris(arylthiolate) uranium(iii) molecules |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9262880/ https://www.ncbi.nlm.nih.gov/pubmed/35798750 http://dx.doi.org/10.1038/s41467-022-31550-7 |
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