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Effect of Support Nature on Ruthenium-Catalyzed Allylic Oxidation of Cycloalkenes

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Abstract

Allylic oxidation of cycloalkenes is a promising route to generate α,β-unsaturated ketones but encounters difficulties in selectivity control. Here, it is demonstrated that ruthenium nanoparticles (1–2 nm sized) decorated on TiO2 nanomaterials with different morphologies (nanoparticles, nanotubes and nanofibers) are demonstrated highly efficiency and selectivity for the selective aerobic oxidation of cyclohexene and indane. The as-prepared Ru/TiO2 nanofibers (NFs) represents higher activity for the allylic oxidation of cyclohexene (conv. 95%) with 78% selectivity toward 2-cyclohexen-1-one at 75 °C under 4 bar O2. Whereas, Ru/TiO2 nanoparticles (NPs) and Ru/TiO2 nanotubes (NTs) show 92 and 84% conversion, respectively. Upon switching to Al2O3 support, catalytic activity with Ru/Al2O3 is decreased significantly to 27%. Very high activity for indane (conv. 70%) toward 2,3-dihydro-1H-inden-1-one (selectivity 85%) has also been observed by using Ru/TiO2 NFs. Ru/TiO2 nanomaterials possess higher catalytic efficiency as compared to Ru NPs and TiO2 nanomaterials individually, representing a positive synergetic effect. Moreover, these reported results suggest that the higher activities of Ru/TiO2 NPs and Ru/TiO2 NFs are related to the crystalline structure, pore volume and surface area of the supports.

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Acknowledgements

The authors are thankful to TWAS, FAPERGS (88887.195052/2018-00), CNPq (406260/2018-4), CAPES (158804/2017-01) for their financial support. The authors acknowledge the use of the infrastructure of the Center for Microscopy and Microanalysis (CMM-UFRGS) and the NULAM/DIMAT at National Institute of Metrology, Quality and Technology (INMETRO). We are also thankful to Prof. Cláudio Radtke from IQ-UFRGS for performing XPS analysis.

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  1. Laboratory of Molecular Catalysis, Institute of Chemistry-UFRGS, Av. Bento Gonçalves, 9500, Porto Alegre, RS, Brazil

    Muhammad I. Qadir & Jairton Dupont

  2. Institute of Physics-UFRGS, Av. Bento Gonçalves, 9500, Porto Alegre, RS, Brazil

    Daniel L. Baptista

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  1. Muhammad I. Qadir
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Qadir, M.I., Baptista, D.L. & Dupont, J. Effect of Support Nature on Ruthenium-Catalyzed Allylic Oxidation of Cycloalkenes. Catal Lett 152, 3058–3065 (2022). https://doi.org/10.1007/s10562-021-03880-6

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