Within the reaction of a metastable Ge(I)Cl solution and Na2Fe2(CO)8 the anionic cubic cluster compound {(thf)14Na6Ge8[Fe(CO)4]8}− (3) is obtained. The open shell character of 3 is proven by EPR spectroscopy....

The reaction of GeCl2·dioxane with the sodium salts NaMCp(CO)3 (M = Cr, Mo, W) leads to new four‐membered ring compounds Ge4Cl4[MCp(CO)3]4, where the remaining chlorine atom cannot be substituted by another MCp(CO)3 substituent. A large excess of the sodium salts only leads to some minor side‐reactions. All Ge4‐compounds exhibit a non‐planar four‐membered Ge4 ring, which can be traced back to electrostatic effects as shown by quantum chemical calculations. Furthermore, cluster build‐up reactions might be possible due to the halide substituents in the new ring compounds of germanium, showing that GeCl2·dioxane is an excellent starting material for the synthesis of cluster compounds of germanium.

The reaction of GeCl2·dioxane with KFeCp(CO)2 leads to polyhedral cluster compounds with six germanium atoms like Ge6[FeCp(CO)2]6 or Ge6Cl2[FeCp(CO)2]6via a complex reaction route.

The synthesis of a variety of cobalt substituted germanes of the composition GeClx[Co(CO)3PR3]4−x (x = 0-3; R = nPr, nBu) is presented, which can be obtained in average to good...