Harnessing the active site triad: merging hemilability, proton responsivity, and ligand-based redox-activity

Metalloenzymes catalyze many important reactions by managing the proton and electron flux at the enzyme active site. The motifs utilized to facilitate these transformations include hemilabile, redox-active, and so called proton responsive sites. Given the importance of incorporating and understanding these motifs in the area of coordination chemistry and catalysis, we highlight recent milestones in the field. Work incorporating the triad of hemilability, redox-activity, and proton responsivity into single ligand scaffolds will be described. Metalloenzymes catalyze important reactions by managing the proton and electron flux at the active site. In synthetic systems; hemilability, proton responsivity, and ligand-based redox-activity can be utilized as a bridge to harness this reactivity.