Mild oxidative C−H functionalization of alkanes and alcohols using a magnetic core-shell Fe3O4@mSiO2@Cu4 nanocatalyst

- Magnetic core-shell nanoparticle catalyst was assembled and fully characterized.
- This hybrid Fe3O4@mSiO2@Cu4 material bears catalytically active tetracopper(II) unit.
- Magnetically recoverable nanocatalyst is active for mild oxidation of cycloalkanes.
- Effects of various reaction parameters were investigated.
- Different selectivity parameters were studied.

A new hybrid Fe3O4@mSiO2@Cu4 material was constructed by loading a bio-inspired tetracopper(II) coordination compound [Cu4(μ4-O){N(CH2CH2O)3}4(BOH)4][BF4]2 (Cu4) onto the Fe3O4@mSiO2 core-shell nanoparticles (NPs) composed of a magnetite (Fe3O4) core and mesoporous silica (mSiO2) shell with perpendicularly aligned channels. The obtained Fe3O4@mSiO2@Cu4 magnetic nanoparticles were characterized by transmission electron microscopy (TEM), FT-IR spectroscopy, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), and field-dependent magnetization. This hybrid material acts as a magnetically recoverable C−H functionalization nanocatalyst, namely for the mild oxidation, by t-butyl hydroperoxide at 50-70 °C in acetonitrile medium, of cycloalkanes (cyclopentane, cyclohexane, cycloheptane, and cyclooctane) to the corresponding alcohols and ketones (with up to ∼15% yields based on cycloalkane; TON 335). A related oxidation process using cyclohexanol as a more reactive substrate leads to the formation of cyclohexanone in up to ∼25% yield (TON 570). The Fe3O4@mSiO2@Cu4 nanocatalyst can be recycled five times without an appreciable loss of activity. The bond-, regio-, and stereoselectivity parameters were investigated in the oxidation of different alkane substrates (n-hexane, n-heptane, n-octane, methylcyclohexane, adamantane, cis- and trans-1,2-demethylcyclohexane), and the obtained results were compared with the homogeneous systems based on the Cu4 catalyst. In particular, the high bond selectivity parameters detected in the oxidation of methylcyclohexane (1°:2°:3° of 1:8:142) and adamantane (2°:3° of 1:21) catalyzed by Fe3O4@mSiO2@Cu4 suggest that the reactions possibly occur in hydrophobic pockets of the nanocatalyst.

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