Intraligand Charge Transfer Enables Visible‐Light‐Mediated Nickel‐Catalyzed Cross‐Coupling Reactions. Issue 46 (21st October 2022)

• Record Type: Journal Article
• Authors: Cavedon, Cristian; Gisbertz, Sebastian; Reischauer, Susanne; Vogl, Sarah; Sperlich, Eric; Burke, John H.; Wallick, Rachel F.; Schrottke, Stefanie; Hsu, Wei‐Hsin; Anghileri, Lucia; Pfeifer, Yannik; Richter, Noah; Teutloff, Christian; Müller‐Werkmeister, Henrike; Cambié, Dario; Seeberger, Peter H.; Vura‐Weis, Josh; van der Veen, Renske M.; Thomas, Arne; Pieber, Bartholomäus
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 46(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-10-21
• Subjects: Flow Chemistry -- Heterogeneous Catalysis -- Homogeneous Catalysis -- Photocatalysis -- Nickel Catalysis; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202211433
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: We demonstrate that several visible‐light‐mediated carbon−heteroatom cross‐coupling reactions can be carried out using a photoactive Ni II 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. Abstract : Visible‐light‐triggered carbon−heteroatom cross‐coupling reactions without exogenous photocatalysts were realized using a nickel catalyst that was activated through intraligand charge transfer. Ligand polymerization afforded a porous, recyclable organic polymer for heterogeneous nickel catalyzed cross‐coupling reactions. The heterogeneous catalyst demonstrates stable performance in a packed‐bed flow reactor during a week of continuous operation.