Sulfur versus Dioxygen: Dinuclear (Trisulfido)copper Complexes

In contrast to dinuclear (disulfido)copper complexes related trisulfido compounds have not been reported so far. Here we describe two new complexes of this type, [Cu2(tmpa)2S3](SbF6)2 {tmpa = tris(2‐pyridylmethyl)amine} and [Cu2(tet b)2S3](OTf)2 (tet b = rac‐5,5,7,12,12,14‐hexamethyl‐1,4,8,11‐tetraazacyclotetradecane), that have been investigated and could be structurally characterized. Furthermore, the reactivity of these complexes towards dioxygen showed that the corresponding (peroxido)copper complexes formed. Depending on the stoichiometric conditions (excess of sulfur) mononuclear end‐on (sulfido)copper complexes were detected spectroscopically. DFT calculations were performed and supported the experimental results. The first examples of structurally characterized (trisulfido)copper complexes (with ligands tmpa and tet b) have been synthesized and characterized. Reactivity studies and DFT calculations were performed with these complexes.