论文部分内容阅读
在密度泛函(DFT)B3LYP/6-311++G**理论水平上,全自由度优化气相和水相中3-(CHO/COF)-吲唑两种反应途径(Path A:分子内质子迁移;Path B:水助质子迁移)质子迁移的各异构体的几何构型,得其气相和水相中的几何结构和电子结构,并将PCM(极化连续介质模型)反应场溶剂模型用于水相计算.在气相和水相中,3-(CHO/COF)-吲唑的N1-H形式比N2-H形式稳定.进一步研究3-(CHO/COF)-吲唑质子迁移的反应机理.研究结果显示:不同的3C取代基对反应物、产物及过渡态的分子几何构型影响不大,但是不同构象的3C取代基对反应物、产物的几何结构和质子迁移的热力学参数有较大影响;溶剂化效应和氢键的形成对质子转移反应的热力学参数有很大影响;Path B所需的活化能较低,约为Path A途径的一半.
In the theory of density functional theory (DFT) B3LYP / 6-311 ++ G **, the two degrees of freedom of 3- (CHO / COF) -indazole in the gas phase and aqueous phase are optimized with full freedom (Path A: Path B: water-assisted proton migration) The geometrical configuration of the isomers of the proton-migrating species gives rise to the geometrical and electronic structures in the gas phase and the aqueous phase. The PCM (Polarization Continuous Media Model) reaction field solvent The model was used for the water phase calculation. The N1-H form of 3- (CHO / COF) -indazole was more stable than the N2-H form in the gas phase and water phase.Further study was made on the proton transfer of 3- (CHO / COF) The results show that the different 3C substituents have little effect on the geometrical configuration of the reactants, products and transition states, but the thermodynamics of reactants, product geometries and proton migration of 3C substituents with different conformations The influence of solvation effect and hydrogen bond on the thermodynamic parameters of proton transfer reaction is significant. Path B requires less activation energy, which is about half of that of Path A pathway.