Using three different approaches, racemic 1-(perfluoroalkyl)ethylamines were synthesized from perfluoroalkyl iodides or perfluoroalkanoic acids, and further transformed to the corresponding N,N'-disubstituted ethane-1,2-diimines and ethane-1,2-diamines as mixtures of diastereoisomers. Their cyclization afforded imidazolium or dihydroimidazolium salts, which led to silver or palladium complexes bearing NHC ligands substituted with secondary polyfluoroalkyl groups. The palladium complexes bearing a throwaway 3-chloropyridine ligand proved to be moderately active in the model Suzuki-Miyaura coupling.