Cooperative Iron–Aluminium Reactivity for Dinitrogen Activation
We report a novel bimetallic approach utilizing cooperative Fe─Al reactivity for N<sub>2</sub> activation on the Cp*Fe(1,2-Cy<sub>2</sub>PC<sub>6</sub>H<sub>4</sub>AlEt) platform, effectively capturing two N<sub>2</sub> molecules through intermolecular Fe─N≡N─Al coordination. Characterizations of the N<sub>2</sub>-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 <sup>n</sup>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<sub>2</sub> activation.
Authors
- Shengfa Ye (ORCID: https://orcid.org/0000-0001-9747-1412)
- Chen‐Ho Tung (ORCID: https://orcid.org/0000-0001-9999-9755)
- Qiu-Cui Zheng
- Li‐Zhu Wu (ORCID: https://orcid.org/0000-0002-5561-9922)
- Jiaxin Zhang (ORCID: https://orcid.org/0000-0003-4859-2001)
- Wenguang Wang (ORCID: https://orcid.org/0000-0002-4108-7865)
- Xuebin Jiang (ORCID: https://orcid.org/0000-0002-2756-4071)
Institutions
- Sun Yat-sen University (CN)
- Dalian Institute of Chemical Physics (CN)
- Chinese Academy of Sciences (CN)
- Beijing Normal University (CN)
- Guangzhou University (CN)
- Technical Institute of Physics and Chemistry (CN)
- University of Chinese Academy of Sciences (CN)
- University of Hong Kong (HK)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2025-04-17
- DOI
- https://doi.org/10.1002/anie.202504538
- Primary Topic
- Inorganic Chemistry and Materials
- Type
- article
- Field-Weighted Citation Impact
- 0.00