Dehydrazinative C (sp ² )‐S Coupling Enabled by a Heterogeneous Iron Carbide Photocatalyst

In this study, a method for the dehydrazinative dithiocarbamation of arylhydrazines was developed by using iron carbide as a recyclable photocatalyst. Notably, the iron carbide nanoparticles were prepared by the Fe/Zn‐MOF precursors via thermal decomposition, which were investigated by TEM, SEM, TG, XPS, XRD, and BET analyses. Various arylhydrazines with diverse functional groups could be readily transformed into the corresponding aryl dithiocarbamates with high efficiency and good yields. Mechanistic studies suggested that the production of an aryl radical and a thiocarbamate radical was the key step in the selective C (sp 2 )‐S bond formation. Moreover, the practicability of this protocol was demonstrated through gram‐scale reactions.