Byron Millet, Weber State University
Physical Sciences
The relative solvolysis rates of norbornenyl derivatives have been of interest. To date, only one other norbornenyl compound has been found that solvolyzes slower than anti-7-norbornene. It has been suggested that through-space interactions between π-bonds plays a significant role in stabilizing the carbocations. However, through-space interactions do not account for the similar observed solvolysis rates of nearly identical compounds both with and without adjacent π-bonds. Studies have shown that the stability of these compounds is significantly affected by σ-bond interactions. We report on our current computational study of the relative energies of several norbornenyl compounds with and without adjacent π-bonds to evaluate both π-bond and σ-bond effects on the stability of the norbornenyl cations. The effect of a ketone functional group on the relative stability of the carbocation is also analyzed. The literature solvolysis rates of the various norbornenyl derivatives and the stability of their respective cations is compared. With some exceptions, a correlation was found between the stability of a derivative’s carbocation and its respective rate of solvolysis.