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 pK _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.