Cubane-Type Clusters with a [MoFe3S3N] Core: Syntheses, Crystal Structures, and Redox Behavior Modulation

Cubane-type iron–sulfur clusters play central roles in biological nitrogen fixation, where precise redox regulation governs multi-electron transfer processes. However, how heterometal centers and terminal ligands cooperatively modulate the electronic structure and redox behavior of such clusters remains insufficiently understood. Herein, we report a systematic study on a series of cubane-type [MoFe3S3N] clusters as structural mimics of nitrogenase cofactors. Using [(Tp*)MoFe3S3(μ3-NSiMe3)Cl3]− as a common precursor, thiolate (RS−; R = Me, Et, Ph) and N-heterocyclic carbene (NHCR; R = Me, Et, iPr) ligands were introduced to probe ligand effects under an invariant cluster framework. All complexes were fully characterized by single-crystal X-ray diffraction and electrochemical measurements. Combined with previously reported tungsten analogues, a direct comparison reveals that both heterometal identity (Mo vs. W) and terminal ligand environment significantly influence local electron density and intermetallic redox cooperativity. Notably, strong σ-donating NHC ligands and heavier heterometal centers induce distinct modulation patterns, highlighting their synergistic roles. This work provides a unified platform for disentangling metal- and ligand-driven effects and offers feasible strategies for the rational tuning of redox properties in heterometallic Fe–S clusters.