Abstract
The interaction of [Et 4N] 2[Cd 4(SPh) 10] with CuI in DMF–MeCN in the presence of PPh 3 gave the metal cluster ion-pair [Cu 8(μ 4-SPh) 6(PPh 3) 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 PPh 3 resulted in the formation of a neutral octanuclear copper(I) cluster [Cu 8(μ-SPh) 4(μ 3-SPh) 4(PPh 3) 4] ( 2), whereas the similar reaction of CuI and NaSPh-4-Me led to the isolation of a neutral tetradecanuclear copper(I) cluster [Cu 14(μ 6-S)(μ-SPh-4-Me) 12(PPh 3) 6] ( 3). Similarly, treatment of AgBr with NaSPh in DMF in the presence of PPh 3 afforded a cationic bromide-centered tetradecanuclear silver(I) cage cluster [Ag 14(μ 6-Br)(μ 3-SPh) 12(PPh 3) 8]Cl ( 4). The structures of the clusters 1– 4 were determined by single-crystal X-ray diffraction analyses.
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