论文部分内容阅读
采用密度泛函理论(DFT)研究了2-甲基-1,3-顺丁二烯在Ni(I)催化下与苯甲醛反应生成高烯丙基醇的反应机理.在B3LYP/6-31+G*水平上对反应过程中所有反应物、过渡态、中间体以及产物的几何构型进行了优化,通过能量和振动分析确认了过渡态的真实性;并且在相同基组水平上应用自然键轨道(NBO)和分子中的原子(AIM)理论分析了这些化合物的成键特征和轨道间的相互作用.研究发现了两条可能的反应通道IA与IB,其控制步骤活化能分别为64.20kJ.mol-1、51.63kJ.mol-1,由以上比较结果可以看出,反应通道IA与IB在整个反应过程可能同时发生,但IB通道具有较低的活化能,即IB通道为整个反应的最优反应通道,与实验结果一致.
The reaction mechanism of 2-methyl-1,3-butadiene catalyzed by Ni (I) catalyzed by benzaldehyde to form allyl alcohol was studied by using density functional theory (DFT). At B3LYP / 6-31 The geometry of all the reactants, transition states, intermediates and products during the reaction was optimized at + + G * level. The authenticity of the transition state was confirmed by energy and vibration analysis. And at the same basic level, (NBO) and atom (AIM) in the molecule, the bonding characteristics and orbital interactions of these compounds were analyzed.The two possible reaction channels, IA and IB, were found to have activation energies of 64.20 kJ.mol-1,51.63kJ.mol-1. As can be seen from the above comparison, the reaction channels IA and IB may occur simultaneously in the whole reaction process, but the IB channel has a lower activation energy, ie, the IB channel is the entire reaction The optimal reaction channel, consistent with the experimental results.