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Ab initio Study on Formation Mechanism of Spiro-Si-Heterocyclic Ring Compound Involving Ge from H2Ge=Si: and Formaldehyde
Xiu-hui Lu,Dang-sheng Wang,Jing-jing Ming
Author NameAffiliationE-mail
Xiu-hui Lu School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, China lxh@ujn.edu.cn 
Dang-sheng Wang School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, China  
Jing-jing Ming School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, China  
Abstract:
H2Ge=Si: and its derivatives (X2Ge=Si:, X=H, Me, F, Cl, Br, Ph, Ar,…) are new species. Its cycloaddition reactions are new area for the study of silylene chemistry. The cycloaddition reaction mechanism of singlet H2Ge=Si: and formaldehyde has been investigated with the MP2/aug-cc-pVDZ method. From the potential energy profile, it could be predicted that the reaction has one dominant reaction pathway. The reaction rule is that two reactants firstly form a four-membered Ge-heterocyclic ring silylene through the [2+2] cycloaddition reaction. Because of the 3p unoccupied orbital of Si: atom in the four-membered Ge-heterocyclic ring silylene and the π orbital of formaldehyde forming a π→p donor-acceptor bond, the four-membered Ge-heterocyclic ring silylene further combines with formaldehyde to form an intermediate. Because the Si: atom in the intermediate undergoes sp3 hybridization after transition state, then the intermediate isomerizes to a spiro-Si-heterocyclic ring compound involving Ge via a transition state. The result indicates the laws of cycloaddition reaction between H2Ge=Si: or its derivatives (X2Ge=Si:, X=H, Me, F, Cl, Br, Ph, Ar,…) and asymmetric π-bonded compounds are significant for the synthesis of small-ring involving Si and Ge and spiro-Si-heterocyclic ring compounds involving Ge.
Key words:  H2Ge=Si:  Four-membered Ge-heterocyclic ring silylene  Spiro-Si-heterocyclic ring compound  Potential energy profile
FundProject:This work was supported by the National Natural Science Foundation of China (No.51102114).
H2Ge=Si:与甲醛生成含锗螺硅杂环化合物反应机理的从头算研究
卢秀慧,王党生,明静静
摘要:
用MP2/AUG-CC-PVDZ 方法研究了单重态H2Ge=Si:与甲醛环加成反应的反应机理,该反应有一条主反应通道. 该反应所呈现的反应规律为:两反应物通过[2+2]环加成反应首先生成了一锗杂四元环硅烯,由于该锗杂四元环硅烯中Si:原子的3p空轨道与甲醛的π轨道形成了π→p授受键,使锗杂四元环硅进一步与甲醛结合生成了一中间体. 由于该中间体中的Si:原子在过渡态之后发生了sp3杂化,该中间体经过渡态异构化为含锗的螺硅杂环化合物. 该研究结果从理论上揭示了单重态H2Ge=Si:及其衍生物(X2Ge=Ge:, X=H, Me, F, Cl, Br, Ph, Ar, …)与非对称性π 键化合物环加成反应的反应机制.
关键词:  H2Ge=Si:  锗杂四元环硅烯  螺硅杂环化合物  势能面
DOI:10.1063/1674-0068/29/cjcp1507139
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