GeClx[Co(CO)3PR3]4-x (x = 0-3; R = nPr, nBu): from cobalt substituted germanes to novel binary cluster compounds.

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 yields from a reaction of GeCl2·dioxane and Co2(CO)8 or KCo(CO)4 in the presence of the respective phosphine. Reductive coupling reactions with potassium/benzophenone lead to ligand scrambling while the reductive coupling with Mg/MgBr2 leads to the pseudo-cubic cluster compound Ge7Co(CO)3[Co(CO)3PnBu3]72, showing that the mixed substituted germanes are powerful precursors to this new class of cluster compounds. All compounds are structurally characterized and well observable via NMR and IR spectroscopy.