The pKa values of N-aryl imidazolinium salts, their higher homologues, and formamidinium salts in dimethyl sulfoxide

A series of imidazolinium salts, their six-, seven- and eight-membered homologues, and the related formamidinium salts were prepared, and their pK(a) values were determined in DMSO at 25 degrees C using the bracketing indicator method. The effect of each type of structural variation on the acidity of each salt was considered, particularly noting the importance of ring size and the effect of the steric and electronic nature of the N-aryl substituents. The effect of a cyclic structure was also probed through comparing the cyclic systems with the corresponding formamidinium salts, noting the importance of conformational flexibility in the latter cases. Along with allowing choice of appropriate bases for deprotonation of these species, it is anticipated that the data presented will aid in the understanding of the nucleophilicity, and potentially catalytic efficacy, of the corresponding carbenes.