Quantum Tunneling Instability in Pericyclic Reactions

Alexander Frenklach, Hila Amlani, Sebastian Kozuch

Research output: Contribution to journalArticlepeer-review

Abstract

Several cycloreversion reactions of the retro-Diels-Alder type were computationally assessed to understand their quantum tunneling (QT) reactivity. N2, CO, and other leaving groups were considered based on their strong exothermicity, as it reduces their thermodynamic and kinetic stabilities. Our results indicate that for many of these reactions, it is essential to take into account their QT decomposition rate, which can massively weaken their molecular stability and shorten their half-lives even at deep cryogenic temperatures. In practical terms, this indicates that many supposedly stable molecules will actually be unsynthesizable or unisolable, and therefore trying to prepare or detect them would be a futile attempt. In addition, we discuss the importance of tunneling to correctly understand the enthalpy of activation and the collective atomic effect on the tunneling kinetic isotope effects to test if third-row atoms can tunnel in a chemical reaction. This project raises the question of the importance of in silico chemistry to guide in vitro chemistry, especially in cases where the latter cannot solve its own uncertainties.

Original languageAmerican English
Pages (from-to)11823-11834
Number of pages12
JournalJournal of the American Chemical Society
Volume146
Issue number17
DOIs
StatePublished - 1 May 2024

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • Biochemistry
  • Catalysis
  • Colloid and Surface Chemistry

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