Characterization of 'Cd_(10)S_4(SPh) _(12)', the thermal decomposition product of (NMe_4) _4[Cd_(10)S_4(SPh)_(16)]: Synthesis of a neutral Cd_(54) sulfide cluster and of a polymeric chain of thiolate-bridged Cd_(17) sulfide clusters

摘要

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 phenylthiolatebridged Cd17 units.