A Novel Family of Cage-like (CuLi, CuNa, CuK)-phenylsilsesquioxane Complexes with 8-Hydroxyquinoline Ligands: Synthesis, Structure, and Catalytic Activity. Nanosized silsesquioxane [RSiO1.5]n units bridge a gap between organics and inorganics with their pure inorganic Si-O-Si main chain, surrounded by various organic substituents. Silsesquioxanes are often regarded as unique molecular models of silica, both for investigations into surface phenomena and heterogeneous catalysis.
The first examples of metallasilsesquioxane complexes, including ligands of the 8-hydroxyquinoline family 1–9, were synthesized, and their structures were established by single crystal X-ray diffraction using synchrotron radiation. Compounds 1–9 tend to form a type of sandwich-like cage of Cu4M2 nuclearity (M = Li, Na, K). Each complex includes two cisoid pentameric silsesquioxane ligands and two 8-hydroxyquinoline ligands. The latter coordinates the copper ions and corresponding alkaline metal ions (via the deprotonated oxygen site). A characteristic (size) of the alkaline metal ion and a variation of characteristics of nitrogen ligands (8-hydroxyquinoline vs. 5-chloro-8-hydroxyquinoline vs. 5,7-dibromo-8-hydroxyquinoline vs. 5,7-diiodo-8-hydroxyquinoline) are highly influential for the formation of the supramolecular structure of the complexes 3a, 5, and 7–9. The Cu6Na2-based compound 2 exhibits high catalytic activity towards the oxidation of (i) hydrocarbons by H2O2 activated with HNO3, and (ii) alcohols by tert-butyl hydroperoxide. Studies of kinetics and their selectivity has led us to conclude that it is the hydroxyl radicals that play a crucial role in this process.