Butadienyl Diiron Complexes: Nonplanar Metalla-Aromatics Involving σ-Type Orbital Overlap.,Angewandte Chemie International Edition

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Butadienyl Diiron Complexes: Nonplanar Metalla-Aromatics Involving σ-Type Orbital Overlap.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-07-19 , DOI: 10.1002/anie.202008986
Chao Yu ₁ , Mingdong Zhong ₁ , Yongliang Zhang ₁ , Junnian Wei ₁ , Wangyang Ma ₁ , Wen-Xiong Zhang ₁ , Shengfa Ye _{2,

3} , Zhenfeng Xi _{1,

4}

Affiliation

A new class of nonplanar metalla‐aromatics, diiron complexes bridged by a 1,3‐butadienyl dianionic ligand, were synthesized in high yields from dilithio reagents and two equivalents of FeBr₂. The complexes consist of two antiferromagnetically coupled high‐spin Fe^II centers, as revealed by magnetometry, Mössbauer spectroscopy, and DFT calculations. Furthermore, experimental (X‐ray structural analysis) and theoretical analyses (NICS, ICSS, AICD, MOs) suggest that the complexes are aromatic. Remarkably, this nonplanar metalla‐aromaticity is achieved by an uncommon σ‐type overlap between the ligand p and metal d orbitals, in sharp contrast to the intensively studied planar aromatic systems featuring delocalized π‐type bonding. Specifically, the σ‐type interaction between the two Fe 3d_xz orbitals and the butadienyl π orbital results in the formation of a six‐electron conjugated system and hence enables the aromatic character.

中文翻译：

丁二烯二铁配合物：涉及σ型轨道重叠的非平面金属芳香族。

一类新型的非平面金属芳香族化合物，由1,3-丁二烯基双阴离子配体桥接的二价铁配合物，是由二硫代试剂和两当量的FeBr ₂高产率合成的。配合物由两个反铁磁耦合的高自旋Fe ^II中心组成，这通过磁力计，Mössbauer光谱法和DFT计算得以揭示。此外，实验（X射线结构分析）和理论分析（NICS，ICCSS，AICD，MO）表明该络合物是芳香族的。值得注意的是，这种非平面的金属芳香性是通过配体p和金属d轨道之间不常见的σ型重叠实现的，与深入研究的具有离域π型键合的平面芳族体系形成鲜明对比。具体来说，两个Fe 3d之间的σ型相互作用_xz轨道和丁二烯π轨道导致形成六电子共轭体系，因此具有芳香性。

更新日期：2020-07-19

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