Very recently it was shown that the metalloid cluster compound {Ge(9)[Si(SiMe(3))(3)](3)}(-) can be used for subsequent reactions as the shielding of the cluster core is rather incomplete. Here further reactions of with M(+) sources of group 11 metals are described, leading to metalloid cluster compounds of the formula {MGe(18)[Si(SiMe(3))(3)](6)}(-) (M = Ag, Cu). These reactions can be seen as first steps into a supramolecular chemistry with metalloid cluster compounds. Beside this feature, the structural properties as well as the bonding situations in these cluster compounds are discussed.

Very recently it was shown that the metalloid cluster compound {Ge(9)[Si(SiMe(3))(3)](3)}(-) can be used for subsequent reactions as the shielding of the cluster core is rather incomplete. So the reaction of with M(+) sources of group 11 metals gives metalloid cluster compounds of the formulae {MGe(18)[Si(SiMe(3))(3)](6)}(-) (M = Au, Ag, Cu). These reactions can be seen as first steps into a supramolecular chemistry with metalloid cluster compounds. However, further build-up reactions lead to insoluble products, thus better soluble starting materials are needed for further build-up reactions. Here the first neutral MGe(18)[Si(SiMe(3))(3)](6) (M = Hg, Cd, Zn) compounds are described, exhibiting a strongly enhanced solubility in inert solvents. Beside the synthesis, the structural properties as well as the bonding situations in these cluster compounds are discussed.

Very recently it was shown that the metalloid cluster compound {Ge(9)[Si(SiMe(3))(3)](3)}(-)1 can be used for subsequent reactions as the shielding of the cluster core is rather incomplete. So the reaction of 1 with Cr(CO)(3)(CH(3)CN)(3) leads to a cluster enlargement where the chromium atom is incorporated into the cluster core. Here further applications of 1 as a flexible ligand in coordination chemistry are presented where the reaction of 1 with Mo(CO)(3)(EtCN)(3) and W(CO)(3)(CH(3)CN)(3) leads to [(CO)(3)MoGe(9)R(3)](-)4 and [(CO)(3)WGe(9)R(3)](-)5 respectively (R = Si(SiMe(3))(3)), showing that 1 can indeed be used as a flexible ligand in coordination chemistry. Structural and electronic properties of the Ge(9)M clusters 4 and 5 are discussed as well as mechanistic aspects of their formation.

Femtosecond pump-probe absorption spectroscopy in tetrahydrofuran solution has been used to investigate the dynamics of a metalloid cluster compound {Ge9[Si(SiMe3)3]3}(-). Upon UV photoexcitation, the transients in the near-infrared spectral region showed signatures reminiscent of excess electrons in THF (bound or quasi-free) whereas in the visible part excited state dynamics of the cluster complex dominates.