Delocalizations in sigma-radical cations: the intriguing structures of ionized [n]rotanes

Andrey A Fokin; Peter R Schreiner; Sergei I Kozhushkov; Kurt W Sattelmeyer; Henry F Schaefer 3rd; Armin De Meijere

doi:10.1021/ol027479f

Delocalizations in sigma-radical cations: the intriguing structures of ionized [n]rotanes

Org Lett. 2003 Mar 6;5(5):697-700. doi: 10.1021/ol027479f.

Authors

Andrey A Fokin¹, Peter R Schreiner, Sergei I Kozhushkov, Kurt W Sattelmeyer, Henry F Schaefer 3rd, Armin De Meijere

Affiliation

¹ Department of Organic Chemistry, Kiev Polytechnic Institute, pr. Pobedy 37, 03056 Kiev, Ukraine. [email protected]

PMID: 12605493
DOI: 10.1021/ol027479f

Abstract

Highly symmetric aliphatic hydrocarbons such as D(4h)-[4]rotane do not necessarily have degenerate HOMOs. According to our predictions based on high-level computations, its radical cation should display a highly delocalized D(4h)-symmetric structure, in contrast to its Jahn-Teller distorted cousin, the radical cation of [3]rotane, which exists in two distonic localized forms with C(2v) and C(s) symmetry.