The flexibility of binding modes of the supersilyl thiolate ligand SSitBu3−

► Treatment of S8 with [Zn(SitBu3)2] yields [Zn(SSitBu3)2]2. ► Supersilyl thiolate ligands in [Zn(SSitBu3)2]2 reveal two different binding modes. ► The structure of [Zn(SSitBu3)2] displays terminal and bridging thiolate ligands.