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 hypo

SUBMITTER: Price AN 

PROVIDER: S-EPMC9262880 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature