Hexacoppergermsesquioxanes as complexes with N-ligands: Synthesis, structure and catalytic properties

A simple and versatile strategy of synthesis of cage metallagermaniumsesquioxanes is demonstrated for isolation of Cu6-based phenylgermsesquioxanes 1–6. Structure of newly synthesized coppergermsesquioxanes was established by single-crystal X-ray diffraction analysis. General principle of these cages' topology implies the presence of two linear Cu3 fragments, coordinated by three pairs of ligands. These are: (i) cyclic germsesquioxanes [PhGeO1,5]5, products 1–6, (ii) 1,10-phenanthrolines, (1, 3–5) or 2,2’-bipyridines, (2, 6), (or and (iii) OX species (X = H, 1–2, CH3, 3, H and C2H5O, 4, HCO, 5, CH3CO, 6). Appearance of non-expected species (formiate for 5, acetate for 6), resulted from corresponding alcohols used as reaction media, points at easyness of oxidation processes in the conditions of such self-assembling reactions. Catalytic tests showed high activity of complexes 1 and 2 as precatalysts in homogeneous oxidations of alkanes (cyclohexane, methylcyclohexane, n-heptane, cis-1,2-dimethylcyclohexane with hydrogen peroxide in acetonitrile solution. Hydroxyl radicals take part in the reaction. The same complexes catalyze oxidation of alcohols (cyclohexanol, 2-heptanol, 1-phenylethanol) to corresponding ketones with tert-butyl hydroperoxide in almost 100% yield. With the addition of various alkyl ammonium salts, complex 2 could also furnish corresponding amides in high yield.