The palladium-catalysed Suzuki–Miyaura reaction is one of the most important methods for C–C cross-coupling, yet the heterogeneous version of this reaction remains poorly understood. More specifically, the question of whether the reaction occurs on the surface of the catalyst (heterogeneous process) or is promoted by leaching of palladium species in solution (homogeneous phase) is still under debate. Here, we use real-time high spatial resolution microscopy to monitor a palladium-catalysed coupling reaction that produces a highly fluorescent BODIPY dye. We show catalyst migration during the reaction, which we attribute to a dissolution/redeposition mechanism where migrating palladium species become true active sites after attachment to the catalyst support. The observed process is heterogeneous, but the active catalysts (atoms or small clusters) have important mobility, as revealed by the observation of migrating catalytic sites. Our report shows the strength of single-molecule studies for unveiling fundamental mechanisms in heterogeneously catalysed reactions that are otherwise difficult to explore with classical ensemble experiments.
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The data supporting the findings of this study are available in the paper and its Supplementary Information; further data are available from the corresponding author on reasonable request.
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This work was supported by the Natural Sciences and Engineering Research Council of Canada, the Canada Foundation for Innovation, the Canada Research Chairs Program and the German National Academy of Sciences Leopoldina (grant no. LPDS 2017-15 to P.C.).
The authors declare no competing interests.
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Costa, P., Sandrin, D. & Scaiano, J.C. Real-time fluorescence imaging of a heterogeneously catalysed Suzuki–Miyaura reaction. Nat Catal 3, 427–437 (2020). https://doi.org/10.1038/s41929-020-0442-0