Jian Jiwen, Li Wei, Wu Xuan, Zhou Mingfei
Department of Chemistry , Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials , Collaborative Innovation Center of Chemistry for Energy Materials , Fudan University , Shanghai 200433 , China . Email:
Chem Sci. 2017 Jun 1;8(6):4443-4449. doi: 10.1039/c7sc01399j. Epub 2017 Apr 19.
The organo-boron species formed from the reactions of boron atoms with acetylene in solid neon are investigated using matrix isolation infrared spectroscopy with isotopic substitutions as well as quantum chemical calculations. Besides the previously reported single C-H bond activation species, a cyclic-HBCBH diboron species is formed double C-H bond activation of acetylene. It is characterized to have a closed-shell singlet ground state with planar symmetry. Bonding analysis indicates that it is a doubly aromatic species involving two delocalized σ electrons and two delocalized π electrons. This finding reveals the very first example of double C-H bond activation of acetylene in forming new organo-boron compounds.
利用基质隔离红外光谱结合同位素取代以及量子化学计算，对硼原子与固态氖中的乙炔反应形成的有机硼物种进行了研究。除了先前报道的单C-H键活化物种外，还通过乙炔的双C-H键活化形成了一种环状-HBCBH二硼物种。其特征是具有平面对称性的闭壳单重基态。键合分析表明，它是一种双芳香物种，涉及两个离域σ电子和两个离域π电子。这一发现揭示了乙炔在形成新的有机硼化合物过程中双C-H键活化的首个实例。
