Ru-Bipyridine Entrapped in the Supercages of EMC-1 Faujasite as Catalyst for the Trifluoromethylation of Arenes

Vincent Lemmens; Christophe Vos; Aram L. Bugaev; Jannick Vercammen; Niels Van Velthoven; Jorge Gascon; Dirk E. De Vos

doi:10.1021/acsami.1c19655

Ru-Bipyridine Entrapped in the Supercages of EMC-1 Faujasite as Catalyst for the Trifluoromethylation of Arenes

Vincent Lemmens, Christophe Vos, Aram L. Bugaev, Jannick Vercammen, Niels Van Velthoven, Jorge Gascon, Dirk E. De Vos

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

Trifluoromethyl (CF3) groups are versatile structural motifs especially in the field of agrochemicals and pharmaceuticals. However, current trifluoromethylation reactions are generally associated with stoichiometric amounts of transition metals/metal oxidants, homogeneous catalysts, high temperatures, and expensive trifluoromethylating agents. In this work, the homogeneous photocatalyst Ru(bipy)32+ is entrapped in the pores of a faujasite support (EMC-1) via a "ship-in-a-bottle"strategy. The formation of the coordination compound was confirmed by Fourier transform infrared (FTIR), UV-Vis spectroscopy, and X-ray absorption spectroscopy (XAS). Due to its high stability toward acidified environments, this single-site heterogeneous catalyst is suitable for the trifluoromethylation of synthetically interesting (hetero)arenes under visible-light irradiation at room temperature. Furthermore, the heterogeneous catalyst could efficiently be reused for at least three times with minimal catalyst leaching/deactivation.

Original language	English (US)
Journal	ACS Applied Materials & Interfaces
DOIs	https://doi.org/10.1021/acsami.1c19655
State	Published - Dec 27 2021

Bibliographical note

KAUST Repository Item: Exported on 2022-01-25
Acknowledged KAUST grant number(s): OSR-2018-CRG7-3741.2
Acknowledgements: The research leading to these results has received funding from the KAUST-CRG Program (OSR-2018-CRG7-3741.2). J.V., N.V.V., and D.E.D.V. thank the FWO (Fonds, voor Wetenschappelijk Onderzoek, Flanders, Belgium) for SB funding (1S17620N, 1S32917N, and G0F2320N). The XAS experiments were performed on beamline BM23 at the European Synchrotron Radiation Facility (ESRF), Grenoble, France. A.L.B. acknowledges the Ministry of Science and Higher Education of the Russian Federation for financial support (075-15-2021-1363). V.L. is thanking Carlos Marquez for SEM and ICP-OES measurements.

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Materials Science(all)

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title = "Ru-Bipyridine Entrapped in the Supercages of EMC-1 Faujasite as Catalyst for the Trifluoromethylation of Arenes",

abstract = "Trifluoromethyl (CF3) groups are versatile structural motifs especially in the field of agrochemicals and pharmaceuticals. However, current trifluoromethylation reactions are generally associated with stoichiometric amounts of transition metals/metal oxidants, homogeneous catalysts, high temperatures, and expensive trifluoromethylating agents. In this work, the homogeneous photocatalyst Ru(bipy)32+ is entrapped in the pores of a faujasite support (EMC-1) via a {"}ship-in-a-bottle{"}strategy. The formation of the coordination compound was confirmed by Fourier transform infrared (FTIR), UV-Vis spectroscopy, and X-ray absorption spectroscopy (XAS). Due to its high stability toward acidified environments, this single-site heterogeneous catalyst is suitable for the trifluoromethylation of synthetically interesting (hetero)arenes under visible-light irradiation at room temperature. Furthermore, the heterogeneous catalyst could efficiently be reused for at least three times with minimal catalyst leaching/deactivation.",

author = "Vincent Lemmens and Christophe Vos and Bugaev, {Aram L.} and Jannick Vercammen and {Van Velthoven}, Niels and Jorge Gascon and {De Vos}, {Dirk E.}",

