Thiolate-bridged polynuclear clusters of copper(I) and silver(I): Syntheses and structures of [Cu8(μ4-SPh)6(PPh3)4(MeCN)4][(CdI)3Cu(μ-SPh)6], [Cu8(μ-SPh)4(μ3-SPh)4(PPh3)4], [Cu14(μ6-S)(μ3-SPhMe-4)12(PPh3)6], and [Ag14(μ6-Br)(μ3-SPh)12(PPh3)8]Cl

The interaction of [Et4N]2[Cd4(SPh)10] with CuI in DMF–MeCN in the presence of PPh3 gave the metal cluster ion-pair [Cu8(μ4-SPh)6(PPh3)4(MeCN)4][Cu(μ-SPh)6(CdI)3] (1), with a cationic octanuclear copper(I) cage cluster and an anionic mixed-metal complex. Reaction of CuI and NaSPh in DMF in the presence of PPh3 resulted in the formation of a neutral octanuclear copper(I) cluster [Cu8(μ-SPh)4(μ3-SPh)4(PPh3)4] (2), whereas the similar reaction of CuI and NaSPh-4-Me led to the isolation of a neutral tetradecanuclear copper(I) cluster [Cu14(μ6-S)(μ-SPh-4-Me)12(PPh3)6] (3). Similarly, treatment of AgBr with NaSPh in DMF in the presence of PPh3 afforded a cationic bromide-centered tetradecanuclear silver(I) cage cluster [Ag14(μ6-Br)(μ3-SPh)12(PPh3)8]Cl (4). The structures of the clusters 1–4 were determined by single-crystal X-ray diffraction analyses.

Graphical abstractThe metal cluster ion-pair [Cu8(μ4-SPh)6(PPh3)4(MeCN)4][Cu(μ-SPh)6(CdI)3] has been characterized. It consists of a cationic octanuclear copper(I) cage cluster, in which eight copper ions are linked by six face-capped μ4-SPh− ligands, and an anionic mixed-metal complex consisting of a six-membered Cd3(SPh)3 ring in a chair conformation that is capped by a nearly trigonal-planar Cu(SPh)3 unit.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► The thiolate-bridged polynuclear clusters of copper(I) and silver(I). ► Syntheses and structures of polynuclear copper(I) and silver(I) clusters stabilized by thiolate and triphenylphosphine ligands. ► Coordination chemistry of polynuclear d10 metal complexes.