【摘要】 采用B3LYP/6-31G**方法在Gaussian03程序下,对氧杂卟啉(OPH),硫杂卟啉(SPH)的结构和能量进行优化,并寻找与内氢迁移反应相关的过渡态构型.计算结果表明,由于分子内氢键的存在,氧或硫杂化均会使卟吩内氢迁移正负反应速率明显降低.更多还原

【Abstract】 A theoretical study of the mechanism and kinetics of the inner hydrogen atom-transfer process in oxa-porphyrin (OPH) and thia-porphyrin (SPH) was presented. The structures and energies of reactants, products and transition-states in the transfer reaction of inner hydrogen atoms in OPH and SPH were calcu- lated with B3LYP/6-31G** method under certain symmetry restriction. The calculated results show that compared with porphine (PH2), oxa- or thia- can decrease speeds of positive and negative reactions, which is due to the existence of intra-molecular hydrogen bonds.更多还原