Ring-Opening Dynamics of the Cyclopropyl Radical and Cation: the Transition State Nature of the Cyclopropyl Cation

Nadav Genossar (1) , P. Bryan Changala (2) , Bérenger Gans (3) , Jean-Christophe Loison (4) , Sebastian Hartweg (5) , Marie-Aline Martin-Drumel (3) , Gustavo Garcia (5) , John Stanton (6) , Branko Ruscic (7) , Joshua Baraban (1)

1 BGU - Ben-Gurion University of the Negev
2 CfA - Harvard-Smithsonian Center for Astrophysics
3 ISMO - Institut des Sciences Moléculaires d'Orsay
4 ISM - Institut des Sciences Moléculaires
5 SSOLEIL - Synchrotron SOLEIL
6 UF - University of Florida [Gainesville]
7 ANL - Argonne National Laboratory [Lemont]

We provide compelling experimental and theoretical evidence for the transition state nature of the cyclopropyl cation. Synchrotron photoionization spectroscopy employing coincidence techniques together with a novel simulation based on high accuracy ab initio calculations reveal that the cation is unstable via its allowed disrotatory ring opening path. The ring strains of the cation and the radical are similar, but both ring opening paths for the radical are forbidden when the full electronic symmetries are considered. These findings are discussed in light of the early predictions by Longuet-Higgins alongside Woodward and Hoffman; we also propose a simple phase space explanation for the appearance of the cyclopropyl photoionization spectrum. The results of this work allow the refinement of the cyclopropane C−H bond dissociation energy, in addition to the cyclopropyl radical and cation cyclization energies, via the Active Thermochemical Tables approach.

Domaines: Chimie-Physique [physics.chem-ph]; Chimie organique

Nadav Genossar, P. Bryan Changala, Bérenger Gans, Jean-Christophe Loison, Sebastian Hartweg, et al.. Ring-Opening Dynamics of the Cyclopropyl Radical and Cation: the Transition State Nature of the Cyclopropyl Cation. Journal of the American Chemical Society, 2022, ⟨10.1021/jacs.2c07740⟩. ⟨hal-03797976⟩