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

Genossar, Nadav; Changala, P. Bryan; Gans, Bérenger; Loison, Jean-Christophe; Hartweg, Sebastian; Martin-Drumel, Marie-Aline; Garcia, Gustavo A.; Stanton, John F.; Ruscic, Branko; Baraban, Joshua H.

doi:10.1021/jacs.2c07740

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

Journal Article · Thu Sep 29 00:00:00 EDT 2022 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.2c07740· OSTI ID:1988620

^[1]; ^[2]; ^[3]; Loison, Jean-Christophe ^[4]; ^[5]; ^[3]; ^[5]; ^[6]; ^[7]; ^[8]

Ben-Gurion University of the Negev (Israel); Israel Atomic Energy Commission (IAEC) (Israel)
Harvard-Smithsonian Center for Astrophysics, Cambridge, MA (United States)
Centre National de la Recherche Scientifique (CNRS), Orsay (France)
Centre National de la Recherche Scientifique (CNRS), Bordeaux (France)
Synchrotron SOLEIL, Gif-sur-Yvette (France)
Univ. of Florida, Gainesville, FL (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)
Ben-Gurion University of the Negev (Israel)

Here, 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.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); European Research Council (ERC); Israel Science Foundation (ISF)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1988620

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 40 Vol. 144; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
active thermochemical tables
allyl group
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cyclopropyl
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mathematical methods
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transition states

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

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