Effect of substituents in the ring on the structure and electron density distribution in benzyl halides

Abstract

The results of calculations for benzyl chlorides and benzyl bromides that contain substituents in the ring by different quantum-chemical methods are compared. The electron density on the benzyl carbon atom increases as the electron-withdrawing properties of substituents are enhanced due to the shift of the electron density from the benzyl halogen atom to the adjacent carbon atom. A topological analysis according to Bader confirmed the main reason for the change in the paramagnetic shielding of the benzyl13C nuclei. The results of calculations provide, for the first time, an explanation for the resonance upfield13C shift of this atom as the Hammett constant of a substituent increases in compounds of the series under consideration.