(36a) Rate-Enhancing Roles of Water Molecules in Methyltrioxorhenium-Catalyzed Olefin Epoxidation By Hydrogen Peroxide | AIChE

(36a) Rate-Enhancing Roles of Water Molecules in Methyltrioxorhenium-Catalyzed Olefin Epoxidation By Hydrogen Peroxide

Authors 

Goldsmith, B. R. - Presenter, Fritz-Haber-Institut der Max-Planck-Gesellschaft
Seritan, S., University of California, Santa Barbara
Peters, B., University of California Santa Barbara
Scott, S. L., University of California, Santa Barbara
Olefin epoxidation catalyzed by methyltrioxorhenium (MTO, CH3ReO3) is strongly accelerated in the presence of H2O. The participation of H2O in each of the elementary steps of the catalytic cycle, involving the formation of the peroxo complexes (CH3ReO22-O2), A, and CH3ReO(η2-O2)2(H2O), B), as well as in their subsequent epoxidation of cyclohexene, was examined in aqueous acetonitrile. Experimental measurements demonstrate that the epoxidation steps exhibit only weak [H2O]-dependence, attributed by DFT calculations to hydrogen-bonding between uncoordinated H2O and a peroxo ligand. The primary cause of the observed H2O acceleration is the strong co-catalytic effect of water on the rates at which A and B are regenerated, and consequently on the relative abundances of the three interconverting Re-containing species at steady-state. Proton transfer from weakly coordinated H2O2 to the oxo ligands of MTO and A, resulting in peroxo complex formation, is directly mediated by solvent H2O molecules. Computed activation parameters and kinetic isotope effects, in combination with proton-inventory experiments, suggest a proton shuttle involving one or (most favorably) two H2O molecules in the key ligand exchange steps to form A and B from MTO and A, respectively.