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

Zi Lang Goo; Nobuto Yoshinari; Yuhei Yasukawa; Katsue Minami; Takumi Konno

doi:10.1002/asia.202400266

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

Chem Asian J. 2024 Apr 28:e202400266. doi: 10.1002/asia.202400266. Online ahead of print.

Authors

Zi Lang Goo¹, Nobuto Yoshinari², Yuhei Yasukawa¹, Katsue Minami¹, Takumi Konno¹

Affiliations

¹ Osaka University, Department of Chemistry, Graduate School of Science, JAPAN.
² Osaka University, Department of Chemistry, Graduate School of Science, 1-1 Machikaneyama, 560-0043, Toyonaka, Osaka, JAPAN.

PMID: 38679869
DOI: 10.1002/asia.202400266

Abstract

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 CuI3RhIII2 pentanuclear complex, [Cu3{Rh(aet)3}2]3+ (aet = 2-aminoethanethiolate), in which a {CuI3}3+ cluster moiety is bound by two fac-[Rh(aet)3] metalloligands, with NaSH in water produced the CuI6RhIII4 decanuclear complex, [Cu6S{Rh(aet)3}4]4+, accompanied by the dimerization of [Cu3{Rh(aet)3}2]3+ and the incorporation of a sulfide ion at the center. While similar treatment using the analogous CuI3IrIII2 complex with fac-[Ir(aet)3] metalloligands, [Cu3{Ir(aet)3}2]3+, produced the isostructural CuI6IrIII4 decanuclear complex, [Cu6S{Ir(aet)3}4]4+, the use of the CuI3RhIII2 complex with fac-[Rh(apt)3] metalloligands, [Cu3{Rh(apt)3}2]3+ (apt = 3-aminopropanethiolate), resulted in the removal of one of the three CuI atoms from {CuI3}3+ to afford the CuI2RhIII2 tetranuclear complex, [Cu2{Rh(apt)3}2]2+.

Keywords: S ligand; copper cluster; metalloligand; structural conversion; sulfide ion.