Dealing at Arm's Length: Catalysis with N‐Heterocyclic Carbene Ligands Bearing Anionic Tethers

The catalytic transformations enabled by bidentate N‐heterocyclic carbenes bearing anionic substituents (tethered NHCs) are presented. The use of tethered NHCs as a ligand class for transition‐metal‐catalyzed reactions and their employment in organocatalytic and Lewis‐base‐catalyzed processes is discussed, with a focus on the influence of the anionic tether on the catalyzed reactions of interest. An overview of the applications of bidentate N‐heterocyclic carbenes (NHCs) bearing anionic heteroatom‐based tethers in catalysis is presented.