Figure 3. UV/Vis spectra of all three Au 32 clusters 1 Et (blue), 1 Pr (orange), and 1 Bu (green) in dichloromethane. The spectra show one clear band at 480 nm, three weak bands at 600, 662, and 727 nm, and five shoulders at 395, 448, 510, 538, and 565 nm. Angewandte ChemieCommunications 5904 www.angewandte.org

The oxidation of [Ge9(Hyp)3](-) (Hyp=Si(SiMe3 )3) with an Fe(II) salt leads to Ge18 (Hyp)6 (1), the largest Group 14 metalloid cluster that has been structurally characterized to date. The arrangement of the 18 germanium atoms in 1 shows similarities to that found in the solid-state structure Ge(cF136). Furthermore, 1 can be described as a macropolyhedral cluster of two Ge9 units. Quantum-chemical calculations further hint at a strained arrangement so that 1 can be considered as a first trapped intermediate on the way from Ge9 units to elemental germanium with the clathrate-II structure (Ge(cF136)).

The reduction of (Ph P)AuCl with NaBH in the presence of HSC(SiMe ) , leads to one of the largest metalloid gold clusters: Au S (PPh ) (1). Within 1 an octahedral Au core of gold atoms arranged as in Au metal is surrounded by 48 oxidized Au atoms of an Au S shell, a novel building block in gold chemistry. The protecting Au S shell is completed by additional 16 Au(PPh ) units, leading to a complete protection of the gold core. Within 1 the Au-Au distances get more molecular on going from the center to the ligand shell. Cluster 1 represents novel structural motives in the field of metalloid gold clusters which also are partly typical for metal atoms in metalloid clusters: M R (n>m).

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Reducing (PhP)AuSC(SiMe) with l-Selectride® gives the medium-sized metalloid gold cluster AuS(PPh). Computational studies show that the phosphine bound Au-atoms not only stabilize the electronic structure of AuS(PPh), but also behave as electron acceptors leading to auride-like gold atoms on the exterior.