Title:

A Journey Between the Extremes of Metal-ligand Relationships

Abstract:

The ability for chemists to rationally design transition metal catalysts is deeply rooted in our fundamental understanding of metal-ligand relationships. To date, the vast majority of transition metal centers are supported by “spectator” ligands that can be synthetically tuned to modulate the reactivity at the metal. While less common, “cooperative” metal-ligand relationships in which both the ligand and the metal participate in chemical or redox reactions have also been developed to drive new transformations. However, the far extreme in which the metal adopts a spectator role and reactivity is solely observed at a “functional” ligand is underexplored. Herein we will interrogate the two extremes of this dichotomy, spectator ligand and spectator metal behavior, and discuss how synthetic tuning in these two regimes influences the functionalization of small molecules.