Anions Formed by Perchlorofluorobenzenes C₆Cl_nF_6–n (n = 0–6)

Abstract

Anions formed by the perhalobenzene series C6Cl n F6–n (n = 0–6) are studied computationally. All members of the series form both stable valence and stable nonvalence anions. At the geometry of the neutral parents, only nonvalence anions are bound, and the respective vertical electron affinities show values in the 20 to 60 meV range. Valence anions show distorted nonplanar structures, and one can distinguish two types of conformers. A-type conformers show puckered-ring structures and excess electrons delocalized over several C–Cl bonds [in the case of C6F6 –, C–F bonds], while B-type conformers possess excess electrons essentially localized in a single C–Cl bond, which is accordingly strongly stretched and bent out of plane. For a specific anion, all conformers are close in energy (relative energies of less than 10 kJ/mol) and are connected by low-lying transition states. Accordingly, A-type and B-type conformers possess similar adiabatic electron affinities; however, their vertical detachment energies exhibit drastically different values, which should ease conformer distinction in photoelectron spectroscopy.