Palanquin-Like Cu4Na4 Silsesquioxane Synthesis (via Oxidation of 1,1-bis(Diphenylphosphino)methane), Structure and Catalytic Activity in Alkane or Alcohol Oxidation with Peroxides

The self-assembly synthesis of copper-sodium phenylsilsesquioxane in the presence of 1,1-bis(diphenylphosphino)methane (dppm) results in an unprecedented cage-like product: [(PhSiO1,5)(6)](2)[CuO](4)[NaO0.5](4)[dppmO(2)](2) 1. The most intriguing feature of the complex 1 is the presence of two oxidized dppm species that act as additional O-ligands for sodium ions. Two cyclic phenylsiloxanolate (PhSiO1,5)(6) ligands coordinate in a sandwich manner with the copper(II)-containing layer of the cage. The structure of 1 was established by X-ray diffraction analysis. Complex 1 was shown to be a very good catalyst in the oxidation of alkanes and alcohols with hydrogen peroxide or tert-butyl hydroperoxide in acetonitrile solution. Thus, cyclohexane (CyH), was transformed into cyclohexyl hydroperoxide (CyOOH), which could be easily reduced by PPh3 to afford stable cyclohexanol with a yield of 26% (turnover number (TON) = 240) based on the starting cyclohexane. 1-Phenylethanol was oxidized by tert-butyl hydroperoxide to give acetophenone in an almost quantitative yield. The selectivity parameters of the oxidation of normal and branched alkanes led to the conclusion that the peroxides H2O2 and tert-BuOOH, under the action of compound (1), decompose to generate the radicals HO center dot and tert-BuO center dot which attack the C-H bonds of the substrate.