The synthesis of novel fluorinated symmetrical and unsymmetrical imidazolium salts as well as their corresponding coinage metal complexes is described. The silver derivatives were prepared using Ag₂O as the metal source and the subsequent (NHC)AgX complexes were successfully employed in the preparation of the corresponding Cu(I) and Au(I) complexes through transmetallation reactions. Halide extrusion from (NHC)AuCl complexes in the presence of labile ligands also allowed the isolation of Au(I) cationic complexes [(NHC)Au(L)]X. The molecular structures of relevant examples of the neutral and ionic complexes have been unambiguously determined by X-ray studies.