Issue 23, 2025

Chalcogenide-centered Cu11 clusters heteroleptically passivated by dichalcogenolates and iodo ligands

Abstract

Halide ligands can serve as auxiliary ligands for the dichalcogenolates ligands, facilitating the formation of novel chalcogen-centered copper clusters. This report presents three chalcogenide-centered copper clusters, namely [Cu11S{S2CNnBu2}6(I)3] (1), [Cu11Se{Se2CNnPr2}6(I)3] (2), and [Cu11Se{Se2CNiBu2}6(I)3] (3). Cluster 1 was isolated from the reaction of [Cu(CH3CN)4](BF4) with dithiocarbamate (dtc) ligands, specifically dtc = {S2CNnBu2}, alongside [NBu4I], in the presence Na2S2O3 as the sulfide source. Clusters 2 and 3 are prepared from diselenocarbamate (dsec) ligands, from which the selenide anion is generated in situ. The structures are characterized using single X-ray diffraction, which demonstrated that clusters 1–3 are iso-structural and feature a chalcogenide-centered Cu11 3,3,4,4,4-pentacapped trigonal prism surrounded by six dichalcogelates ligand, co protected by iodo ligands. The structural study demonstrated that the central chalcogenide (S2− and Se2−) in clusters 1–3 enhances the host–guest interaction, with the order of effectiveness being S < Se. Furthermore, the replacement of dichalcogenolate ligand, dtc with dsec, elongates metallic interactions within the copper host cage. The structural characteristics of clusters 1–3 demonstrate notable similarities, providing a basis for comparing the inverse coordination of chalcogenide-centered clusters protected by various dichalcogenolates and iodide ligands, which affect the host–guest distances within the Cu11 framework.

Graphical abstract: Chalcogenide-centered Cu11 clusters heteroleptically passivated by dichalcogenolates and iodo ligands

Supplementary files

Article information

Article type
Paper
Submitted
11 Apr 2025
Accepted
20 May 2025
First published
21 May 2025

New J. Chem., 2025,49, 9965-9972

Chalcogenide-centered Cu11 clusters heteroleptically passivated by dichalcogenolates and iodo ligands

R. P. Brocha Silalahi, Y. Kuo, T. Chiu, M. N. Pillay and C. W. Liu, New J. Chem., 2025, 49, 9965 DOI: 10.1039/D5NJ01571E

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