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.