Photoactivation of Molecular Oxygen by an Iron(III) Porphyrin with a Magnesium Aluminum Layered Double Hydroxide for the Aerobic Epoxidation of Cyclohexene

Authors

  • Prof. Dr. Kentaro Teramura,

    Corresponding author
    1. Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Kyotodaigaku Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan), Fax: (+81) 75-383-2561
    2. Elements Strategy Initiative for Catalysts & Batteries (ESICB), Kyoto University, 1-30 Goryo-Ohara, Nishikyo-ku, Kyoto 615-8245 (Japan)
    3. Precursory Research for Embryonic Science and Technology (PRESTO) (Japan) Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, Saitama 332-0012 (Japan)
    • Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Kyotodaigaku Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan), Fax: (+81) 75-383-2561

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  • Hideo Tsuneoka,

    1. Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Kyotodaigaku Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan), Fax: (+81) 75-383-2561
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  • Kentaro Ogura,

    1. Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Kyotodaigaku Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan), Fax: (+81) 75-383-2561
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  • Takashi Sugimoto,

    1. Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Kyotodaigaku Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan), Fax: (+81) 75-383-2561
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  • Prof. Dr. Tetsuya Shishido,

    1. Elements Strategy Initiative for Catalysts & Batteries (ESICB), Kyoto University, 1-30 Goryo-Ohara, Nishikyo-ku, Kyoto 615-8245 (Japan)
    2. Department of Applied Chemistry, Graduate School of Urban Environmental Sciences, Tokyo Metropolitan University, 1-1 Minami-Osawa, Hachioji, Tokyo 192-0397 (Japan)
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  • Prof. Dr. Tsunehiro Tanaka

    Corresponding author
    1. Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Kyotodaigaku Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan), Fax: (+81) 75-383-2561
    2. Elements Strategy Initiative for Catalysts & Batteries (ESICB), Kyoto University, 1-30 Goryo-Ohara, Nishikyo-ku, Kyoto 615-8245 (Japan)
    • Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Kyotodaigaku Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan), Fax: (+81) 75-383-2561

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Abstract

The photocatalytic aerobic epoxidation of cyclohexene proceeded under visible-light irradiation only if 5,10,15,20tetrakis(pentafluorophenyl)porphyrin iron(III) chloride ([FeIII(TPFPP)Cl]) was combined with Mg-Al layered double hydroxide (Mg-Al LDH) as a solid base in chloroform. The OH groups in the Mg-Al LDH exchanged with the axial Cl ligands in [FeIII(TPFPP)Cl] to afford [FeIII(TPFPP)OH], which functioned photocatalytically in the presence of Mg-Al LDH but was inactive in its absence. The band in the action spectrum agreed well with the Soret band in the UV/Vis absorption spectrum of [FeIII(TPFPP)OH]. The spectral changes indicated the reduction of [FeIII(TPFPP)OH] to [FeII(TPFPP)] under visible-light irradiation, which in turn activates O2 that could be used for the epoxidation of cyclohexene.

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