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 I 3 Rh III 2 pentanuclear complex, [Cu 3 {Rh(aet) 3 } 2 ] 3+ (aet=2-aminoethanethiolate), in which a {Cu I 3 } 3+ cluster moiety is bound by two fac-[Rh(aet) 3 ] metalloligands, with NaSH in water produced the Cu I 6 Rh III 4 decanuclear complex, [Cu 6 S{Rh(aet) 3 } 4 ] 4+ , accompanied by the dimerization of [Cu 3 {Rh(aet) 3 } 2 ] 3+ and the incorporation of a sulfide ion at the center. While similar treatment using the analogous Cu I 3 Ir III 2 complex with fac-[Ir(aet) 3 ] metalloligands, [Cu 3 {Ir(aet) 3 } 2 ] 3+ , produced the isostructural Cu I 6 Ir III 4 decanuclear complex, [Cu 6 S{Ir(aet) 3 } 4 ] 4+ , the use of the Cu I 3 Rh III 2 complex with fac-[Rh(apt) 3 ] metalloligands, [Cu 3 {Rh(apt) 3 } 2 ] 3+ (apt=3-aminopropanethiolate), resulted in the removal of one of the three Cu I atoms from {Cu I 3 } 3+ to afford the Cu I 2 Rh III 2 tetranuclear complex, [Cu 2 {Rh(apt) 3 } 2 ] 2+ .