Sulfide-Induced Dimerization Versus Demetallation of Tricopper(I) Clusters Protected by Tris-Thiolato Metalloligands.

Here, we report the reactivity of copper(I) clusters toward sulfide ions; these sulfide copper(I) clusters have attracted much attention due to their relevance to biologically active centers and their fascinating structural and photophysical properties. Treatment of the Cu Rh pentanuclear complex, [Cu{Rh(aet)}] (aet=2-aminoethanethiolate), in which a {Cu } cluster moiety is bound by two fac-[Rh(aet)] metalloligands, with NaSH in water produced the Cu Rh decanuclear complex, [CuS{Rh(aet)}], accompanied by the dimerization of [Cu{Rh(aet)}] and the incorporation of a sulfide ion at the center. While similar treatment using the analogous Cu Ir complex with fac-[Ir(aet)] metalloligands, [Cu{Ir(aet)}], produced the isostructural Cu Ir decanuclear complex, [CuS{Ir(aet)}], the use of the Cu Rh complex with fac-[Rh(apt)] metalloligands, [Cu{Rh(apt)}] (apt=3-aminopropanethiolate), resulted in the removal of one of the three Cu atoms from {Cu } to afford the Cu Rh tetranuclear complex, [Cu{Rh(apt)}].