Effects of geminal disubstitution on C–H and N–H bond dissociation energies

Abstract

Composite ab initio methods including G3, CBS-Q, and G3B3 were used to calculate the C–H and N–H bond dissociation energies (BDEs) of a variety of disubstituted methane and ammonia molecules. The calculated BDEs were in excellent agreement with the available experimental data. Using these reliable BDEs we studied the effects of geminal disubstitution on C–H and N–H BDEs. It was found that the effects of the two substituents were not additive. Detailed separation of the substituent effects on BDEs to those associated with the parent molecules and those associated with the radicals was then performed using appropriate isodesmic reactions. It was found the geminal substitution effects on the stabilities of methanes, methyl radicals, amines, and amine radicals were all governed by five basic types of energetic effects, namely, hyperconjugation effect (stabilizing), electrostatic attraction (stabilizing) or repulsion (destabilizing), conjugation saturation effect (destabilizing), captodative effect (stabilizing), and steric effect (destabilizing). The conformations of the species played an essential role in determining whether a particular energetic effect could take place. Because the carbon-centered and nitrogen-centered species often had quite different conformational preferences, the geminal substitution effects on these two classes of species were quite dissimilar to each other.