Icosahedral Pt-Centered Pt13 and Pt19 Carbonyl Clusters Decorated by [Cd5(μ-Br)5Br5−x(solvent)x]x+ Rings Reminiscent of the Decoration of Au−Fe−CO and Au-Thiolate Nanoclusters: A Unifying Approach to Their Electron Counts

The new [Pt13(CO)12{Cd5(μ-Br)5Br2(dmf)3}2]2− and [Pt19(CO)17{Cd5(μ-Br)5Br3(Me2CO)2}{Cd5(μ-Br)5Br(Me2CO)4}]2− clusters have been obtained in good yields by reaction of [Pt12(CO)24]2− with CdBr2·H2O in dmf at 90 °C and structurally characterized by X-ray diffraction. Their structures consist of a Pt-centered Pt13(CO)12 icosahedron and a Pt19(CO)17 interpenetrated double icosahedron, respectively, decorated by two Cd5(μ-Br)5Br5−x(solvent)x rings. Their surface decoration may be related to that of Au−Fe−CO clusters as well as to the staple motifs stabilizing gold−thiolates nanoclusters. An oversimplified and unifying approach to interpret their electron count is suggested.