Intraligand Charge Transfer Enables Visible-Light-Mediated Nickel-Catalyzed Cross-Coupling Reactions

    • Cristian Cavedona,b, Sebastian Gisbertza,b,Susanne Reischauera,b, Sarah Voglc, Eric Sperlichd, John H. Burkee, Rachel F. Wallicke, Stefanie Schrottkef, Wei-Hsin Hsua, Lucia Anghileria,b, Yannik Pfeiferd, Noah Richtera, Christian Teutlofff, Henrike Müller-Werkmeisterd, Dario Cambiéa, Peter H. Seebergera,b, Josh Vura-Weise, Renske M. van der Veene,g, Arne Thomasc, Bartholomäus Piebera
    • aDepartment of Biomolecular Systems, Max-Planck-Institute of Colloids and Interfaces, Am Mühlenberg 1, 14476 Potsdam, Germany
    • bDepartment of Chemistry and Biochemistry, Freie Universität Berlin, Arnimallee 22, 14195 Berlin, Germany
    • cDepartment of Chemistry, Functional Materials, Technische Universität Berlin, Hardenbergstraße 40, 10623 Berlin, Germany
    • dInstitute of Chemistry, University of Potsdam, Karl-Liebknecht-Strasse 24–25, 14476 Potsdam, Germany
    • eDepartment of Chemistry, University of Illinois Urbana-Champaign, Urbana, Illinois, 61801 USA
    • fDepartment of Physics, Freie Universität Berlin, Arnimallee 22, 14195 Berlin, Germany
    • gHelmholtz Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, 14109 Berlin, Germany

    We demonstrate that several visible-light-mediated carbon−heteroatom cross-coupling reactions can be carried out using a photoactive NiII precatalyst that forms in situ from a nickel salt and a bipyridine ligand decorated with two carbazole groups (Ni(Czbpy)Cl2). The activation of this precatalyst towards cross-coupling reactions follows a hitherto undisclosed mechanism that is different from previously reported light-responsive nickel complexes that undergo metal-to-ligand charge transfer. Theoretical and spectroscopic investigations revealed that irradiation of Ni(Czbpy)Cl2 with visible light causes an initial intraligand charge transfer event that triggers productive catalysis. Ligand polymerization affords a porous, recyclable organic polymer for heterogeneous nickel catalysis of cross-coupling reactions. The heterogeneous catalyst shows stable performance in a packed-bed flow reactor during a week of continuous operation.

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