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

Publication date: Available online 24 January 2019Source: Journal of Organometallic ChemistryAuthor(s): Alena N. Kulakova, Alexander A. Korlyukov, Yan V. Zubavichus, Victor N. Khrustalev, Xavier Bantreil, Lidia S. Shul'pina, Mikhail M. Levitsky, Nikolay S. Ikonnikov, Elena S. Shubina, Frédéric Lamaty, Alexey N. Bilyachenko, Georgiy B. Shul'pinAbstractA 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 complexe...

Source: Journal of Organometallic Chemistry - January 25, 2019 Category: Chemistry Source Type: research