Theoretical and Computational Chemistry

Trapping the Transition State in a [2,3]-Sigmatropic Rearrangement by Applying Pressure



Transition states are of central importance in chemistry. While they are, by definition, transient species, it has been shown before that it is possible to “trap” transition states by applying stretching forces. We here demonstrate that the task of transforming a transition state into a minimum on the potential energy surface can be achieved by using hydrostatic pressure. We apply the computational eXtended Hydrostatic Compression Force Field (X- HCFF) approach to the educt of a [2,3]-sigmatropic rearrangement in both static and dynamic calculations and find that the five-membered cyclic transition state of this reaction becomes a minimum at pressures in the range between 100 and 150 GPa. Slow decompression leads to a 70:30 mix of the product and the educt of the sigmatropic rearrangement. Our findings are discussed in terms of geometric parameters and electronic rearrangements throughout the reaction. We speculate that the trapping of transition states by using pressure is generally possible if the transition state of a chemical reaction has a more condensed geometry than both the educt and the product, which paves the way for new ways of initiating chemical reactions.


Thumbnail image of Paper_2021-07-23.pdf

Supplementary material

Thumbnail image of
Supporting Information
Computational details, supplementary data, geometries at the stationary points