Intraligand Charge Transfer Enables Visible‐Light‐Mediated Nickel‐Catalyzed Cross‐Coupling Reactions**
Abstract
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.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- Oct 21, 2022
- Source ID
- 10.1002/anie.202211433
Entities
People
- Arne Thomas
- Bartholomäus Pieber
- Christian Teutloff
- Cristian Cavedon
- Dario Cambié
- Eric Sperlich
- Henrike M Mueller-Werkmeister
- John H. Burke
- Josh Vura-Weis
- Lucia Anghileri
- Noah Richter
- Peter Seeberger
- Rachel F. Wallick
- Renske M. Van Der Veen
- Sarah Vogl
- Sebastian Gisbertz
- Stefanie Schrottke
- Susanne Reischauer
- Wei‐hsin Hsu
- Yannik Pfeifer
Organizations
- David and Lucile Packard Foundation
- Freie Universität Berlin
- Functional Materials
- German Research Foundation
- Office of Basic Energy Sciences
- University of Illinois Urbana–Champaign
- University of Potsdam
- Verband der Chemischen Industrie