Stereoinversion of tetrahedral p-block element hydrides

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

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

38 Downloads (Pure)

Abstract

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.
Original languageEnglish
Article number194113
Number of pages11
JournalThe Journal of Chemical Physics
Volume156
Issue number19
Early online date20 May 2022
DOIs
Publication statusPublished - 21 May 2022

Fingerprint

Dive into the research topics of 'Stereoinversion of tetrahedral p-block element hydrides'. Together they form a unique fingerprint.

Cite this