一种无路易斯碱的三铝环烷：基于三个铝原子上连续空轨道的增强亲电性。
A Lewis Base-Free Trialumane: Enhanced Electrophilicity Based on Consecutive Vacant Orbitals Over Three Aluminum Atoms.
作者信息
Yamanashi Ryotaro, Chen Chaoqi, Moriyama Takumi, Muratsugu Satoshi, Tada Mizuki, Ozaki Taisuke, Yamashita Makoto
机构信息
Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Tokai National Higher Education and Research System, Furo-cho, Chikusa-ku, Nagoya, Aichi, 464-8603, Japan.
Department of Chemistry, Graduate School of Science, Nagoya University, Tokai National Higher Education and Research System, Furo-cho, Chikusa-ku, Nagoya, Aichi, 464-8602, Japan.
出版信息
Chemistry. 2025 May 19;31(28):e202501315. doi: 10.1002/chem.202501315. Epub 2025 Apr 21.
A Lewis base-free trialumane having a 2,4,6-triisopropylphenyl (Tip) substituent was synthesized by a reaction of alumanyl anion with TipAlBr. The structure, bonding, and electronic properties of the Tip-substituted trialumane were estimated by NMR spectra, X-ray crystallographic analysis, DFT calculations, X-ray photoelectron spectra, and electrochemical study to reveal its two consecutive Al─Al covalent bonds and overlapped vacant orbitals of three Al atoms. Chemical reduction of Tip-substituted trialumane gave a series of alumanyl anions via the cleavage of the Al─Al bonds. This study shows the low-lying characteristic LUMO that consists of vacant orbitals of three Al atoms in the base-free trialumane.
通过铝烷基阴离子与三异丙基苯基铝溴化物（TipAlBr）反应合成了具有2,4,6-三异丙基苯基（Tip）取代基的无路易斯碱三铝烷。通过核磁共振光谱、X射线晶体学分析、密度泛函理论计算、X射线光电子能谱和电化学研究对Tip取代的三铝烷的结构、键合和电子性质进行了评估，以揭示其两个连续的Al─Al共价键和三个Al原子重叠的空轨道。Tip取代的三铝烷的化学还原通过Al─Al键的断裂产生了一系列铝烷基阴离子。这项研究表明，在无碱三铝烷中，由三个Al原子的空轨道组成的低能最低未占分子轨道具有低能特性。
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