English

The role of steric effects on hydrogen atom transfer reactions

Chemical Physics 2022-12-14 v3

Abstract

We explored how steric effects influence the rate of hydrogen atom transfer (HAT) reactions between oxyradicals and alkanes. Quantum chemical computations of transition states show that activation barriers and reaction enthalpies are both influenced by bulky substituents on the radical, but less so by substituents on the alkane. The activation barriers correlate with reaction enthalpies via the Evans-Polanyi relationship, even when steric effects are important. Dispersion effects can additionally stabilize transition states in some cases.

Keywords

Cite

@article{arxiv.2211.12609,
  title  = {The role of steric effects on hydrogen atom transfer reactions},
  author = {Yi Sun and Jacob N. Sanders and K. N. Houk},
  journal= {arXiv preprint arXiv:2211.12609},
  year   = {2022}
}