A library of 14 heterobis(carbene) complexes of the general formula [Au(iPr2-bimy)(ADC)]BF4 (7-20) containing the N-heterocyclic carbene reporter iPr2-bimy and various protic acyclic diaminocarbenes (ADCs) have been prepared to estimate their stereoelectronic properties by 13C NMR spectroscopy and percentage buried volume (%Vbur) determinations. Their preparation was achieved by nucleophilic attack of five secondary amines on six mixed NHC/isocyanide complexes of the type [Au(iPr2-bimy)(CN-R)]BF4 (1-6). Analyses of the iPr2-bimy carbene signals reveal that protic ADCs are stronger donors than classical and expanded-ring NHCs. On the other hand, they are weaker donating compared to NHCs with reduced-heteroatom stabilization. Moreover, stereoelectronic fine-tuning of these ligands is possible by a diverse range of substituents originating from the employed isocyanides and amines.