Ligand‐Level Chemical Activation: Coordination with Benefits

Influencing electron distribution within a coordination complex bearing redox‐active ligands offers the possibility to foster new reactivities. This redistribution can involve electrons but also protons or more elaborate chemical groups. Often perceived as a liability, chemical non‐innocence can actually be considered a synthetic tool in which the synergy between metal and ligand leads to chemical reactivity at the ligand that is part of a streamlined process, rather than an unwanted side reaction. This concept article aims at providing examples of how redistributing electron density within a metal complex bearing redox‐active ligands can foster interesting functionalization chemistry. This seemingly fundamental question has very practical applications in the fields of hydrogenation and energy‐related catalytic reactions such as small‐molecule activation, solar fuels, or to make new (photo)catalysts and noncanonical redox cofactors.