Estimations of Fe–N(2) Intrinsic Interaction Energies of Iron–Sulfur/Nitrogen–Carbon Sites: A Deeper Bonding Insight by EDA-NOCV Analysis of a Model Complex of the Nitrogenase Cofactor

[Image: see text] The MoFe(7)S(9)C(1–) unit of the nitrogenase cofactor (FeMoco) attracts chemists and biochemists due to its unusual ability to bind aerial dinitrogen (N(2)) at ambient condition and catalytically convert it into ammonia (NH(3)). The mode of N(2) binding and its reaction pathways are yet not clear. An important conclusion has been made based on the very recent synthesis and isolation of model Fe(I/0)-complexes with sulfur-donor ligands under the cleavage of one Fe–S bond followed by binding of N(2) at the Fe(0) center. These complexes are structurally relevant to the nitrogenase cofactor (MoFe(7)S(9)C(1–)). Herein, we report the EDA-NOCV analyses and NICS calculations of the dinitrogen-bonded dianionic complex Fe(0)–N(2) (1) (having a C(Ar) ← Fe π-bond) and monoanionic complex Fe(I)–N(2) (2) (having a C(Ar)–Fe σ-bond) to provide a deeper insight into the Fe–N(2) interacting orbitals and corresponding pairwise interaction energies (EDA-NOCV = energy decomposition analysis coupled with natural orbital for chemical valence; NICS = nucleus-independent chemical shifts). The orbital interaction in the Fe–N(2) bond is significantly larger than Coulombic interactions, with major pairwise contributions coming from d(Fe) orbitals to the empty π* orbitals of N(2) (three Fe → N(2)). ΔE(int) values are in the range of −61 to −77 kcal mol(–1). Very interestingly, NICS calculations have been carried out for the fragments before and after binding of the N(2) molecule. The computed σ- and π-aromaticity values are attributed to the position of the Fe atoms, oxidation states of Fe centers, and Fe–C bond lengths of these two complexes.