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Cooperative Iron-Aluminium Reactivity for Dinitrogen Activation
Shengfa Ye1, Qiucui Zheng2,3, Xuebin Jiang1,4
1College of Chemistry, Beijing Normal University, Beijing, 100875, China.
None:
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 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 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.
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