Substituent effects on the stability of extended benzylic carbocations: a computational study of conjugation.

A set of design rules for the prediction of relative stabilities of methoxy substituted naphthyl methyl carbocations are presented based on a series of DFT calculations. The peri-effect, over-crowding, substitutions on the ring carrying the CH(2)(+) group and substitution on the opposite ring are the principal factors that influence the stability of the carbocations. All of these factors have to be taken simultaneously into account. The most pronounced destabilization occurs when the methyl part of the methoxy substituent lies out of the plane of the aromatic core because this causes the resonance stabilization of the carbocation to become hindered. The performance of the DFT-calculations was assessed on the results of a G3(MP2)//B3LYP calculation-a method that is known to predict energies to within chemical accuracy. These values were found to compare well with those obtained at the B3LYP/6-31G(d) level. Thus, a computationally inexpensive method such as the B3LYP/6-31G(d) might prove to be a powerful tool in the design of future complex extended aromatic systems.