Unusual S=1 Four‐Coordinate Fe(IV) Complexes Supported by Bisamide Ligands: Syntheses, Characterization, and Electronic Structures.

The catalytic relevance of Fe(IV) species in non‐heme iron catalysis has motivated synthetic advances in well‐defined five‐ and six‐coordinate Fe(IV) complexes for a better understanding of their fundamental electronic structures and reactivities. Herein, we report the syntheses of FeDipp2 and FeMes2, a pair of unusual four‐coordinate non‐heme formally Fe(IV) complexes with S=1 ground states supported by strongly donating bisamide ligands. By combining spectroscopic characterization and computational modeling, we found that small variations in ligand aryl substituents resulted in substantial changes in both structures and bonding. This work highlights the strong donor capabilities and modularity of the bisamide ligand set. More broadly, it is a critical contribution to the utilization of ligand design to modulate molecular geometries and electronic structures of low‐coordinate, high‐valent iron complexes. [ABSTRACT FROM AUTHOR]