title: Structure/energy correlation of bowl depth and inversion barrier in corannulene derivatives: combined experimental and quantum mechanical analysis.
abstract: Synthesis of a series of corannulene derivatives with varying bowl depths has allowed for a study correlating the structure (bowl depth) and the energy of bowl inversion. Substituents placed in the peri positions are repulsive and flatten the bowl, thus causing a decrease in the bowl inversion barrier. Conversely, annelation across the peri positions causes a deepening of the bowl, thus an increase in the bowl inversion barrier. Barriers between 8.7 and 17.3 kcal/mol have been measured, and their structures have been calculated using a variety of ab initio methods. The energy profile of an individual corannulene derivative is assumed to fit a mixed quartic/quadratic function from which an empirical correlation of bowl depth and inversion barrier that follows a quartic function is derived. Structure/energy correlations of this type speak broadly of the nature of enzymatic and catalytic activation of substrates.
authors.affiliation: Contribution from the Department of Chemistry, University of California-San Diego, La Jolla, California 92093-0358, USA.
authors.forename: T J
authors.initials: TJ
authors.lastname: Seiders
authors.forename: K K
authors.initials: KK
authors.lastname: Baldridge
authors.forename: G H
authors.initials: GH
authors.lastname: Grube
authors.forename: J S
authors.initials: JS
authors.lastname: Siegel
mesh_terms: D055598:Chemical Phenomena; D002627:Chemistry, Physical; D011084:Polycyclic Aromatic Hydrocarbons / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D011084:Polycyclic Aromatic Hydrocarbons; C434863:corannulene