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Ab initio Study of Mechanism of Forming Germanic Bis-Heterocyclic Compound Between Dichloro-Germylene Carbene (Cl2Ge=C:) and Formaldehyde
Xiu-hui Lu*,Xin Che,Zhen-xia Lian,Yong-qing Li
Author NameAffiliationE-mail
Xiu-hui Lu* School of Chemistry and Chemical Engineering, University of Ji'nan, Ji'nan 250022, China lxh@ujn.edu.cn 
Xin Che School of Chemistry and Chemical Engineering, University of Ji'nan, Ji'nan 250022, China lxh@ujn.edu.cn 
Zhen-xia Lian 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 lxh@ujn.edu.cn 
Abstract:
The mechanism of the cycloaddition reaction of forming germanic bis-heterocyclic compound between singlet dichloro-germylene carbene and formaldehyde has been investigated with CCSD(T)//MP2/6-31G* method, from the potential energy profile, we predict that the re-action has two competitive dominant reaction pathways. The presented rule of this reaction: the 2p unoccupied orbital of the C atom in dichloro-germylene carbene insert the π orbital of formaldehyde from oxygen side, resulting in the formation of intermediate. In the interme-diate and between two reactants, because of the two bonding π orbital in dichloro-germylene carbene and formaldehyde have occurred [2+2] cycloaddition reaction, forming two four-membered ring compounds in which Ge and O are in the opposite orientation and in the syn-position, respectively. Because of the unsaturated property of C atom from carbene in the two four-membered ring compounds, they further reacts with formaldehyde, resulting in the generation of two germanic bis-heterocyclic compounds.
Key words:  Dichloro-germylene carbene, Reaction mechanism, Potential energy surface
FundProject:
二氯亚锗基卡宾与甲醛生成锗杂双环化合物反应的从头算研究
卢秀慧*,车昕,廉贞霞,李永庆
摘要:
用CCSD(T)//MP2/6-31G*方法研究了单重态二氯亚锗基卡宾(Cl2Ge=C:)与甲醛生成锗杂双环化合物的环加成反应机理,根据该反应的势能面可以预言,该反应有两条相互竞争的主反应通道.该反应所呈现的反应规律为:二氯亚锗基卡宾中C原子的2p空轨道因从氧端插入甲醛的π轨道而造成了中间体的形成;在中间体和两反应物之间,因二氯亚锗基卡宾和甲醛中的两成键π轨道发生了[2+2]环加成作用,从而分别生成了Ge-O对位的和Ge-O顺位的两四元环化合物;由于四元环化合物中卡宾C原子的不饱和性,进一步与甲醛作用,从而生成了两锗杂双环化合物.
关键词:  二氯亚锗基卡宾,反应机理,势能面
DOI:10.1088/1674-0068/23/04/402-408
分类号: