High-nuclearity Cu14 ionic complex featuring 1,3-bis(diphenylphosphino)propane and methylsilsesquioxane ligands: highly efficient catalysis of mild peroxidative alkane fuctionalizations.

The first metallacomplex containing both 1,3-bis(diphenylphosphino)propane and silsesquoxane ligands is presented, which adopts an intriguing three-component ionic structure. According to X-ray diffraction studies, the central dianionic CuII12-methylsilsesquioxane cage is balanced by two external cationic [CuI(dppp)2] species, giving a total Cu14 nuclearity. The cage component of the complex encapsulates hydroxyl, carbonate, and chloride species. The complex was evaluated as a catalyst for the effective oxidation of alkanes to alkyl hydroperoxides and of alcohols to ketones using peroxides.