note = "KAUST Repository Item: Exported on 2022-01-25 Acknowledged KAUST grant number(s): OSR-2018-CRG7-3741.2 Acknowledgements: The research leading to these results has received funding from the KAUST-CRG Program (OSR-2018-CRG7-3741.2). J.V., N.V.V., and D.E.D.V. thank the FWO (Fonds, voor Wetenschappelijk Onderzoek, Flanders, Belgium) for SB funding (1S17620N, 1S32917N, and G0F2320N). The XAS experiments were performed on beamline BM23 at the European Synchrotron Radiation Facility (ESRF), Grenoble, France. A.L.B. acknowledges the Ministry of Science and Higher Education of the Russian Federation for financial support (075-15-2021-1363). V.L. is thanking Carlos Marquez for SEM and ICP-OES measurements.",

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AU - Lemmens, Vincent

AU - Vos, Christophe

AU - Bugaev, Aram L.

AU - Vercammen, Jannick

AU - Van Velthoven, Niels

AU - Gascon, Jorge

AU - De Vos, Dirk E.

N1 - KAUST Repository Item: Exported on 2022-01-25 Acknowledged KAUST grant number(s): OSR-2018-CRG7-3741.2 Acknowledgements: The research leading to these results has received funding from the KAUST-CRG Program (OSR-2018-CRG7-3741.2). J.V., N.V.V., and D.E.D.V. thank the FWO (Fonds, voor Wetenschappelijk Onderzoek, Flanders, Belgium) for SB funding (1S17620N, 1S32917N, and G0F2320N). The XAS experiments were performed on beamline BM23 at the European Synchrotron Radiation Facility (ESRF), Grenoble, France. A.L.B. acknowledges the Ministry of Science and Higher Education of the Russian Federation for financial support (075-15-2021-1363). V.L. is thanking Carlos Marquez for SEM and ICP-OES measurements.

PY - 2021/12/27

Y1 - 2021/12/27

N2 - Trifluoromethyl (CF3) groups are versatile structural motifs especially in the field of agrochemicals and pharmaceuticals. However, current trifluoromethylation reactions are generally associated with stoichiometric amounts of transition metals/metal oxidants, homogeneous catalysts, high temperatures, and expensive trifluoromethylating agents. In this work, the homogeneous photocatalyst Ru(bipy)32+ is entrapped in the pores of a faujasite support (EMC-1) via a "ship-in-a-bottle"strategy. The formation of the coordination compound was confirmed by Fourier transform infrared (FTIR), UV-Vis spectroscopy, and X-ray absorption spectroscopy (XAS). Due to its high stability toward acidified environments, this single-site heterogeneous catalyst is suitable for the trifluoromethylation of synthetically interesting (hetero)arenes under visible-light irradiation at room temperature. Furthermore, the heterogeneous catalyst could efficiently be reused for at least three times with minimal catalyst leaching/deactivation.

AB - Trifluoromethyl (CF3) groups are versatile structural motifs especially in the field of agrochemicals and pharmaceuticals. However, current trifluoromethylation reactions are generally associated with stoichiometric amounts of transition metals/metal oxidants, homogeneous catalysts, high temperatures, and expensive trifluoromethylating agents. In this work, the homogeneous photocatalyst Ru(bipy)32+ is entrapped in the pores of a faujasite support (EMC-1) via a "ship-in-a-bottle"strategy. The formation of the coordination compound was confirmed by Fourier transform infrared (FTIR), UV-Vis spectroscopy, and X-ray absorption spectroscopy (XAS). Due to its high stability toward acidified environments, this single-site heterogeneous catalyst is suitable for the trifluoromethylation of synthetically interesting (hetero)arenes under visible-light irradiation at room temperature. Furthermore, the heterogeneous catalyst could efficiently be reused for at least three times with minimal catalyst leaching/deactivation.

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ER -

Ru-Bipyridine Entrapped in the Supercages of EMC-1 Faujasite as Catalyst for the Trifluoromethylation of Arenes

Abstract

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