【摘要】 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N₁-H形式比N₂-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。更多还原

【Abstract】 The molecular structures of indazole and 3-halogeno-indazole tautomers were calculated by the B3LYP method at the 6-31 IG^** level,both in the gaseous and aqueous phases,with full geometry optimization.The geometry and electronic structure of the tautomers of indazole,3-halogeno-indazole and their transition states were obtained.The PCM solvate theory model was employed for the aqueous solution calculations.The results of the calculation indicate that the N₁-H form of the studied molecule is more stable than that of the N₂-H form.The influences of the different 3-halogeno and the solvent effects on the geometry,energy,charge and activation energy were discussed.The reaction mechanism of water-assisted intermolecular transfer of indazole and 3-halogeno-indazole was also studied and a five-member cyclic transition state of the water-assisted intermolecular transfer reaction was obtained.更多还原