Stereoinversion of tetrahedral p -block element hydrides


The potential energy surfaces of 15 tetrahedral p-block element hydrides were screened on the multireference level. It was addressed whether stereoinversion competes against other reactions, such as reductive H2-elimination or hydride loss, and if so, along which pathway the stereomutation occurs. Importantly, stereoinversion transition structures for the ammonium cation (C4v) and the tetrahydridoborate anion (Cs) were identified for the first time. Revisiting methane’s Cs symmetric inversion transition structure with the mHEAT+ protocol revealed an activation enthalpy for stereoinversion, in contrast to all earlier studies, which is 5 kJ mol−1 below the C–H bond dissociation enthalpy. Square planar structures were identified lowest in energy only for the inversion of AlH4−, but a novel stepwise Cs-inversion was discovered for SiH4 or PH4+. Overall, the present contribution delineates essentials of the potential energy surfaces of p-block element hydrides, while structure–energy relations offer design principles for the synthetically emerging field of structurally constrained compounds.


DOI: 10.1063/5.0090267

Projects: Computational Carbon Chemistry

Publication type: Journal

Journal: The Journal of Chemical Physics

Citation: J. Chem. Phys. 156(19):194113

Date Published: 21st May 2022

Registered Mode: by DOI

Authors: Lukas M. Sigmund, Christopher Ehlert, Ganna Gryn’ova, Lutz Greb

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Sigmund, L. M., Ehlert, C., Gryn’ova, G., & Greb, L. (2022). Stereoinversion of tetrahedral p-block element hydrides. In The Journal of Chemical Physics (Vol. 156, Issue 19, p. 194113). AIP Publishing.

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Created: 11th Nov 2022 at 08:29

Last updated: 11th Nov 2022 at 08:29

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