The thermal elimination reactions of ethyl formate, ethyl xanthate, and ethyl phosphinate were examined in order to address the mechanistic details in this class of E(i) reactions. The reactants, products, and transition structures were fully optimized at the RHF/6-31G* level with MP2/6-31G* single point energies calculated on the HF optimized structures. In addition, the electrostatic potential derived atomic charges were calculated for each reactant and transition structure. The results of this study show that the C-alpha-O bond is lengthened to a greater degree than the CbetaH bond in the transition structure and that the degree of the lengthening correlates with both calculated and experimental rate trends. It appears that the C-alpha-O bond dissociates in advance of the CbetaH bond in this asynchronous reaction and that the relative rates of these reactions depend primarily on the ease with which the C-alpha-O bond can dissociate.