Revisiting Aromaticity and Chemical Bonding of Fluorinated Benzene Derivatives

The electron delocalization of benzene (C6H6) and hexafluorobenzene (C6F6) was analyzed in terms of the induced magnetic field, nucleus‐independent chemical shift (NICS), and ring current strength (RCS). The computed out‐of‐plane component of the induced magnetic field at a distance (r) greater than or equal to 1.0 Å above the ring center correlates well (R2>0.99) with the RCS value. According to these criteria, fluorination has two effects on the C6 skeleton; concomitantly, the resonant effects diminish the π electron delocalization and the inductive effects decrease the charge density at the ring center and therefore reduce the magnitude of the paratropic current generated in this region. The equilibrium between both effects decreases aromaticity in the fluorinated benzene derivatives. These results can be extrapolated to determine the aromaticity of any derivative within the series of fluorinated benzene derivatives (C6H(6−n)Fn, where n=1–5). Determining aromaticity: Here, we analyzed the electron delocalization in fluorinated benzene derivatives (C6H(6−n)Fn) in terms of the induced magnetic field, nucleus‐independent chemical shift (NICS), and ring current strength (RCS). Fluorination was found to decrease the paratropic ring current through inductive effects and to decrease the diatropic ring current through resonance effects, and the balance between these two effects decreases aromaticity with increased fluorination.