Heptanuclear Fe5Cu2-Phenylgermsesquioxane containing 2,2′-Bipyridine: Synthesis, Structure, and Catalytic Activity in Oxidation of C–H Compounds

A new representative of an unusual family of metallagermaniumsesquioxanes, namely the heterometallic cagelike phenylgermsesquioxane (PhGeO2)12Cu2Fe5(O)OH(PhGe)2O5(bipy)2(2), was synthesized and structurally characterized. Fe(III) ions of the complex are coordinated by oxa ligands: (i) cyclic (PhGeO2)12and acyclic (Ph2Ge2O5) germoxanolates and (ii) O2–and (iii) HO–moieties. In turn, Cu(II) ions are coordinated by both oxa (germoxanolates) and aza ligands (2,2′-bipyridines). This “hetero-type” of ligation gives in sum an attractive pagoda-like molecular architecture of the complex 2. Product 2showed a high catalytic activity in the oxidation of alkanes to the corresponding alkyl hydroperoxides (in yields up to 30%) and alcohols (in yields up to 100%) and in the oxidative formation of benzamides from alcohols (catalyst loading down to 0.4 mol % in Cu/Fe).