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本文在确定各反应体系反应物和产物稳定构象的基础上,采用B3LYP/6-31G~(**)方法利用Gaussian 03程序,对质子化的双氧/硫杂紫菜嗪的内氢迁移反应进行了研究,寻找并优化相应的过渡态,比较了其迁移反应速率的差异。计算结果表明,在中心空穴较小的体系中,空间位阻和静电作用对构象稳定性的影响显著增强,并有可能超越共轭效应而成为影响构象的首要因素。另外,在体系的总电子不变的前提下,缩小中心空穴,提高芳香性,有助于电荷的平均分布,可以明显减弱取代基对IHAT反应速率的影响。
Based on the determination of the stable conformations of reactants and products in each reaction system, the B3LYP / 6-31G ~ (**) method was used to carry out the internal hydrogen transfer reaction of protonated dioxygen / sulfur porphyrazine using Gaussian 03 program The study, to find and optimize the corresponding transition state, compared with the migration reaction rate differences. The calculated results show that the effect of steric hindrance and electrostatic interaction on the conformational stability is significantly enhanced in the system with smaller central hole, which may surpass the conjugate effect and become the primary factor affecting the conformation. In addition, under the premise of the total electronic constant of the system, reducing the center hole, increasing the aromaticity, contributing to the average charge distribution can significantly reduce the influence of the substituent on the IHAT reaction rate.