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在密度泛函B3LYP/6-311G~(**)理论水平上,对气相和水相中3-卤代吲唑互变异构体进行几何构型全自由度优化,获得它们在气相和水相中的几何结构和电子结构,PCM反应场溶剂模型用于水相计算。结果显示在气相和水相中,3-卤代吲唑的N_1-H形式比N_2-H形式稳定。探讨了不同的3-取代基团和溶剂化效应对互变异构体的几何结构,能量,电荷分布以及互变异构反应活化能的影响等。进一步研究了3-卤代吲唑水催化质子迁移的反应机理,提出了平面五元环的过渡态结构。
At B3LYP / 6-311G ~ (**) level, the geometrical configurations of the 3-haloindazole tautomers in the gas phase and the aqueous phase were optimized for their full degrees of freedom. Their gas phase and water Phase geometry and electronic structure, PCM reaction field solvent model for the calculation of the water phase. The results show that the N 1 -H form of 3-haloindazole is more stable than that of N 2 -H in both gas phase and aqueous phase. The effects of different 3-substituent groups and solvating effects on the tautomer geometry, energy, charge distribution and activation energy of tautomerism were discussed. The mechanism of proton transfer catalyzed by 3-haloindazole was further investigated. The transition state of 5-membered ring was proposed.