Correlation of Gas-Phase Stability of Bridgehead Carbocations with Rates of Solvolysis and <i>ab Initio</i> Calculations

Abstract

The stability of bridgehead carbocations has been determined by Fourier transform ion cyclotron resonance spectroscopy (FT ICR) based on dissociative proton attachment (DPA) of bromides and alcohols. The stability of the ions correlates with the solvolytic reactivity of bridgehead derivatives over a rate range of 23 log units, and with theoretical calculations for hydride transfer of bridgehead hydrocarbons at the MP2/6-311G** level.