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Ab initio Study on Mechanism of Forming a Silicic Bis-Heterocyclic Compound Between Dimethylmethylenesilylene and Ethene
Xiu-hui Lu*,Jun-feng Han,Hai-bin Yu,Zhen-xia Lian
Author NameAffiliationE-mail
Xiu-hui Lu* School of Chemistry and Chemical Engineering, University of Ji'nan, Ji'nan 250022, China lxh@ujn.edu.cn 
Jun-feng Han School of Chemistry and Chemical Engineering, University of Ji'nan, Ji'nan 250022, China  
Hai-bin Yu School of Chemistry and Chemical Engineering, University of Ji'nan, Ji'nan 250022, China  
Zhen-xia Lian School of Chemistry and Chemical Engineering, University of Ji'nan, Ji'nan 250022, China  
Abstract:
The mechanism of the cycloaddition reaction of forming a silicic bis-heterocyclic compound between singlet dimethylmethylenesilylene (Me2C=Si:) and ethene has been investigated with the CCSD(T)//MP2/6-31G* method. From the potential energy profile, it can be predicted that, this reaction has one dominant channel. The presented rule of this dominant channel: the 3p unoccupied orbital of Si in dimethylmethylenesilylene and the π orbital of ethene forming the π→p donor-acceptor bond, resulting in the formation of three-membered ring intermediate (INT1); INT1 then isomerizes to a four-membered ring silylene (P2), which is driven by ring-enlargement effect; due to sp3 hybridization of Si atom in P2, P2 further combines with ethene to form a silicic bis-heterocyclic compound.
Key words:  Dimethylmethylenesilylene, Reaction mechanism, Potential energy surface
FundProject:
二甲基亚甲基硅烯与乙烯生成硅杂双环化合物反应机理的从头算研究
卢秀慧*,韩军锋,于海彬,廉贞霞
摘要:
用CCSD(T)//MP2/6-31G*方法研究了单重态二甲基亚烷基硅烯与乙烯生成硅杂双环化合物环加成反应的机理,根据该反应的势能面可以预言,该反应只有一条主反应通道. 该主反应通道所呈现的反应规律为:二甲基亚烷基硅烯中Si原子的3p空轨道与乙烯中的π轨道形成了π→p授受键,生成三元环中间体(INT1);扩环作用使INT1异构化为四元环硅烯(P2);P2中Si原子的sp3杂化使P2进一步与乙烯结合生成了硅杂双环化合物.
关键词:  二甲基亚甲基硅烯,反应机理,势能面
DOI:10.1088/1674-0068/23/05/533-537
分类号: