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利用密度泛函理论(DFT)研究了Cu Cl催化下苯炔与环己烯乙炔偶联反应的微观反应机理.在B3LYP/6-31+G*基组水平上(Cu采用了赝势基组Lan L2DZ)优化了反应过程中所有化合物的几何构型并计算了频率,通过能量、频率和振动方式确定了中间体和过渡态的真实性.此外,在同等基组水平上还运用了分子中的原子理论讨论了成键临界点的电荷密度的变化,运用了自然键轨道理论讨论了键的性质与轨道间的相互作用.为了提高计算精度,在6-311+G*基组水平上计算了反应机理中所有物质在气相及溶剂化下的单点能,得到与6-31+G*基组计算相同的结论.结论表明Cu Cl对苯炔与1-乙炔基环己烯偶联反应起到了有效的催化作用,且计算所得结论与实验结果相符合.
The microreactor mechanism of the coupling reaction between benzoxine and cyclohexene acetylene catalyzed by CuCl was studied by using density functional theory (DFT). At the B3LYP / 6-31 + G * basis group level Lan L2DZ) optimizes the geometry of all compounds in the reaction process and calculates the frequency, the authenticity of the intermediates and transition states are determined by energy, frequency and vibration. In addition, at the same basis level, The atomic theory discussed the change of charge density at the critical point of bond formation and discussed the nature of the bond and the orbital interaction using the theory of natural bond orbital.In order to improve the calculation precision, The single point energy of all the species in the reaction mechanism in the gas phase and the solvation show the same conclusion as that of the 6-31 + G * group. The results show that the coupling reaction of CuCl with 1-ethynylcyclohexene Played an effective catalytic role, and the calculated conclusion is consistent with the experimental results.