Contrasting behaviour under pressure reveals the reasons for pyramidalization in tris(amido)uranium(III) and tris(arylthiolate) uranium(III) molecules
Abstract
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 UX3 molecules, in which X is a bulky anionic ligand, show opposite behaviour upon pressurisation in the solid state. UN"3 (UN3, N" = N(SiMe3)2) increases in pyramidalization between ambient pressure and 4.08 GPa, while U(SAr)3 (US3, SAr = S-C6H2-tBu3–2,4,6) 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.
- Authors:
-
[1];
[2];
[3];
[2];
[1]
- Univ. of Edinburgh, Scotland (United Kingdom); Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Univ. of Manchester (United Kingdom)
- Univ. of Edinburgh, Scotland (United Kingdom)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Engineering and Physical Sciences Research Council (EPSRC); European Research Council (ERC); Science and Technology Facilities Council (STFC); Japan Society for the Promotion of Science (JSPS)
- OSTI Identifier:
- 1896698
- Grant/Contract Number:
- AC02-05CH11231; EP/ N022122/1; EP/N021932/1; 740311
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Communications
- Additional Journal Information:
- Journal Volume: 13; Journal Issue: 1; Journal ID: ISSN 2041-1723
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemical bonding; Density functional theory
Citation Formats
Price, Amy N., Berryman, Victoria, Ochiai, Tatsumi, Shephard, Jacob J., Parsons, Simon, Kaltsoyannis, Nikolas, and Arnold, Polly L. Contrasting behaviour under pressure reveals the reasons for pyramidalization in tris(amido)uranium(III) and tris(arylthiolate) uranium(III) molecules. United States: N. p., 2022.
Web. doi:10.1038/s41467-022-31550-7.
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. United States. https://doi.org/10.1038/s41467-022-31550-7
Price, Amy N., Berryman, Victoria, Ochiai, Tatsumi, Shephard, Jacob J., Parsons, Simon, Kaltsoyannis, Nikolas, and Arnold, Polly L. Thu .
"Contrasting behaviour under pressure reveals the reasons for pyramidalization in tris(amido)uranium(III) and tris(arylthiolate) uranium(III) molecules". United States. https://doi.org/10.1038/s41467-022-31550-7. https://www.osti.gov/servlets/purl/1896698.
@article{osti_1896698,
title = {Contrasting behaviour under pressure reveals the reasons for pyramidalization in tris(amido)uranium(III) and tris(arylthiolate) uranium(III) molecules},
author = {Price, Amy N. and Berryman, Victoria and Ochiai, Tatsumi and Shephard, Jacob J. and Parsons, Simon and Kaltsoyannis, Nikolas and Arnold, Polly L.},
abstractNote = {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 UX3 molecules, in which X is a bulky anionic ligand, show opposite behaviour upon pressurisation in the solid state. UN"3 (UN3, N" = N(SiMe3)2) increases in pyramidalization between ambient pressure and 4.08 GPa, while U(SAr)3 (US3, SAr = S-C6H2-tBu3–2,4,6) 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.},
doi = {10.1038/s41467-022-31550-7},
journal = {Nature Communications},
number = 1,
volume = 13,
place = {United States},
year = {Thu Jul 07 00:00:00 EDT 2022},
month = {Thu Jul 07 00:00:00 EDT 2022}
}
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Fig. 1 : Summary of the pyramidal molecules studied in this work and the factors thought to contribute to pyramidalization in Ln and AnX3 complexes. a Out of plane (oop) distance between the M and the X3 plane is described as oop, shown in blue, is used to provide amore »
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