Synthesis of bis(trithio)phosphines by oxidative transfer of phosphorus(i) Electronic supplementary information (ESI) available: Structural data in CIF format. CCDC 1543742-1543744. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7dt01345k

The synthesis of novel bis(trithio)phosphines is achieved by oxidative addition of tetrathiocins to the phosphorus( i ) reagent [P I dppe][Br] in good yields under ambient conditions. These bis(trithio)phosphines and the related intermediate diphosphine species are characterized by X-ray diffraction and multinuclear NMR and a mechanism is proposed for the formation of these molecules. In contrast, the related reaction with diphenyldisulfide produces a mononuclear tris(phenylthio)phosphine. We report the oxidative transfer of the phosphorus( i ) centre in [P I dppe][Br] to tetrathiocin and disulfide ligands. Characterization of the resulting bis(trithio)phosphines and mechanistic insight into the formation of these products is provided.