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采用密度泛函理论(DFT)方法在B3LYP/6-311G(d,p)水平上研究2-硅萘与乙烯和四氰基乙烯的杂D iels-A lder反应的微观机理和势能剖面,考察反应的取代基效应和溶剂效应.计算结果表明,所研究反应均以协同非同步的方式进行.乙烯分子中碳原子上的吸电子基团对反应活化能垒的影响取决于2-硅萘中硅上所连接基团的类型.2-硅萘分子中硅原子上的C(CH3)3取代基对反应势能剖面的影响比较小,而其上的CC l3和NH2取代基对反应势能剖面的影响则与亲二烯体分子中碳原子上的取代基的类型有关.苯溶剂对所研究反应的势能剖面影响不大.2-硅萘作为杂二烯烃参与杂D iels-A lder反应的反应性远低于硅苯.
The density functional theory (DFT) method was used to study the microscopic mechanism and potential energy profile of hetero-D iels-Alder reaction of 2-silanaphthalene with ethylene and tetracyanoethylene at the B3LYP / 6-311G (d, p) The substituent effect and the solvent effect of the reaction.The calculated results show that the studied reactions are carried out in a synergetic and asynchronous manner.Effects of electron-withdrawing groups on the carbon atoms of the ethylene molecule on the reactive energy barrier depend on the content of 2-silanaphthalene The type of the groups attached to silicon. The C (CH3) 3 substituents on the silicon atom of 2-silicon naphthalene have a relatively small influence on the potential energy profile of the reaction, but the CC13 and NH2 substituents on the The effect is related to the type of substituents on the carbon atom of the dienophile molecule. The benzene solvent has little effect on the potential energy profile of the investigated reaction.2- The reaction of silanaphthalene as a heterodiene in the Diel-Alder reaction Much lower than the silicon benzene.