Surface decorated platinum carbonyl clusters

Four molecular Pt–carbonyl clusters decorated by Cd–Br fragments, i.e., [Pt13(CO)12{Cd5(m- Br)5Br2(dmf)3}2]2 (1), [Pt19(CO)17{Cd5(m-Br)5Br3(Me2CO)2}{Cd5(m-Br)5Br(Me2CO)4}]2 (2), [H2Pt26(CO)20(CdBr)12]8 (3) and [H4Pt26(CO)20(CdBr)12(PtBr)x]6 (4) (x ¼ 0–2), have been obtained from the reactions between [Pt3n(CO)6n]2 (n ¼ 2–6) and CdBr2$H2O in dmf at 120 C. The structures of these molecular clusters with diameters of 1.5–2 nm have been determined by X-ray crystallography. Both 1 and 2 are composed of icosahedral or bis-icosahedral Pt–CO cores decorated on the surface by Cd–Br motifs, whereas 3 and 4 display a cubic close packed Pt26Cd12 metal frame decorated by CO and Br ligands. An oversimplified and unifying approach to interpret the electron count of these surface decorated platinum carbonyl clusters is suggested, and extended to other low-valent organometallic clusters and Au–thiolate nanoclusters.