16585-35-6Relevant articles and documents
Nonadditivity of secondary deuterium isotope effects on basicity of trimethylamine
Perrin, Charles L.,Dong, Yanmei
supporting information; experimental part, p. 11143 - 11148 (2009/02/05)
Secondary deuterium isotope effects (IEs) on basicities of isotopologues of trimethylamine have been accurately measured by an NMR titration method applicable to a mixture. Deuteration definitely increases the basicity, by ～0.021 in the ΔpK per D. The IE is attributed to the lowering of the CH stretching frequency and zero-point energy by delocalization of the nitrogen lone pair into the C-H antibonding orbital. Because this depends on the dihedral angle between the lone pair and the C-H, a further consequence is a preference for conformations with H antiperiplanar to the lone pair and D gauche. This leads to a predicted nonadditivity of IEs, which is confirmed experimentally. It is found that the decrease in basicity, per deuterium, increases with the number of deuteriums. The nonadditivity of IEs is a violation of the widely assumed Rule of the Geometric Mean.
