Cu 12 -Methylsilsesquioxane Cage Decorated with Cu(dppe) 2 Moieties for Mild Oxidative Functionalization of Alkanes.

We report a high nuclear (Cu ₁₄ ) complex synthesized via the self-assembly of copper-methylsilsesquioxane induced by the complexation with 1,2-bis(diphenylphosphino)ethane (dppe). The structure includes two cationic Cu ^I (dppe) ₂ moieties and an anionic silsesquioxane cage of an unprecedented Cu ^II ₁₂ structural type. The Cu ₁₂ cage fragment exhibits a unique ( i ) combination of Si ₄ -cyclic/Si ₂ -acyclic silsesquioxane ligands and ( ii ) encapsulation of two different chloride and carbonate species. This complex acts as a promising precatalyst in the mild oxidation and carboxylation of light alkanes to produce alkyl hydroperoxides, alcohols, ketones, or carboxylic acids. The present study widens the family of copper-methylsilsesquioxane clusters with prospective use in oxidation catalysis.