Epoxidation of the Commercially Relevant Divinylbenzene with [tetrakis-(Pentafluorophenyl)porphyrinato]iron(III) Chloride and Its Derivatives

Fluorinated Fe-porphyrins, especially [tetrakis(pentafluorophenyl)­porphyrinato]­iron­(III) chloride (tetrakis(pentafluorophenyl)­porphyrinato = TPFPP) (TPFPP)­FeCl (Fepor-2a), were found to be highly efficient for catalyzing the double epoxidation of divinylbenzene (DVB) to divinylbenzene dioxide (DVBDO), a novel component of epoxy resin formulation. The electronic properties of the catalysts are highly dependent on the substituents on the phenyl groups of these metalloporphyrins. The electron-rich fluorinated Fe-porphyrins are more selective toward epoxidation but are more vulnerable toward decomposition in H2O2. On the other hand, the electron deficient Fe-porphyrins are more stable, yet more Lewis acidic, which facilitates the formation of byproducts such as epoxide ring opening and overoxidation.