µ-Oxido-bis[triphenylphosphinenitrosyliridium(I)]–C₆H₆ has been prepared by the reaction of trans-Ir(CO)Cl(PPh₃)₂ and nitrite ion in benzene–aqueous alcohol: its structure contains the first example of a bent iridium–iridium bond and a nitrosyl group π-bonded to an iridium atom.