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The Non-innocent Role of Spin Traps in Monitoring Radical Formation in Copper-Catalyzed Reactions

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Abstract

Spin traps, like 5,5-dimethyl-1-pyrroline N-oxide (DMPO), are commonly used to identify radicals formed in numerous chemical and biological systems, many of which contain metal-ion complexes. In this study, continuous wave electron paramagnetic resonance and hyperfine spectroscopy are used to prove the equatorial ligation of DMPO(-derived) molecules to Cu(II), even in the presence of competing nitrogen bases. The experimental data are corroborated with density functional theory calculations. It is shown that 14N HYSCORE can be used as a fingerprint method to reveal the coordination of DMPO(-derived) molecules to Cu(II), an interaction that might influence the outcome of spin-trapping experiments and consequently the conclusion drawn on the mechanism under study.

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Acknowledgments

The authors want to acknowledge the Research Foundation Flanders (FWO-Vlaanderen) for support of this work through the project G093317N. This project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie Grant agreement no. 792946 (H2020-MSCA-IF iSPY to H. Y. V. Ching). S. Van Doorslaer and B. Maes are members of the Excellence centre CASCH—Catalysis for sustainable organic chemistry of the University of Antwerp.

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Authors and Affiliations

  1. Department of Chemistry, BIMEF, University of Antwerp, Universiteitsplein 1, 2610, Antwerp, Belgium

    Mohammad Samanipour, H. Y. Vincent Ching & Sabine Van Doorslaer

  2. Janssen Pharmaceutica, Turnhoutseweg 30, 2340, Beerse, Belgium

    Hans Sterckx

  3. Department of Chemistry, ORSY, University of Antwerp, Groenenborgerlaan 171, 2020, Antwerp, Belgium

    Bert U. W. Maes

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  1. Mohammad Samanipour
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Correspondence to Sabine Van Doorslaer.

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Samanipour, M., Ching, H.Y.V., Sterckx, H. et al. The Non-innocent Role of Spin Traps in Monitoring Radical Formation in Copper-Catalyzed Reactions. Appl Magn Reson 51, 1529–1542 (2020). https://doi.org/10.1007/s00723-020-01284-0

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  • DOI: https://doi.org/10.1007/s00723-020-01284-0

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