A family of hexacopper phenylsilsesquioxane/acetate complexes: synthesis, solvent‐controlled cage structures, and catalytic activity

Convenient self‐assembly synthesis of copper(II) complexes via double (phenylsilsesquioxane and acetate) ligation allows to isolate a family of impressive sandwich‐like cage compounds. An intriguing feature of these complexes is the difference in the structure of a pair of silsesquioxane ligands despite identical (Cu6) nuclearity and number (four) of acetate fragments. Formation of particular combination of silsesquioxane ligands (cyclic/cyclic vs condensed/condensed vs cyclic/condensed) was found to be dependent on the synthesis/crystallization media. A combination of Si4‐cyclic and Si6‐condensed silsesquioxane ligands is a brand new feature of cage metallasilsesquioxanes. A representative Cu6‐complex (4) (with cyclic silsesquioxanes) exhibited high catalytic activity in the oxidation of alkanes and alcohols with peroxides. Maximum yield of the products of cyclohexane oxidation attained 30%. The compound 4 was also tested as catalyst in the Baeyer‐Villiger oxidation of cyclohexanone by m‐chloroperoxybenzoic acid: maximum yields of 88% and 100% of ε‐caprolactone were achieved upon conventional heating at 50 °C for 4 h and MW irradiation at 70 or 80 °C during 30 min, respectively. It was also possible to obtain the lactone (up to 16% yield) directly from the cyclohexane via a tandem oxidation/Baeyer‐Villiger oxidation reaction using the same oxidant.