[Si(SiMe3)3]3Ge9M(CO)3(-) (M=Cr, Mo, W): coordination chemistry with metalloid clusters.

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.

[Si(SiMe3)3]6Ge18M (M = Zn, Cd, Hg): neutral metalloid cluster compounds of germanium as highly soluble building blocks for supramolecular chemistry.

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.

[Si(SiMe(3))(3)](6)Ge(18)M (M = Cu, Ag, Au): metalloid cluster compounds as unusual building blocks for a supramolecular chemistry.

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.