Cooperative Iron–Aluminium Reactivity for Dinitrogen Activation

Abstract

Abstract We report a novel bimetallic approach utilizing cooperative Fe─Al reactivity for N 2 activation on the Cp*Fe(1,2‐Cy 2 PC 6 H 4 AlEt) platform, effectively capturing two N 2 molecules through intermolecular Fe─N≡N─Al coordination. Characterizations of the N 2 ‐bridged Fe─Al dimer ( 2 ) using Mössbauer spectroscopy coupled to density functional theory (DFT) calculations reveals its electronic structure as a resonance hybrid between Fe(II)‐Al(I) and Fe(0)‐Al(III). The flexible, covalent Fe─Al bonding facilitates the subsequent alkylation of the Al site with n BuLi, 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 N 2 activation.