Cobalt‐Mediated SS Bond Formation: Crystal Structure and Spectroscopic Properties of [Co2(S2)2(tren)2]3[SbS4]2·21.5 H2O Containing a Co2S4 Heterocycle
Year: 2025
Type: article
Abstract: The reaction of an aqueous solution of Na3SbS4·9H2O with a Co(II) salt dissolved in acetonitrile in the presence of tris(2‐aminoethyl)amine affords crystallization of [Co2(S2)2(tren)2]3[SbS4]2·21.5 H2O which contains in situ formed S22− anions and Co(III) cations formed by oxidation of Co(II). The Co(III) centers of the two independent [Co2S4]2+ cores are complemented by the tetradentate amine molecules and distorted CoN4S2 octahedra are formed. Charge compensation is achieved by the tetrahedral [SbS4]3− anions. The two intriguing experimental findings, i.e., the oxidation of Co(II) and the formation of S22− dumbbells, are explained on the basis of the detailed calculation of the reaction mechanism indicating SS bond formation by radical coupling of two terminal thiyl ligands. The bands of the Co2S4 heterocycle in the infrared and Raman spectra can also be assigned with density functional theory calculations.
Institution: Christian-Albrechts-Universität zu Kiel
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,050
OpenAlex ID: W4409870941