Dinickelaferrocene: A Ferrocene Analogue with Two Aromatic Nickeloles Realized by Electron Back-Donation from Iron.,Angewandte Chemie International Edition

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Dinickelaferrocene: A Ferrocene Analogue with Two Aromatic Nickeloles Realized by Electron Back-Donation from Iron.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-06-08 , DOI: 10.1002/anie.202007222
Zhe Huang ₁ , Yu Zheng ₁ , Wen-Xiong Zhang ₁ , Shengfa Ye _{2,

3} , Liang Deng ₄ , Zhenfeng Xi _{1,

4}

Affiliation

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.

中文翻译：

Dinickelaferroceneene：二茂铁类似物，具有两个芳香镍，通过铁的电子反向捐赠实现。

（二茂铁类似物与通式的两种过渡金属的配体metallole第一示例η ⁵ -C ₄ - [R ₄ M）₂的Fe中的夹层结构被报告。具体来说，一种双金属硅茂铁烯类型的二茂铁2是由二锂离子油菜籽1与FeBr ₂或FeCl ₂的反应有效合成的，大概是通过氧化还原过程进行的，并进行了详细的实验（单晶X射线结构分析，ICP- OES，磁力分析，⁵⁷FeMössbauer，XPS）和理论上的描述（MO，CDA，NICS，ICCSS和AICD）。与二茂铁及其Cp配体不同，二镍基二茂铁及其镍原子配体的芳香性是通过从Fe 3d轨道向镍原子的π*轨道进行电子反向供电来实现的。两者合计，这项工作描述了一类新的金属茂铁夹心复合物，并提供了一种新的方法来实现芳香性，这将有助于金属茂化学的进一步发展。

更新日期：2020-08-10

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