不饱和硼烯HClN=B:重排反应的DFT研究

采用量子化学中的密度泛函方法, 在B3LYP/6-311G**水平上研究了不饱和硼烯HClN=B:的重排反应机理。结果表明, 无论是氢原子H迁移还是氯原子Cl迁移都经过1个三元环过渡态,生成直线型产物。但氢原子H迁移是在面内进行, 而氯原子Cl迁移是在面外进行。根据计算结果,详细研究了不饱和硼烯HClN=B:重排反应的热力学及动力学函数, 在此基础上讨论了不饱和硼烯HClN=B:的存在寿命问题。

Study on the Rearrangement Reaction of HClN=B: Using DFT Method

The mechanism of the rearrangement reaction of HClN=B: has been studied using DFT method of quantum chemistry at B3LYP/6-311G** level. The result shows that the Transition States of the H-transfer and Cl-transfer of the title compound are both three-membered ring structure, and both products are linear molecules. The H-transfer is at the internal molecular plane, but the Cl-transfer at the external one. According to the results at B3LYP/6-311G** level, thermodynamic and kinetic properties of the rearrangement reaction have been calculated. The half life of HClN=B: has been calculated using the rate of reaction HClN=B: →H-N≡B-Cl, and the value at 300K is 3.46?0-9s.