Mechanistic study of iron(III) [tetrakis(pentafluorophenyl)porphyrin triflate (F(20)TPP)Fe(OTf) catalyzed cyclooctene epoxidation by hydrogen peroxide.
We have recently proposed a mechanism for the epoxidation of cyclooctene by H2O2 catalyzed by iron(III) [tetrakis(pentafluorophenyl)]porphyrin chloride, (F20TPP)FeCl, in solvent containing methanol [Stephenson, N. A.; Bell, A.T. Inorg. Chem. 2006, 45, 2758-2766]. In that study, we found that catalysis did not occur unless (F20TPP)FeCl first dissociated, a process facilitated by the solvation of the Cl- anion by methanol and the coordination of methanol to the (F20TPP)Fe+ cation. Methanol as well as other alcohols was also found to facilitate the heterolytic cleavage of the O-O bond of H2O2 coordinated to the (F20TPP)Fe+ cation via a generalized acid mechanism. In the present study, we have shown that catalytic activity of the (F20TPP)Fe+ cation can be achieved in aprotic solvent by displacing the tightly bound chloride anion with a weakly bound triflate anion. By working in an aprotic solvent, acetonitrile, it was possible to determine the rate of heterolytic O-O bond cleavage in coordinated H2O2 unaffected by the interaction of the peroxide with methanol. A mechanism is proposed for this system and is shown to be valid over a range of reaction conditions. The mechanisms for cyclooctene epoxidation and H2O2 decomposition for the aprotic and protic solvent systems are similar with the only difference being the mechanism of proton-transfer prior to heterolytic cleavage of the oxygen-oxygen bond of coordinated hydrogen peroxide. Comparison of the rate parameters indicates that the utilization of hydrogen peroxide for cyclooctene epoxidation is higher in a protic solvent than in an aprotic solvent and results in a smaller extent of porphyrin degradation due to free radical attack. It was also shown that water can coordinate to the iron porphyrin cation in aprotic systems resulting in catalyst deactivation; this effect was not observed when methanol was present, since methanol was found to displace all of the coordinated water.
Stephenson
Ned A
NA
Chemical Sciences Division, Lawrence Berkeley Laboratory and Department of Chemical Engineering, University of California, Berkeley, California 94720-1462.
Bell
Alexis T
AT
D002384:Catalysis; D034242:Cyclooctanes / Q000737:chemistry*; D004852:Epoxy Compounds / Q000737:chemistry*; D005290:Ferric Compounds / Q000737:chemistry*; D006861:Hydrogen Peroxide / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008665:Metalloporphyrins / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet; D005464:Fluorobenzenes; D005466:Fluorocarbons
D034242:Cyclooctanes; D004852:Epoxy Compounds; D005290:Ferric Compounds; D006861:Hydrogen Peroxide; D008665:Metalloporphyrins; C093411:tetrakis(pentafluorophenyl)porphyrinato iron(III) chloride; D005464:Fluorobenzenes; D005466:Fluorocarbons