Olefin Epoxidation by the Hydrogen Peroxide Adduct of a Novel Non-heme Mangangese(IV) Complex:  Demonstration of Oxygen Transfer by Multiple Mechanisms

Olefin epoxidations are a class of reactions appropriate for the investigation of oxygenation processes in general. Here, we report the catalytic epoxidation of various olefins with a novel, cross-bridged cyclam manganese complex, Mn(Me2EBC)Cl2 (Me2EBC is 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane), using hydrogen peroxide as the terminal oxidant, in acetone/water (ratio 4:1) as the solvent medium. Catalytic epoxidation studies with this system have disclosed reactions that proceed by a nonradical pathway other than the expected oxygen-rebound mechanism that is characteristic of high-valent, late-transition-metal catalysts. Direct treatment of olefins with freshly synthesized [MnIV(Me2EBC)(OH)2](PF6)2 (pKa = 6.86) in either neutral or basic solution confirms earlier observations that neither the oxo−MnIV nor oxo−MnV species is responsible for olefin epoxidization in this case. Catalytic epoxidation experiments using the 18O labels in an acetone/water (H218O) solvent demonstrate that no 18O from water (H218O) is incorporated into epoxide products even though oxygen exchange was observed between the MnIV species and H218O, which leads to the conclusion that oxygen transfer does not proceed by the well-known oxygen-rebound mechanism. Experiments using labeled dioxygen, 18O2, and hydrogen peroxide, H218O2, confirm that an oxygen atom is transferred directly from the H218O2 oxidant to the olefin substrate in the predominant pathway. The hydrogen peroxide adduct of this high-oxidation-state manganese complex, MnIV(Me2EBC)(O)(OOH)+, was detected by mass spectra in aqueous solutions prepared from MnII(Me2EBC)Cl2 and excess hydrogen peroxide. A Lewis acid pathway, in which oxygen is transferred to the olefin from that adduct, MnIV(Me2EBC)(O)(OOH)+, is proposed for epoxidation reactions mediated by this novel, non-heme manganese complex. A minor radical pathway is also apparent in these systems.