南方科技大学刘柳团队制备了具有不同σ-供体和双σ/π-接受配体特征的游离亚铝烯。相关研究成果发表在2021年10月6日出版的《德国应用化学》。

该文报道了一种游离的N-铝烯，即咔唑基铝烯 2b的合成、表征和配位化学。该物种通过相应的咔唑基二碘化铝的还原反应制备。2b对过渡金属中心（W，Cr）的配位行为显示出一系列具有不同配位模式的新型铝烯配合物3-6。研究人员证明2b中的Al中心可以表现为：1.σ-供体和双π-受体配体；2.σ-供体、σ-受体和π-受体配体；3.一个σ-供体和双σ-受体配体。

此外，研究人员还发现，在不改变配位原子的情况下，铝烯中心的配体交换可以调节过渡金属的电子性质。用IDippCuCl（IDipp=1,3-双（2,6-二异丙基苯基）咪唑-2-亚基）对2b进行的研究表明，一种前所未有的铝酰铝酰基转化导致一种罕见的末端铜铝酰基络合物8。通过密度泛函理论（DFT）计算，研究了这类配合物的电子结构和铝烯-铝酰基转化机理。

附：英文原文

Title: A Free Aluminylene with Diverse σ-Donating and Doubly σ/π-Accepting Ligand Features for Transition Metals

Author: Liu Leo Liu, Xin Zhang

Issue&Volume: 2021-10-06

Abstract: We report herein the synthesis, characterization, and coordination chemistry of a free N-aluminylene, namely a carbazolylaluminylene 2b. This species is prepared via a reduction reaction of the corresponding carbazolyl aluminium diiodide. The coordination behavior of 2b towards transition metal centers (W, Cr) is shown to afford a series of novel aluminylene complexes 3-6 with diverse coordination modes. We demonstrate that the Al center in 2b can behave as: 1. a σ-donating and doubly π-accepting ligand; 2. a σ-donating, σ-accepting and π-accepting ligand; and 3. a σ-donating and doubly σ-accepting ligand. Additionally, we show ligand exchange at the aluminylene center providing access to the modulation of electronic properties of transition metals without changing the coordinated atoms. Investigations of 2b with IDippCuCl (IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) show an unprecedented aluminylene-alumanyl transformation leading to a rare terminal Cu-alumanyl complex 8. The electronic structures of such complexes and the mechanism of the aluminylene-alumanyl transformation are investigated through density functional theory (DFT) calculations.

DOI: 10.1002/anie.202111975

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202111975