Chlorocarbocations and Concept of the Electron Donating Ability

Stabilization effects and the electron donating ability of α-substituents in carbocations are considered as different Chemical concepts. The discussion is based on quantum Chemical and spectroscopic investigations of methyl- and chlorosubstituted carbocations. It has been demonstrated that the methyl group affords a better stabilizing effect but that chlorine acts as a better electron donor. These effects are studied in classical α-chlorocarbocations as well as in chloroallyl cations and aromatic systems