Title烯烃亲电加成反应机理的理论探讨
Other TitlesTheoretical study for the mechanism of electrophilic addition to alkenes reactions
Authors周志刚
戴乾圜
Affiliation北京大学环境科学中心!北京
100871
北京工业大学癌化学与生物工程中心
北京
100022
Keywords烯烃亲电加成
反应机理
d-π配位键
立体化学
区域化学
PM3
electrophilic addition to alkene
reaction mechanism
d-pi coordination bond
stereochemistry
regionchemistry
PM3
Issue Date1999
Publisher物理化学学报
Citation物理化学学报.1999,(06),500-505.
Abstract采用PM3方法计算了不同亲电试剂与乙烯生成的中间体正离子的势能曲线.结果显示,当亲电中心原子为价电子层没有d轨道的第一、二周期元素时,开放型中间体正离子的能量比桥型中间体正离子的能量低;此类加成经历开放中间体离子机制进行更为有利,表现出立体非专一性和区域选择性;当亲电中心原子为价电子层有d轨道的第三、四、五周期的元素时,桥型中间体正离子的能量比开放型中间体正离子的能量低;此类加成经历桥型中间体离子机制进行更为有利,表现出立体专一性和区域非专一性.以d-π和s-p-π配位键轨道模型,尝试阐述其内在的轨道控制机制,较好地解释了实验事实.
The potential intermediates of a series of electrophilic agents reacting with ethene have been computed with PM3 semiempirical method. The results show that the energy of the bridged structure intermediates is lower than that of the open structure intermediates as the central atom of electrophilio agents is the third, fourth or fifth periodic element, but higher as the central atom is the first or second periodic element. Thereby, the electrophilic agents with third, fourth or fifth periodic element as central atoms should give stereospecific and non-regionspecific products and those with first or second periodic element as central atoms should give non-stereospecific and regionspecific products, it is well an accordance with experimental results. Meanwhile, the model of d- pi* and s-p - pi coordination bond has been put forward to try to explain the molecular mechanism.
URIhttp://hdl.handle.net/20.500.11897/4003
ISSN1000-6818
DOI10.3866/PKU.WHXB19990604
IndexedSCI(E)
中文核心期刊要目总览(PKU)
中国科学引文数据库(CSCD)
Appears in Collections:环境科学与工程学院

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