The Core Difference between a Mesoionic and a Normal N -Heterocyclic Carbene.

The properties of the abnormal N -heterocyclic carbene (NHC) 1,4-dimesityl-3-methyl-1,2,3-triazolin-5-ylidene were comprehensively compared to those of the related normal carbene 1,3-dimesitylimidazolin-2-ylidene using a range of steric and electronic probe techniques (% V bur , steric maps, Tolman electronic parameter, alane, Huynh electronic parameter, selone, and p K a values). The two NHCs were determined to be sterically equivalent (isostructural), while the triazolin-5-ylidene was found to be a stronger σ-electron donor and a much weaker π-electron acceptor. These results were used to demonstrate that the electronic properties of these NHCs could affect the stereochemical outcome of an NHC-catalyzed reaction.