Computational studies of benzyl-substituted halonium ions

Density functional computations were carried out whose objectives were to quantify the interactions of chlorine and bromine with neighboring cationic centers in a series of 1-aryl-2-haloethyl cations. Analysis of structural changes and bonding interactions gave rise to linear correlations with σ+ values of the aryl substituents. Electron-donating groups diminished bridging and electron-withdrawing groups gave rise to stronger bridging.