Estimations of Fe0/−1–N2 interaction energies of iron(0)-dicarbene and its reduced analogue by EDA-NOCV analyses: crucial steps in dinitrogen activation under mild conditions

Abstract

Metal complexes containing low valence iron atoms are often experimentally observed to bind with the dinitrogen (N₂) molecule. This phenomenon has attracted the attention of industrialists, chemists and bio-chemists since these N₂-bonded iron complexes can produce ammonia under suitable chemical or electrochemical conditions. The higher binding affinity of the Fe-atom towards N₂ is a bit ‘mysterious’ compared to that of the other first row transition metal atoms. Fine powders of α-Fe⁰ are even part of industrial ammonia production (Haber–Bosch process) which operates at high temperature and high pressure. Herein, we report the EDA-NOCV analyses of the previously reported dinitrogen-bonded neutral molecular complex (cAAC^R)₂Fe⁰–N₂ (1) and mono-anionic complex (cAAC^R)₂Fe⁻¹–N₂ (2) to give deeper insight of the Fe–N₂ interacting orbitals and corresponding pairwise intrinsic interaction energies (cAAC^R = cyclic alkyl(amino) carbene; R = Dipp or Me). The Fe⁰ atom of 1 prefers to accept electron densities from N₂ via σ-donation while the comparatively electron rich Fe⁻¹ centre of 2 donates electron densities to N₂ via π-backdonation. However, major stability due to the formation of an Fe–N₂ bond arises due to Fe → N₂ π-backdonation in both 1 and 2. The cAAC^R ligands act as a charge reservoir around the Fe centre. The electron densities drift away from cAAC ligands during the binding of N₂ molecules mostly via π-backdonation. EDA-NOCV analysis suggests that N₂ is a stronger π-acceptor rather than a σ-donor.