Structure/energy correlation of bowl depth and inversion barrier in corannulene derivatives: combined experimental and quantum mechanical analysis.
J Am Chem Soc
; 123(4): 517-25, 2001 Jan 31.
Article
in En
| MEDLINE
| ID: mdl-11456563
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.
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Collection:
01-internacional
Database:
MEDLINE
Main subject:
Polycyclic Aromatic Hydrocarbons
Language:
En
Journal:
J Am Chem Soc
Year:
2001
Document type:
Article
Affiliation country:
Estados Unidos