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Density Functional Theory Study on Mechanism of Forming Spiro-Ge-heterocyclic Ring Compound from Me2Ge=Ge: and Acetaldehyde
Xiu-hui Lu*,Yong-qing Li,Wei-jie Bao,Dong-ting Liu
Author NameAffiliationE-mail
Xiu-hui Lu* School of Chemistry and Chemical Engineering, University of Ji'nan, Ji'nan 250022, China lxh@ujn.edu.cn 
Yong-qing Li School of Chemistry and Chemical Engineering, University of Ji'nan, Ji'nan 250022, China  
Wei-jie Bao School of Chemistry and Chemical Engineering, University of Ji'nan, Ji'nan 250022, China  
Dong-ting Liu School of Chemistry and Chemical Engineering, University of Ji'nan, Ji'nan 250022, China  
Abstract:
The H2Ge=Ge:, as well as and its derivatives (X2Ge=Ge:, X=H, Me, F, Cl, Br, Ph, Ar, : : :) is a kind of new species. Its cycloaddition reactions is a new area for the study of germy-lene chemistry. The mechanism of the cycloaddition reaction between singlet Me2Ge=Ge: and acetaldehyde was investigated with the B3LYP/6-31G* method in this work. From the potential energy profile, it could be predicted that the reaction has one dominant re-action pathway. The reaction rule is that the two reactants firstly form a four-membered Ge-heterocyclic ring germylene through the [2+2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge: atom in the four-membered Ge-heterocyclic ring germylene and the π orbital of acetaldehyde forming a π→p donor-acceptor bond, the four-membered Ge-heterocyclic ring germylene further combines with acetaldehyde to form an intermedi-ate. Because the Ge atom in intermediate happens sp3 hybridization after transition state, then, intermediate isomerizes to a spiro-Ge-heterocyclic ring compound via a transition state. The research result indicates the laws of cycloaddition reaction between Me2Ge=Ge: and ac-etaldehyde, and lays the theory foundation of the cycloaddition reaction between H2Ge=Ge: and its derivatives (X2Ge=Ge:, X=H, Me, F, Cl, Br, Ph, Ar, : : :) and asymmetric π-bonded compounds, which are significant for the synthesis of small-ring and spiro-Ge-heterocyclic ring compounds.
Key words:  Me2Ge=Ge:, Four-membered Ge-heterocyclic ring germylene, Spiro-Ge-heterocyclic compound, Potential energy profile
FundProject:
二甲基亚锗基锗烯与乙醛生成螺锗杂环化合物反应机理的密度泛函理论研究
卢秀慧*,李永庆,鲍伟杰,刘东婷
摘要:
用B3LYP/6-31G*方法研究了单重态二甲基亚锗基锗烯(Me2Ge=Ge:)与乙醛环加成反应的反应机理,根据该反应的势能面可以预言,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锗烯,由于该锗杂四元环锗烯中Ge:原子的4p空轨道与乙醛的?轨道形成了π→p授受键,从而使锗杂四元环锗烯进一步与乙醛结合生成了一中间体. 由于该中间体中的Ge:原子在过渡态之后发生了sp3杂化,从而使该中间体经过渡态异构化为了一螺锗杂环化合物. 该研究结果从理论上揭示了单重态二甲基亚锗基锗烯(Me2Ge=Ge:)与乙醛环加成反应的反应机制,奠定了亚锗基锗烯(H2Ge=Ge:)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理论基础.
关键词:  Me2Ge=Ge:,锗杂四元环锗烯,螺锗杂环化合物,势能面
DOI:10.1063/1674-0068/26/01/43-50
分类号: