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)}].

Heterometallation of Photoluminescent Silver(I) Sulfide Nanoclusters Protected by Octahedral Iridium(III) Thiolates.

The recently-increasing interest in coinage metal clusters stems from their photophysical properties, which are controlled via heterometallation. Herein, we report homometallic Ag S clusters protected by octahedral fac-[Ir(aet) ] (aet=2-aminoethanethiolate) molecules and their conversion to heterometallic Ag M S (M=Cu, Au) clusters. The reactions of fac-[Ir(aet) ] with Ag and penicillamine produced [Ag S {Ir(aet) } ] ([1] ), where a spherical Ag S cluster is covered by fac-[Ir(aet) ] octahedra through thiolato bridges.

Controlled Formation of Thiol-Thiolate Hydrogen versus Disulfide Bonds between Two Iridium(III) Centers.

Here, we report an iridium(III) coordination system with 2-aminoethanethiolate (aet), which shows the formation of S-H⋅⋅⋅S hydrogen and S-S disulfide bonds in a controlled manner. Treatment of fac-[Ir(aet) ] with aqueous HBF under aerobic conditions gave dinuclear [Ir (aet) (cysta)] ([1] ; cysta=cystamine) with a single S-S disulfide bond, while dimeric [Ir (aet) (Haet) ](BF ) ([2](BF ) ) with a triple S-H⋅⋅⋅S hydrogen bond was formed by similar treatment under anaerobic conditions. Upon exposure to air, [2] was converted to dinuclear [Ir (aet) (Haet) (cysta)] ([3] ), in which two Ir centers are spanned by a double S-H⋅⋅⋅S hydrogen bond and a single S-S disulfide bond.

Structurally Precise Silver Sulfide Nanoclusters Protected by Rhodium(III) Octahedra with Aminothiolates.

A 60-nuclear silver sulfide nanocluster with a highly positive charge (1) has been synthesized by mixing an octahedral Rh complex with 2-aminoethanethiolate ligands, silver(I) nitrate, and d-penicillamine in water under mild conditions. The spherical surface of 1 is protected by the chiral octahedral Rh complex, with cleavage of the C-S bond of the d-penicillamine supplying the sulfide ions. Although 1 does not contain d-penicillamine, it is optically active because of the enantiomeric excess of the Rh molecules induced by chiral transfer from d-penicillamine.