The reaction of 2-(2-bromoethyl)-1,3-dioxane with 1-alkylbenzimidazole derivatives results in the formation of the new benzimidazolium salts (1). The reaction of Pd(OAc) 2 with 1,3-dialkylbenzimidazolium salts (1a-c) yields palladium N-heterocyclic carbene (NHC) complexes (2a-c). All synthesized compounds were characterized by 1 H NMR, 13 C NMR, IR and elemental analysis techniques which support the proposed structures. As catalysts, these new palladium complexes offer a simple and efficient methodology for the synthesis of triarylamines and secondary amines from anilines and amines and in a single step with potassium tertiary butoxide as a base.