Computational studies of benzyl-substituted halonium ions

Density functional computations were carried out with the objective of quantifying the interactions of bromine and chlorine atoms with neighboring cationic centers in a series of 1-aryl-2-haloethyl cations. Analyses of structural changes and bonding interactions between the positive center and the halogen gave rise to linear correlations with σ+ values. Electron-donating groups diminished bridging and electron-withdrawing groups enhanced bridging.