摘要
文章利用Gaussian03程序,采用密度泛函理论(DFT),结合B3LYP方法和组合基组水平上研究了噻吩分子在过渡金属Co或Mo的催化作用下裂解开环反应的机理。计算结果表明,反应物中硫原子首先与过渡金属原子结合而形成稳定的中间体,然后进行分子内裂解,而脱硫过程主要依赖了高活性Co-H或Mo-H基团的参与。反应途径的势能剖面分析得知,两种金属上噻吩的裂解脱硫有不同的通道,过渡金属Mo较Co更容易促进噻吩的开环裂解,需要克服的最大势垒仅为48.63 kJ/mol,最大活化能仅为40.93kJ/mol,共同的产物为丁二烯碳正离子基团。
The thiophene ring cleavage reaction by the transition metal-catalyed is a hot focus in natural re-search. we use the density functional theory（DFT） method and combine B3 LYP method and compositions basedgroup level, in order to study the thiophene ring cleavage reaction by transition metal as Co or Mo by Gaussian03 program. The calculation results shows the sulfur atom in the reactant combine to transition metal form a stable in-termediate at first, and the ring cleavage reaction will carry on in the intra molecule, while the process of desulfu-rization depend the highly active radical as Co-H or Mo-H. It is showed that the thiophene ring cleavage into des-ulfurization have different channel from the potential energy surface analysis of the reaction pathway, the thiophenering cleavage reaction on Mo is more easier take place than on Co, and the largest potential barrier is 48.63 kJ/mol, and the maximum activation energy is only 40.93kJ/ mol, but the same product is 1,3-butadiene with a posi-tive charge.
出处
《新疆师范大学学报（自然科学版）》
2015年第2期30-35,共6页
Journal of Xinjiang Normal University(Natural Sciences Edition)
基金
衡阳市科技局项目(2013KJ23)资助
关键词
噻吩裂解
量子化学
密度泛函
反应机理
Thiophene cracking
Quantum chemistry
Density functional
Reaction mechanism
