LAUSR

Binding of dinitrogen (N2) to a transition metal center (M) and followed by its activation under milder conditions is no longer impossible; rather, it is routinely studied in laboratories by transition metal complexes. In contrast, binding of N2 by main group elements has been a challenge for decades, until very recently, an exotic cAAC‐borylene (cAAC = cyclic alkyl(amino) carbene) species showed similar binding affinity to kinetically inert and non‐polar dinitrogen (N2) gas under ambient conditions. Since then, N2 binding by short lived borylene species has made a captivating news in different journals for its unusual features and future prospects. Herein, we carried out different types of DFT calculations, including EDA‐NOCV analysis of the relevant cAAC‐boron‐dinitrogen complexes and their precursors, to shed light on the deeper insight of the bonding secret (EDA‐NOCV = energy decomposition analysis coupled with natural orbital for chemical valence). The hidden bonding aspects have been uncovered and are presented in details. Additionally, similar calculations have been carried out in comparison with a selected stable dinitrogen bridged‐diiron(I) complex. Singlet cAAC ligand is known to be an exotic stable species which, combined with the BAr group, produces an intermediate singlet electron‐deficient (cAAC)(BAr) species possessing a high lying HOMO suitable for overlapping with the high lying π*‐orbital of N2 via effective π‐backdonation. The BN2 interaction energy has been compared with that of the FeN2 bond. Our thorough bonding analysis might answer the unasked questions of experimental chemists about how boron compounds could mimic the transition metal of dinitrogen binding and activation, uncovering hidden bonding aspects. Importantly, Pauling repulsion energy also plays a crucial role and decides the binding efficiency in terms of intrinsic interaction energy between the boron‐center and the N2 ligand.