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Influence of the substitution on the inversion barrier of corannulene: a theoretical study.
1 , 2 , * 2
1  Departamento de Química Física, Facultade de Química, Universidade de Santiago de Compostela. Avda. das Ciencias s/n, 15782 Santiago de Compostela (Spain).
2  Departamento de Química Física, Facultade de Ciencias, Universidade de Santiago de Compostela. Campus de Lugo. Avda. Alfonso X El Sabio s/n 27002 Lugo (Spain).

Abstract: The lower molecular weight hydrocarbons that can be mapped on the buckminsterfullerene (C60) structure are commonly known as "buckybowls" or "geodesic polyarenes" and have the distinctive characteristics of preserving the curvature and aromaticity of fullerene. These bowl-shaped structures are expected to be quite rigid. Nevertheless, the smaller members of the family, in spite of its substantial curvature are surprisingly flexible undergoing rapid bowl-to-bowl inversion in solution as evidenced by the dynamic NMR behavior of C20H10 (corannulene) and several of its derivatives. With the aim of gaining understanding in the bowl-to-bowl inversion, the present theoretical study has explored the effect that substitution of some of the hydrogen atoms of corannulene has on this process. The model systems studied have the formula C20H10-nRn with R = -Cl, -Br, -C≡CH, -CH3 and n = 0, 2, 4, 5, 6, 8, and 10. It is observed that the bowl depth is reduced only by high substitution levels or by a substitution pattern that conduces to important peri interactions. Full substitution with bulky groups causes a pronounced repulsion and the deformation of the transition structure for bowl inversion that otherwise is planar. The activation barrier for the inversion – bowl depth data fit an empirical quartic/quadratic function used previously in similar systems but the coefficients of the fitting don\'t follow the predicted substituent independency.