【摘要】 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.更多还原

【Abstract】 The reaction mechanism of Arynes with Alkynes catalyzed by Cu Cl has been investigated by density functional theory( DFT). The geometries and the frequencies of reactants,intermediates,transition states,and products have been calculated at the B3 LYP /6 – 31 + G* level,and the Lan L2 DZ basis has been used as the extrabasis. The vibration analysis demonstrates that the authenticity of transition states,and the reaction processes are confirmed by the changes of charge density at bond- forming critical point which analyzed by the atoms in molecules theory. In addition,the nature bond orbital has been used to discuss the bond nature and orbital interactions at the same level. Meanwhile,the single point energy of the reaction process in gas and solvent at 6- 311+ G* level has been individually investigated with higher precision. The results indicate that the reaction mechanism and the change trend of correspondence energy at two different levels are consistent. The result of the theory study agrees with the experimental data,it indicates that the Cu Cl is an effective catalyst in this reaction.更多还原