Characterization of "Cd₁₀S₄(SPh)₁₂" , the Thermal Decomposition Product of (NMe₄)₄[Cd₁₀S₄(SPh)₁₆]: Synthesis of a Neutral Cd₅₄ Sulfide Cluster and of a Polymeric Chain of Thiolate-Bridged Cd₁₇ Sulfide Clusters

Abstract

Contrary to claims in the literature that a cluster of the composition of Cd₁₀S₄(SPh)₁₂ was formed by thermal treatment of (NMe₄)₄[Cd₁₀S₄(SPh)₁₆], experimental evidence was gathered that the core structure of the cluster is not exclusively retained and other CdS species are also formed. When Cd₁₀S₄(SPh)₁₂ was treated with PhSH/NEt₃ only a part of the material was converted into (NHEt₃)₄[Cd₁₀S₄(SPh)₁₆]. From solutions of Cd₁₀S₄(SPh)₁₂ in strongly coordinating solvents the new neutral CdS clusters Cd₅₄S₂₈(SPh)₅₂Lₓ (L = pyridine, DMSO or DMF) and [Cd₁₇S₄(SPh)₂₆py] were crystallized. The latter forms polymeric chains of phenylthiolate-bridged Cd₁₇ units.