Halide Effects in Transition Metal Catalysis

Among the most common ligands found on transition metal catalysts are halide ions. Of the commercially available catalysts or pre‐catalysts, most are halo–metal complexes. In recent years, manipulation of this metal‐halide functionality has revealed that this can be used as a highly valuable method of tuning the reactivity of the complex. Variation of the halide ligand will usually not alter the nature of the system to the extent that it becomes unreactive but will impart sufficiently large changes that differences in reactivity or selectivity occur. These differences are a product of the steric and electronic properties of the halide ligand which has the ability to donate electron density to the metal occurs in a predictable manner. Despite the common perception in asymmetric catalysis that halide ligands are of secondary importance compared to chiral ligands, halide ligands have been found to exert dramatic effects on the enantioselectivity of asymmetric transformations. While the mechanism of action is known for relatively few of the cases, many intriguing and potentially synthetically useful trends are apparent. This review discusses the physical properties of the halides and their effects on stoichiometric and catalytic transition metal processes. The metal‐halide moiety thus emerges as a tunable functionality on the transition metal catalyst that can be used in the development of new catalytic systems.