Thanks to the onio-substitution strategy, tricationic imidazolium salt (1•H)(OTf) 3 featuring two N-cyclopropenio substituents was readily prepared in a two-step procedure from 1H-imidazole. The influence of the two cyclopropenium moieties on the electronic properties of the related dicationic NHC 1 2+ was evaluated on the basis of the 1 J CH , δ 77 Se, and Tolman electronic parameter (TEP) values obtained, respectively, from NHC precursor (1•H)(OTf) 3 , NHC�Se adduct (5)(OTf) 2 , and NHC− Rh(CO) 2 complex (7)(OTf) 2 , leading to the conclusion that carbene 1 2+ is one of the least-donating cationic NHCs reported to date. The coordinating ability of 1 2+ was extended to Pd(II) and Au(I) centers, providing dicationic [PdCl(allyl)(1)](OTf) 2 (8)(OTf) 2 and [AuCl(1)](OTf) 2 (10)(OTf) 2 complexes, respectively, which were fully characterized. While Pd complex (8)(OTf) 2 was found to exhibit the lability of a cyclopropenium substituent upon the cleavage of a C + −N bond, Au complex (10)(OTf) 2 was implemented in model Au-catalyzed intramolecular cyclization reactions, showing moderate activity.