Synthesis and Crystal Structures of the Ligand‐Stabilized Silver Chalcogenide Clusters [Ag₁₅₄Se₇₇(dppxy)₁₈], [Ag₃₂₀(StBu)₆₀S₁₃₀(dppp)₁₂], [Ag₃₅₂S₁₂₈(StC₅H₁₁)₉₆], and [Ag₄₉₀S₁₈₈(StC₅H₁₁)₁₁₄]

The reaction of silver thiolates with Se(SiMe3)2 or S(SiMe3)2 in the presence of bidentate phosphanes leads to the formation of very large cluster molecules with distorted spherical metal–chalcogenide cores with diameters of 2–4 nm. The surfaces of these cores are protected by thiolate and phosphane ligands. Structural analyses show a higher degree of disorder with increasing number of Ag atoms. The compound with the highest silver content (see figure) has an idealized formulation [Ag490S188(StC5H11)114].