Coordinated nitroxyl anion is produced and released as nitrous oxide by the decomposition of iridium-coordinated nitrosothiols

► The decomposition of Ir-nitrosothiol complexes produces NO−, sulfenic acids and NO2−. ► Nitrous oxide (N2O) and nitrogen were detected in the gas phase. ► Free nitroxyl (HNO) is proposed as an intermediate. ► The decomposition involves attack of H2O on the S atom of the coordinated nitrosothiol. ► The decomposition occurs through a different mechanism than for free nitrosothiols.