The quest for a triplet ground-state alkene: Highly twisted C═C double bonds

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Details zur Publikation

Autorinnen und Autoren: Wu JI, van Eikema Hommes N, Lenoir D, Bachrach SM
Zeitschrift: Journal of Physical Organic Chemistry
Jahr der Veröffentlichung: 2019
ISSN: 0894-3230


Abstract

Density functional theory and extrapolated CCSD(T) computations of several “anti-Bredt” alkenes were carried to explore possible 1,2-diyl “alkene” candidates with a triplet ground state. Ten candidates containing twisted double bonds at the bridgehead positions of bicyclic structures (1-6) or adamantene (7-10) derivatives were studied. Based on a combination of ring strain, rigid scaffolding, and steric crowding, four species were identified to have surprisingly low singlet-triplet energy gaps (lower than 4 kcal/mol). A tert-butyl substituted bicyclic structure (4) was identified to have a near-zero singlet-triplet energy gap, but no triplet ground-state alkene was found. Ring strain energy (RSE) calculations, π-orbital axis vector (POAV) analyses, and multiple linear regression models were performed to elucidate the geometric and energetic effects of double bond twisting in 1-10. Based on our computational exploration, it appears unlikely that there is a ground-state triplet olefin.


FAU-Autorinnen und Autoren / FAU-Herausgeberinnen und Herausgeber

van Eikema Hommes, Nico Dr.
Computer-Chemie-Centrum


Einrichtungen weiterer Autorinnen und Autoren

Helmholtz Zentrum München - Deutsches Forschungszentrum für Gesundheit und Umwelt (HMGU)
Monmouth University
University of Houston


Zitierweisen

APA:
Wu, J.I., van Eikema Hommes, N., Lenoir, D., & Bachrach, S.M. (2019). The quest for a triplet ground-state alkene: Highly twisted C═C double bonds. Journal of Physical Organic Chemistry. https://dx.doi.org/10.1002/poc.3965

MLA:
Wu, Judy I., et al. "The quest for a triplet ground-state alkene: Highly twisted C═C double bonds." Journal of Physical Organic Chemistry (2019).

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Zuletzt aktualisiert 2019-24-05 um 08:08