A Cu8Na2-silsesquioxane/acetylacetonate precatalyst for the one-pot cyclohexane to ε-caprolactone transformation.

Self-assembly of heterometallic (copper/sodium) complexes stabilized by phenylsiloxanolate and acetylacetonate ligands resulted in Cu8Na2-cage structures. Their unprecedented cage-like geometry features two peripheral Cu3 and one central Na-Cu2-Na linear fragments surrounded by two Si5-cyclic silsesquioxanes and four acetylacetonate ligands. To evaluate its catalytic performance, the Cu8Na2-precatalyst was explored in the oxidation of cyclohexane, selected as a model substrate, under a range of experimental conditions. The best results were obtained at 80 °C for 0.5 h under MW irradiation, affording ε-caprolactone (TON = 145, TOF = 290 h-1) along with cyclohexanol and cyclohexanone, in an overall yield of 15%. These promising preliminary findings highlight the potential of the heterometallic Cu8Na2 system as an efficient and selective precatalyst for rapid MW-assisted single-pot oxidation, under mild conditions, of cyclohexane to ε-caprolactone, a compound with a marked industrial interest.