The 4-RN-1,3-Ar2-imidazolium salt, R = iPr, tBu, Ar = Mes, Dipp, Mes = mesityl, Dipp = 2,6-bis-diisopropyl-phenyl was metalated by AuI at the C2-, C5- and 4-RN positions depending on the reactants and conditions employed; a rare direct rearrangement of a AuI aminide to an abnormal imidazol-5-ylidene AuI complex was also observed and based on a DFT study it may involve TfO− facilitated H+ transfer.