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

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DOIResolve DOI: http://doi.org/10.1139/v85-543
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TypeArticle
Journal titleCanadian Journal of Chemistry
Volume63
Issue12
Pages32833289; # of pages: 7
AbstractThe 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.
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NPARC number12327560
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Record identifier4179457f-cc99-4283-acd9-5082122dd7e7
Record created2009-09-10
Record modified2016-05-09
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