Intrinsic (gas phase) thermodynamic stability of 2-adamantyl cation. Its bearing on the solvolysis rates of 2-adamantyl derivatives

The standard enthalpy of formation of gaseous 2-adamantyl chloride(2-Ad-Cl) was determined by calorimetric techniques. The standard Gibbs energy change for the chloride anion exchange between 1-adamantyl (1-Ad+) and 2-adamantyl (2-Ad+) cations in the gas phase was obtained by Fourier transform ion cyclotron resonance spectroscopy (FT ICR). Theoretical calculations at the G2(MP2) level were performed on these and other relevant species. This and data from the literature provided three highly consistent independent estimates of the relative stabilities of 2-Ad+ and 1-Ad+. This difference in gas-phase stability was compared to the differential structural effects on the rates of solvolysis of the corresponding chlorides and tosylates, and it was shown that the thermodynamic stability of the secondary cation is the leading factor determining the solvolytic reactivity of the precursors in the absence of solvent effects. Thus, under these conditions, the previously established linear free energy correlation between carbenium ion stability and solvolytic reactivity of bridgehead derivatives applies also to secondary derivatives.