Language selection

Government of Canada / Gouvernement du Canada

Search

1,n-Radical ions: an abinitio study of racemization and isomerization of the cyclopropane radical cation

From National Research Council Canada

DOIResolve DOI: https://doi.org/10.1139/v85-543
AuthorSearch for: ; Search for: ; Search for:
FormatText, Article
Abstract
The surfaces for cis-trans isomerization and racemization of the cyclopropane radical cation (1+) are determined using abinitio calculations. It is found that polarization functions and electron correlation have large effects on the relative energies of 1+. Orbital symmetry arguments predict that conrotatory closure of the 0,0 conformer of 1+ should be preferred. These predictions are supported by the calculations; however, even the conrotatory closure has a significant activation barrier. Conformational changes that accompany single methylene rotation are also discussed. The implication of these results to ion cyclotron resonance and mass spectral experiments is that isomerization of 1+ to the 0,0 conformer can occur at energies far below the barrier required to isomerize 1+ to the propylene radical cation. However, the 0,0 conformer of 1+ and the propylene radical cation should display similar reactivities (e.g. deprotonation). The results also indicate that, contrary to reported esr evidence, 1+ should not exist preferentially in the 90,0 conformation.
Publication date
In
  • Canadian Journal of Chemistry 63, no. 12 (1985): 3283–3289.
LanguageEnglish
NRC publication
This is a non-NRC publication

"Non-NRC publications" are publications authored by NRC employees prior to their employment by NRC.

NPARC number12327560
Export citationExport as RIS
Report a correctionReport a correction (opens in a new tab)
Record identifier4179457f-cc99-4283-acd9-5082122dd7e7
Record created2009-09-10
Record modified2023-05-04
Date modified: