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Journal Article

Catalytic Hydrodefluorination via Oxidative Addition, Ligand Metathesis, and Reductive Elimination at Bi(I)/Bi(III) Centers

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Pang,  Yue
Research Group Cornellà, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Leutzsch,  Markus
Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Nöthling,  Nils
Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

Katzenburg,  Felix
Research Group Cornellà, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Cornella,  Josep
Research Group Cornellà, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Pang, Y., Leutzsch, M., Nöthling, N., Katzenburg, F., & Cornella, J. (2021). Catalytic Hydrodefluorination via Oxidative Addition, Ligand Metathesis, and Reductive Elimination at Bi(I)/Bi(III) Centers. Journal of the American Chemical Society, 143(32), 12487-12493. doi:10.1021/jacs.1c06735.


Cite as: https://hdl.handle.net/21.11116/0000-0009-1678-8
Abstract
Herein, we report a hydrodefluorination reaction of polyfluoroarenes catalyzed by bismuthinidenes, Phebox-Bi(I) and OMe-Phebox-Bi(I). Mechanistic studies on the elementary steps support a Bi(I)/Bi(III) redox cycle that comprises C(sp2)–F oxidative addition, F/H ligand metathesis, and C(sp2)–H reductive elimination. Isolation and characterization of a cationic Phebox-Bi(III)(4-tetrafluoropyridyl) triflate manifests the feasible oxidative addition of Phebox-Bi(I) into the C(sp2)–F bond. Spectroscopic evidence was provided for the formation of a transient Phebox-Bi(III)(4-tetrafluoropyridyl) hydride during catalysis, which decomposes at low temperature to afford the corresponding C(sp2)–H bond while regenerating the propagating Phebox-Bi(I). This protocol represents a distinct catalytic example where a main-group center performs three elementary organometallic steps in a low-valent redox manifold.