Binuclear Cage‐Like Copper(II) Silsesquioxane (“Cooling Tower”) – Its High Catalytic Activity in the Oxidation of Benzene and Alcohols

Abstract

Abstract A new method of metallasilsesquioxane synthesis is described for the first time. According to this method, a partial nucleophilic cleavage of polymeric copper phenylsilsesquioxane by the use of sym‐cis ‐tetraphenylcyclotetrasiloxanolate nonaethanolate ( 1 ) gave previously unknown binuclear cage‐like copper silsesquioxane [(PhSiO 1.5 ) 10 (CuO) 2 (NaO 0.5 ) 2 · 4EtOH] ( 2 ). The unprecedented structure of 2 , the so called “Cooling Tower” structure, was confirmed by single‐crystal X‐ray diffraction analysis. Compound 2 was found to be an excellent catalyst in oxidation reactions of benzene and alcohols with peroxides in acetonitrile solution at 50–70 °C.