Adam T. Fiedler

With the aim of constructing hydrogen‐bonding networks in synthetic complexes, two new ligands derived from cis,cis ‐1,3,5‐triaminocyclohexane (TACH) have been prepared that feature pendant pyrrole or indole rings as outer‐sphere H‐bond donors. The TACH framework offers a facial arrangement of three N ‐donors, thereby mimicking common coordination motifs in the active sites of nonheme Fe and Cu enzymes. X‐ray structural characterization of a series of Cu I ‐X complexes (X=F, Cl, Br, NCS) revealed that these neutral ligands (H 3 L R , R=pyrrole or indole) coordinate in the intended facial N 3 manner, yielding four‐coordinate complexes with idealized C 3 symmetry. The N−H units of the outer‐sphere heterocycles form a hydrogen‐bonding cavity around the axial (pseudo)halide ligand, as verified by crystallographic, spectroscopic, and computational analyses. Treatment of H 3 L pyrrole and H 3 L indole with divalent transition metal chlorides (M II Cl 2 , M=Fe, Cu, Zn) causes one heterocycle to deprotonate and coordinate to the M(II) center, giving rise to tetradentate ligands with two remaining outer‐sphere H‐bond donors. Further ligand deprotonation is observed upon reaction with Ni(II) and Cu(II) salts with weakly coordinating counteranions. The reported complexes highlight the versatility of TACH‐based ligands with pendant H‐bond donors, as the resulting scaffolds can support multiple protonation states, coordination geometries, and H‐bonding interactions.