The First Olefin-Substituted Peroxomolybdenum Complex: Insight into a New Mechanism for the Molybdenum-Catalyzed Epoxidation of Olefins


  • Metal-Catalyzed Oxidations, Part 3. We thank Professor W. A. Herrmann and the Deutsche Forschungsgemeinschaft (Schwerpunktprogramm “Peroxidchemie”) for support of our work. Part 2: ref. [1].

  • Dedicated to Professor Henri Brunner on the occasion of his 60th birthday


original image

What is the source of the epoxide oxygen in the Mo-catalyzed epoxidation of olefins? The olefinic side chain [BOND]CH2CH[DOUBLE BOND]CH2[BOND] of the isolated complex 1 (structure shown on the right) is epoxidized only on addition of hydroperoxides. Thus in complex 1, in contrast to previously proposed mechanisms for the title reaction, an oxygen atom from the η2-peroxo ligand is not transferred to the olefin.