位阻效应对N-(4-脱氢苯基)吡啶离子与氮氧自由基反应的理论计算研究

应用量子化学密度泛函理论(DFT),在B3LYP/cc-pVDZ基组水平上,对N-(4-脱氢苯基)吡啶离子与不同结构的氮氧自由基反应进行了热动力学研究.优化了反应通道上反应物、中间体、过渡态和产物的几何构型并计算出它们的零点振动能( Ezpv)和焓值,分析数据研究位阻效应对反应的影响.研究表明3类氮氧自由基均与N-(4...

Theoretical study on the reaction of N-(4-dehydrophenyl)pyridinium ion with nitroxides within the steric effects

The reaction of N-(4-dehydrophenyl)pyridinium ion with nitroxides by using DFT method.At B3LYP/cc-pVDZ level,the reaction heat dynamics research on different structure of N-(4-dehydrophenyl) pyridinium ion and nitroxides have been calculated.The geometries of reactants,transition states and products of reactions mentioned above have been optimized.Further considering zero-point energy correction and thermal enthalpies.Analyzing data bits effect how to effect the reaction.The result of the research indicates that a series of this effect is the main influence factors.It shows that N-(4-dehydrophenyl)pyridinium ionwith different nitroxides undergo a process that without barrier generates a intermediates,then rearrangement to two new free radicals.Compared with the closed nitroxides(TEMPO and TMIO),the chemical properties of open loop nitroxides is more complex.solvent effect also has effects,and the formation of the relevant product among reaction.