四苯并卟啉/酞菁结构及其内氢反应迁移理论研究

Theoretical study on transfer reaction of inner hydrogen atoms in Tetrabenzoporphyrin and Phthalocyanine

采用B3LYP/6-31G"法在Gaussian03程序下,优化四苯并卟啉/酞菁的结构和能量,并寻找与内氢迁移反应相关的过渡态构型。计算结果表明,中心空穴缩小、共轭效应的增强都有利于内氢迁移,但中心空穴的影响要大很多。

A theoretical study of the mechanism and kinetics of the inner hydrogen atom-transfer process in tetrabenzoporphyrin （ TB- PH2 ） and phthalocyanine（PTCH2 ） is presented. The structures and energies of reactants, products and transition-states in the transfer reaction of inner hydrogen atoms in TBPH2 and PTCH2 are calculated with B3LYP/6-31 G^＊＊ method under certain symmetry restriction. The calculated results show that the smaller central hole and the bigger conjugate effect are all advantageous to IHAT reactions, but the influence of central hole is greater.