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

Contrary to claims in the literature that a cluster of the composition of “Cd 10 S 4 (SPh) 12 ” was formed by thermal treatment of (NMe 4 ) 4 [Cd 10 S 4 (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 “Cd 10 S 4 (SPh) 12 ” was treated with PhSH/NEt 3 only a part of the material was converted into (NHEt 3 ) 4 [Cd 10 S 4 (SPh) 16 ]. From solutions of “Cd 10 S 4 (SPh) 12 ” in strongly coordinating solvents the new neutral CdS clusters Cd 54 S 28 (SPh) 52 L x (L = pyridine, DMSO or DMF) and [Cd 17 S 4 (SPh) 26 py] ∞ were crystallized. The latter forms polymeric chains of phenylthiolate‐bridged Cd 17 units.