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用量子化学的密度泛函理论(DFT)在6-311G(d,p)水平上对亚烷基卡宾及取代亚烷基卡宾与环氧乙烷的氧转移反应机理进行了系统的研究.用IRC对过渡态进行了确认.并用组态混合模型讨论了反应势垒(△E~≠)与XYC=C:的单-三态能量差△E_(ST)之间的关系,结果表明,取代基的电负性是控制反应的主要因素,取代基的电负性越大,取代基越多,π电子给予体越多,单-三态能量差△E_(ST)就越小,该反应的活化能就越小,反应越容易发生.同时还研究了该反应中环氧乙烷中C—O键的解离过程.发现两个C—O键解离是一个不同步的协同过程.
The mechanism of oxygen transfer reaction of alkylene carbenes and substituted alkylene carbenes with ethylene oxide was studied systematically at the level of 6-311G (d, p) by using quantum chemical density functional theory (DFT) The transition state was confirmed by the IRC, and the relationship between the reaction potential barrier (ΔE ~ ≠) and the one-tristate energy difference ΔE_ (ST) of XYC = C: was discussed by using the hybrid model. The electronegativity of the group is the main factor controlling the reaction. The more the electronegativity of the substituent is, the more the substituent is, the more the π electron donor, the smaller the energy difference ΔE_ (ST) The smaller the activation energy is, the easier the reaction takes place.The dissociation of C-O bond in ethylene oxide is also studied.The dissociation of two C-O bonds is an asynchronous process.