Icosahedral Pt-centered Pt13 and Pt19 carbonyl clusters decorated by [Cd5(μ-Br)5Br(5-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 [Pt(13)(CO)(12){Cd(5)(μ-Br)(5)Br(2)(dmf)(3)}(2)](2-) and [Pt(19)(CO)(17){Cd(5)(μ-Br)(5)Br(3)(Me(2)CO)(2)}{Cd(5)(μ-Br)(5)Br(Me(2)CO)(4)}](2-) clusters have been obtained in good yields by reaction of [Pt(12)(CO)(24)](2-) with CdBr(2)·H(2)O in dmf at 90 °C and structurally characterized by X-ray diffraction. Their structures consist of a Pt-centered Pt(13)(CO)(12) icosahedron and a Pt(19)(CO)(17) interpenetrated double icosahedron, respectively, decorated by two Cd(5)(μ-Br)(5)Br(5-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.