Ab Initio Studies of Thermal Syn-Elimination Reactions in Carbonates:  Effect of Structure on Reactivity

V. Van Speybroeck, Y. Martele, E. Schacht, M. Waroquier
Journal of Physical Chemistry A
106 (51), 12370–12375


Thermal elimination reactions in carbonates are investigated from a theoretical point of view with density functional theory methods to obtain insight into the reaction mechanism and structural factors that influence the kinetics. Carbonate systems are good model systems for the kinetics of thermal degradable polycarbonates. Special attention is given to the influence of para-substituents placed either at Cα or Cβ. The results enable prediction of ρ values of the Hammett equation and confirm earlier experimental data.