Expanded Scorpionate and Siderophore‐Inspired Ligands: From Foundational Designs to Modern Applications

Scorpionate ligands have been advanced significantly through systematic modifications of their apical atoms and heterocyclic arms, expanding their structural diversity and chemical reactivity. Recent biologically inspired variants now enable accurate modeling of complex bioinorganic motifs, such as the Fe 4 S 4 clusters of nitrogenase, and support enzyme‐like reactivity under mild aqueous conditions. These developments have broadened the impact of scorpionate chemistry across bioinorganic modeling, homogeneous catalysis, and biorthogonal transformations. In particular, expanded tripodal scaffolds provide modular, tunable platforms for mimicking enzyme active sites and probing biological nitrogen fixation pathways. Beyond fundamental insight, these ligands present practical opportunities for sustainable catalysis by enabling selective transformations in environmentally benign media. This concept article highlights triscatecholates as a new strategy for constructing expanded scorpionate ligand design that can guide future innovation.