2-硅萘与乙烯和四氰基乙烯杂iDels-Alder反应的理论研究
Theoretical Studies on the Hetero-Diels-Alder Reactions of 2-Silanaphthalenes with Ethylene and Tetr
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摘要: 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Abstract: The mechanism,potential energy surface,substituent effect and solvent effect of hetero-Diels-Alder reactions of 2-silanaphthalenes with ethylene and tetracyanoethylene were investigated using density functional theory(DFT) calculation at the B3LYP/6-311G(d,p) level of theory.The results show that all of studied reactions proceed in a concerted but nonsynchronous way.The influence of electron-withdrawing group at C atoms of ethylene on the activation barrier is determined by the type of substitue..
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