title: Rate-Enhancing Roles of Water Molecules in Methyltrioxorhenium-Catalyzed Olefin Epoxidation by Hydrogen Peroxide.
abstract: 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 (CH3ReO2(η(2)-O2), A, and CH3ReO(η(2)-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.
authors.affiliation: †Department of Chemical Engineering, University of California, Santa Barbara, California 93106-5080, United States.
authors.forename: Bryan R
authors.initials: BR
authors.lastname: Goldsmith
authors.affiliation: †Department of Chemical Engineering, University of California, Santa Barbara, California 93106-5080, United States.
authors.forename: Taeho
authors.initials: T
authors.lastname: Hwang
authors.affiliation: ‡Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106-9510, United States.
authors.forename: Stefan
authors.initials: S
authors.lastname: Seritan
authors.affiliation: †Department of Chemical Engineering, University of California, Santa Barbara, California 93106-5080, United States.|‡Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106-9510, United States.
authors.forename: Baron
authors.initials: B
authors.lastname: Peters
authors.affiliation: †Department of Chemical Engineering, University of California, Santa Barbara, California 93106-5080, United States.|‡Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106-9510, United States.
authors.forename: Susannah L
authors.initials: SL
authors.lastname: Scott
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D004852:Epoxy Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D006861:Hydrogen Peroxide / Q000737:chemistry*; D008968:Molecular Conformation; D056004:Molecular Dynamics Simulation; D009942:Organometallic Compounds / Q000737:chemistry*; D011789:Quantum Theory; D014867:Water / Q000737:chemistry*
chemical_list: D000475:Alkenes; D004852:Epoxy Compounds; D009942:Organometallic Compounds; D014867:Water; C411866:methyltrioxorhenium VII; D006861:Hydrogen Peroxide