Density ＇Functional Theory Study on Mechanism of Forming Spiro-Geheterocyclic Ring Compound from Me2Ge--Ge： and Acetaldehyde  

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

作　　者：卢秀慧[1] 李永庆[1] 鲍伟杰[1] 刘东婷[1] 

机构地区：[1]济南大学化学化工学院,济南250022

出　　处：《Chinese Journal of Chemical Physics》2013年第1期43-50,I0003,共9页化学物理学报（英文）

摘　　要：The H2Ge=Ge：, as well as and its derivatives （X2Ge=Ge：, X=H, Me, F, C1, Br, Ph, At, ...） is a kind of new species. Its cycloaddition reactions is a new area for the study of germylene 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 reaction 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 ~ orbital of acetaldehyde forming a r^--~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, C1, Br, Ph, At, ...） and asymmetric ^-bonded compounds, which are significant for the synthesis of small-ring and spiro-Ge-heterocyclic ring compounds.

关 键 词：Me2Ge=Ge： Four-membered Ge-heterocyclic ring germylene Spiro-Ge-heterocyclic compound Potential energy profile 

分 类 号：O[理学]