Controlled Incorporation of Nitrides into W-Fe-S Clusters

Incorporation of monatomic 2p ligands into the core of iron-sulfur clusters has been researched since the discovery of interstitial carbide in the FeMo cofactor of Mo-dependent nitrogenase, but has proven to be a synthetic challenge. Herein, two distinct synthetic pathways are rationalized to install nitride ligands into targeted positions of W-Fe-S clusters, generating unprecedented nitride-ligated iron-sulfur clusters, namely [(Tp*)₂ W₂ Fe₆ (μ₄ -N)₂ S₆ L₄ ]^2- (Tp*=tris(3,5-dimethyl-1-pyrazolyl)hydroborate(1-), L=Cl^- or Br^- ). ⁵⁷ Fe Mössbauer study discloses metal oxidation states of W^IV₂ Fe^II₄ Fe^III₂ with localized electron distribution, which is analogous to the mid-valent iron centres of FeMo cofactor at resting state. Good agreement of Mössbauer data with the empirical linear relationship for Fe-S clusters indicates similar ligand behaviour of nitride and sulfide in such clusters, providing useful reference for reduced nitrogen in a nitrogenase-like environment.