Bicyclo[2.2.1]hepta-2-ene-5-yl-7-ylium Radical Cation: A Theoretical Validation of a Bishomoaromatic Radical Cation Intermediate
2003 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 5, no 8, 1329-1331 p.Article in journal (Refereed) Published
[structure: see text] A natural bond orbital analysis of the distonic bicyclo[2.2.1]hepta-2-ene-5-yl-7-ylium radical cation interprets its structure and radical character by a three-center two-electron bond between C2, C3, and C7 (a bishomoaromatic stabilization) and a singly occupied orbital on C5, n(5). Moreover, B3LYP/6-311+G(d,p) ESR parameters, which agree excellently with experiment, are interpreted in terms of spin polarization in the natural hybrids of sigma(C5-H5), and a dual hyperconjugative effect involving n(5), sigma(C1-H1a), sigma(C1-H1b), and antibonding counterparts.
Place, publisher, year, edition, pages
2003. Vol. 5, no 8, 1329-1331 p.
Organic Chemistry Theoretical Chemistry
IdentifiersURN: urn:nbn:se:uu:diva-47148DOI: 10.1021/ol034272tPubMedID: 12688751OAI: oai:DiVA.org:uu-47148DiVA: diva2:75055