LAUSR

The factors/structural features which are responsible for the binding, activation and reduction of N2 to NH3 by FeMoco of nitrogenase have not been completely understood well. Several relevant model complexes by Holland et al. and Peters et al. have been synthesized, characterized and studied by theoretical calculations. For a matter of fact, those complexes are much different than real active N2‐binding Fe‐sites of FeMoco, which possesses a central C(4‐) ion having an eight valence electrons as an μ6‐bridge. Here, a series of [(S3C(0))Fe(II/I/0)‐N2]n‐ complexes in different charged/spin states containing a coordinated σ‐ and π‐donor C(0)‐atom which possesses eight outer shell electrons [carbone, (Ph3P)2C(0); Ph3P→C(0)←PPh3] and three S‐donor sites (i.e. ‐S‐Ar), have been studied by DFT, QTAIM, and EDA‐NOCV calculations. The effect of the weak field ligand on Fe‐centres and the subsequent N2‐binding has been studied by EDA‐NOCV analysis. The role of the oxidation state of Fe and N2‐binding in different charged and spin states of the complex have been investigated by EDA‐NOCV analyses. The intrinsic interaction energies of the Fe−N2 bond are in the range from −42/−35 to −67 kcal/mol in their corresponding ground states. The S3C(0) donor set is argued here to be closer to the actual coordination environment of one of the six Fe‐centres of nitrogenase. In comparison, the captivating model complexes reported by Holland et al. and Peter et al. possess a stronger π‐acceptor C‐ring (S2Cring donor, π‐C donor) and stronger donor set like CP3 (σ‐C donor) ligands, respectively.