Reaction of [Ir(μ-Cl)(ppy) ₂] ₂ (1) with 4 equivs of CNC ₆H ₄X (X = F 2a, Cl 2b, Br 2c, I 2d) in the presence of 2 equivs of AgOTf in dichloromethane at 20-25 °C furnished the bisisocyanide complexes [Ir(ppy) ₂(CNC ₆H ₄X) ₂](OTf) ([3a-d](OTf); 72-87%). Reaction of [3a-d](OTf) with an excess of gaseous ammonia at room temperature gave the bisdiaminocarbene species [Ir(ppy) ₂{C(NH ₂)NHC ₆H ₄X} ₂](OTf) [5a-d](OTf) (73-83%); the two-step addition proceeds through an intermediate formation of appropriate monocarbene complexes [4a-d](OTf). Further reaction of [5a-d](OTf) with an excess of gaseous ammonia at 50 °C led to the cleavage of one diaminocarbene ligand to the cyanide ligand in [Ir(ppy) ₂(CN){C(NH ₂)NHC ₆H ₄X}] (6a-d) and this transformation is accompanied with the elimination of a substituted aniline. Treatment of [5a-d](OTf) with N(CH ₂CH ₂OH) ₃ at 50 °C resulted in the cleavage of the diaminocarbene ligand to the isocyanide and uncomplexed NH ₃; isocyanide remains bound to the iridium(iii) center in [Ir(ppy) ₂{C(NH ₂)NHC ₆H ₄X}(CNC ₆H ₄X)](OTf) (4a-d). All isolated compounds were characterized by elemental analyses (C, H, N), molar conductivity measurements, TG/DTA, HRESI ^+/--MS, FTIR, 1D ( ¹H, ¹³C{ ¹H}, ¹⁹F{ ¹H}) and 2D ( ¹H, ¹H-COSY, ¹H, ¹³C-HMQC/ ¹H, ¹³C-HSQC, ¹H, ¹³C-HMBC) NMR, and also by X-ray diffraction (for the bisisocyanide 3, the diaminocarbene/isocyanide 4, the bisdiaminocarbene 5, and the diaminocarbene/cyanide 6 type complexes).