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A new crown ether appended Fe(Ⅲ) porphyrin complex was prepared by sulfuryl chloride appended benzo- 15-crown-5 to the meso position of meso-5,10,15,20-tetra(4-hydrophenyl)porphyrin,and it was applied to catalytic oxidation of cyclohexene with molecular oxygen without reductant,showing a remarkable catalytic activity (conversion is up to 94%) and selectivity for 2-cyclohexen- 1-ol (73%).