Dinickelaferrocene: A Ferrocene Analogue with Two Aromatic Nickeloles Realized 
by Electron Back‐Donation from Iron

Huang, Zhe; Zheng, Yu; Zhang, Wen-Xiong; Ye, Shengfa; Deng, Liang; Xi, Zhenfeng

doi:10.1002/anie.202007222

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Dinickelaferrocene: A Ferrocene Analogue with Two Aromatic Nickeloles Realized by Electron Back‐Donation from Iron

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Ye, Shengfa
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences;
Research Group Ye, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Huang, Z., Zheng, Y., Zhang, W.-X., Ye, S., Deng, L., & Xi, Z. (2020). Dinickelaferrocene: A Ferrocene Analogue with Two Aromatic Nickeloles Realized by Electron Back‐Donation from Iron. Angewandte Chemie International Edition, 59(34), 14394-14398. doi:10.1002/anie.202007222.

Cite as: https://hdl.handle.net/21.11116/0000-0006-D539-A

Abstract

The first example of ferrocene analogues with two transition‐metal metallole ligands of the general formula (η⁵‐C₄R₄M)₂Fe in a sandwich structure are reported. Specifically, dinickelaferrocene 2 , a type of dimetallametallocene, is efficiently synthesized from the reaction of dilithionickelole 1 with FeBr₂ or FeCl₂, presumably via a redox process, and is subjected to detailed experimental (single‐crystal X‐ray structural analysis, ICP‐OES, magnetometry, ⁵⁷Fe Mössbauer, XPS) and theoretical (MOs, CDA, NICS, ICSS, and AICD) characterizations. Unlike ferrocene and its Cp ligands, the aromaticity of dinickelaferrocene and its nickelole ligands is accomplished by electron back‐donation from the Fe 3d orbitals to the π* orbitals of nickelole. Taken together, this work describes a new class of metallaferrocene sandwich complexes and provides a novel approach to effect aromaticity that will contribute to further development of metallocene chemistry.