Oxidant-free Au-catalyzed reactions are emerging as a new synthetic tool for innovative organic transformations. Still, a deeper mechanistic understanding is needed for a rational design of these processes. Here we describe the synthesis of two Au(I) complexes bearing bidentated hemilabile MICˆN ligands, [AuI(MICˆN)Cl], and their ability to stabilize square-planar Au(III) species (MIC = mesoionic carbene).