Systematic Access of Ternary Organotetrel‐Copper Chalcogenide Clusters by [PhTE(3)](3−) Anions (T=Si, Sn; E=S, Se)

Fragmentation reactions of organotetrel chalcogenide heteroadamantane‐type clusters [(PhT)(4)E(6)] (T/E=Si/S (1); Si/Se; Sn/S, and Sn/Se) by addition of the corresponding sodium chalcogenide gave salts of the general formula Na(3)[PhTE(3)], with T/E=Si/S (2); Si/Se (3); Sn/S (A); Sn/Se (4). Reaction of these salts with [Cu(PPh(3))(3)Cl] gave a series of organotetrel–copper chalcogenide clusters [(CuPPh(3))(6)(PhTE(3))(2)] with T/E=Si/S; (5), Si/Se (6), Sn/S (7) and Sn/Se (8). Compounds 5–8 share a common structural motif with two intact {PhTE(3)} units coordinating a Cu(6) moiety, which was previously reported with other ligands, and for the Sn and Ge congeners only. If the Sn/Se reaction system was allowed to crystallize more slowly, single crystals of compound [(CuPPh(3))(6)(PhSnSe(3))(3)Cu(3)SnSe] (9) were obtained, which are based on a larger cluster structure. Hence, 9 might form from 8 through incorporation of additional cluster fragments. The experimentally and quantum chemically determined optical properties were compared to related clusters.