Structure/energy correlation of bowl depth and inversion barrier in corannulene derivatives: combined experimental and quantum mechanical analysis

J Am Chem Soc. 2001 Jan 31;123(4):517-25. doi: 10.1021/ja0019981.

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.

Publication types

  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Chemical Phenomena
  • Chemistry, Physical
  • Polycyclic Aromatic Hydrocarbons / chemistry*
  • Thermodynamics

Substances

  • Polycyclic Aromatic Hydrocarbons
  • corannulene