Missing Link in the Growth of Lead-Based Zintl Clusters: Isolation of the Dimeric Plumbaspherene [Cu(4)Pb(22)](4–)

[Image: see text] We report here the structure of an endohedral plumbaspherene, [Cu(4)Pb(22)](4–), the gold analogue of which was previously postulated to be a “missing link” in the growth of larger clusters containing three and four icosahedral subunits. The cluster contains two [Cu(2)Pb(11)](2–) subunits linked through a Cu(2)Pb(4) trigonal antiprism. Density functional theory reveals that the striking ability of mixed Pb/coinage metal Zintl clusters to oligomerize and, in the case of Au, to act as a site of nucleation for additional metal atoms, is a direct consequence of their nd(10)(n + 1)s(0) configuration, which generates both a low-lying (n + 1)s-based LUMO and also a high-lying Pb-centered HOMO. Cluster growth and nucleation is then driven by this amphoteric character, allowing the clusters to form donor–acceptor interactions between adjacent icosahedral units or to additional metal atoms.