Green bismuthinidene 1 was reacted with 2,6-bis(trifluoromethyl)iodobenzene 2 at -70°C in dry and degassed n-hexane. Upon warming to -65°C the appearance of a red colour in the reaction mixture was apparent after several minutes. Cooling to -70°C led to the formation of red crystals, while warming to room temperature led to discoloration, oxidation to Bi(III) and crystallization of known RBiI2 4. The highly unstable red species 3 crystallizes in the monoclinic space group P21/n, and the solid-state structure obtained by X-ray crystallography reveals a trinuclear complex formed by interaction of two intact aryl iodide molecules with the bismuth center. The alignment of the bismuth and two iodine atoms is almost linear (I-Bi-I angle of 160.659(12)°), implying the presence of interactions with the filled p-orbital of bismuth perpendicular to the NCN plane (Figure ).