Yan Chenting, Kinjo Rei
School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University, Singapore, 637371, Singapore.
Angew Chem Int Ed Engl. 2022 Oct 17;61(42):e202211800. doi: 10.1002/anie.202211800. Epub 2022 Sep 19.
[1+2] cycloaddition between a cyclic (alkyl)(amino)aluminyl anion (3) and diaryldiazomethane affords an AlN three-membered ring species (4). Compound (4) is thermally unstable and spontaneously releases N gas under the mild reaction condition to generate an ion-separated species 5. An X-ray study shows that the anionic part of 5 bears a considerable short exocyclic Al-C bond, and computational studies involving molecular orbital and natural bond orbital analysis indicate the Al=C π bonding character. The Al=C moiety of 5 undergoes intramolecular C-H activation. Moreover, reaction of 5 with a diazo compound leads to the reduction and complete cleavage of the N=N double bond.
环状（烷基）（氨基）铝阴离子（3）与二芳基重氮甲烷之间的[1+2]环加成反应生成了一个AlN三元环物种（4）。化合物（4）热不稳定，在温和的反应条件下会自发释放氮气，生成离子分离物种5。X射线研究表明，5的阴离子部分具有相当短的环外Al-C键，涉及分子轨道和自然键轨道分析的计算研究表明存在Al=C π键特征。5的Al=C部分发生分子内C-H活化。此外，5与重氮化合物的反应导致N=N双键的还原和完全断裂。
