Photochemical Valence Isomerization to High Energy Products—Bicyclobutanes and Oxabicyclobutanes

Author/Creator ORCID

Date

2021-06-18

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Citation of Original Publication

Rágyanszki, Anita et al.; Photochemical Valence Isomerization to High Energy Products—Bicyclobutanes and Oxabicyclobutanes; Photochemistry & Photobiology, 18 June, 2021; https://doi.org/10.1111/php.13472

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This is the peer reviewed version of the following article: Rágyanszki, Anita et al.; Photochemical Valence Isomerization to High Energy Products Bicyclobutanes and Oxabicyclobutanes; Photochemistry & Photobiology, 18 June, 2021; https://onlinelibrary.wiley.com/doi/10.1111/php.13472, which has been published in final form at https://doi.org/10.1111/php.13472.
Access to this item will begin on 2022-06-18

Subjects

Abstract

DFT calculations were used to determine the structures and energies of bicyclobutane and oxabicyclobutane as valence isomers derived from electronic excitation of their corresponding precursors, 1,3-butadiene and acrolein, respectively. Proton affinities of these strained compounds were determined and compared with their simple ring components, cyclopropane and ethylene oxide. The basicity as determined from proton affinities showed that bicyclobutane is the most basic saturated hydrocarbon, even more basic than oxabicyclobutane. Strain energies of these valence tautomers were computed which showed oxabicyclobutane to be significantly more strained than bicyclobutane. Qualitative reasons are provided to account for the difference in strain energies.