2-甲基-1,3-顺丁二烯在Ni (I)催化下与苯甲醛反应机理的研究

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64.20 kJ.mol-1、51.63 kJ.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。

Theoretical investigation on the reaction mechanism of 2-methyl-1,3-cis-butadiene with benzaldehyde catalyzed by Ni(I)

The reaction mechanism of 2-methyl-1,3-cis-butadiene with benzaldehyde catalyzed by Ni(I) was studied using the density functional theory at B3LY P/6-31+G* level. The geometric configurations of reactants, intermediates, transition states and products were optimized. Nature bond orbital (NBO) and atoms in molecules (AIM) theories were used to discuss the bond nature and orbital interactions at the same levels. Two possible reaction pathways, IA and IB, were investigated and their activation energies of the limiting steps are 64.20 and 51.63 kJ.mol-1, respectively. The reaction is the rate determining step. From the above results, it can be seen that throughout the course of the reaction the IA and IB channels occur at the same time, but the IB channel has lower activation energy. So IB channel is the main reaction channel in the whole reaction. These points are in agreement with the experimental results.