Zhu Lizhao, Kinjo Rei
School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University, Nanyang Link 21, Singapore, 637371, Singapore.
Angew Chem Int Ed Engl. 2023 Aug 14;62(33):e202306519. doi: 10.1002/anie.202306519. Epub 2023 Jul 6.
Triboraazabutenyne 3 is synthesized by the reaction of diboraazabutenyne 1 with aryl boron dibromide followed by the reduction. The ligand exchange to replace phosphine on the terminal sp B atom with carbene furnishes 4. B NMR, solid-state structures, and computational studies disclose that 3 and 4 feature the extremely polarized B=B bond. 4 readily splits the N=N bond of both diazo compound and diazirine under ambient conditions, whereby one nitrogen atom is incorporated into the B=B moiety leading to a neutral diboraazaallene 6. The mechanism of the reaction between 4 and diazo compound is extensively investigated by density functional theory (DFT) calculations, as well as the isolation of an intermediate.
三硼氮杂丁炔3是通过二硼氮杂丁炔1与芳基二溴化硼反应然后还原而合成的。用卡宾取代末端sp杂化硼原子上的膦进行配体交换得到4。硼核磁共振、固态结构和计算研究表明，3和4具有极度极化的B=B键。4在环境条件下能轻易地断裂重氮化合物和二氮烯的N=N键，其中一个氮原子并入B=B部分，生成中性的二硼氮杂丙二烯6。通过密度泛函理论（DFT）计算以及中间体的分离，对4与重氮化合物之间的反应机理进行了广泛研究。
