Cooperative Iron‐Aluminium Reactivity for Dinitrogen Activation

We report a novel bimetallic approach utilizing cooperative Fe‐Al reactivity for N2 activation on the Cp*Fe(1,2‐Cy2PC6H4AlEt) platform, effectively capturing two N2 molecules through intermolecular Fe‐N≡N‐Al coordination. Characterizations of the N2‐bridged Fe‐Al dimer (2) using Mössbauer spectroscopy and density functional theory calculations reveals its electronic structure as a resonance hybrid between Fe(+2)‐Al(+1) and Fe(0)‐Al(+3). The flexible, covalent Fe‐Al bonding facilitates the subsequent alkylation of the Al site with nBuLi, leading to the formation of a dinitrogen‐lithiated complex (3) that enables the silylation of the terminal N atom. Our findings highlight the significance of leveraging Fe‐Al effects as an electron buffer to achieve facile N2 activation.