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DFT Study of Mechanism of Extraction Reaction Between Germylene Carbene (H2Ge=C:) and Its Derivatives and Ethylene Oxide
Xiu-hui Lu*,Xin Che,Yong-qing Li,Zhi-na Wang
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  
Yong-qing Li School of Chemistry and Chemical Engineering, University of Ji'nan, Ji'nan 250022, China  
Zhi-na Wang School of Chemistry and Chemical Engineering, University of Ji'nan, Ji'nan 250022, China  
Abstract:
The mechanism of the oxide extraction reaction between singlet germylene carbene and its derivatives X2Ge=C: (X=H, F, Cl, CH3) and ethylene oxide has been investigated with B3LYP/6-311G(d,p) method. The results show that this kind of reaction has similar mecha-nism, the shift of 2p lone electron pair of O in ethylene oxide to the 2p unoccupied orbital of C in X2Ge=C: gives a p→p donor-acceptor bond, thereby leading to the formation of inter-mediate. As the p→p donor-acceptor bond continues to strengthen, that is the C-O bond continues to shorten, the intermediate generates product (P+C2H4) via transition state. It is the substituent electronegativity that mainly affect the extraction reactions. When the substituent electronegativity is greater, the energy barrier is lower, and the reaction rate is greater.
Key words:  Germylene carbene, Extraction reaction, Ethylene oxide, Potential energy surface
FundProject:
亚锗基卡宾及取代亚锗基卡宾与环氧乙烷抽提反应机理的密度泛函理论研究
卢秀慧*,车昕,李永庆,王智娜
摘要:
采用B3LYP/6-311G(d,p)方法研究了单重态亚锗基卡宾及取代亚锗基卡宾X2Ge=C:(X=H, F, Cl, CH3)与环氧乙烷的氧转移反应机理. 结果表明, 由于环氧乙烷中氧上的2p孤对电子向X2Ge=C:中C上的2p空轨道迁移,形成了p→p授受键,从而生成了各中间体. 随着p→p授受键的不断加强(即C-O键的逐渐缩短),中间体经过渡态生成了抽提产物. 取代基的电负性是影响该类反应的主要因素,取代基的电负性越大,反应的活化能越小
关键词:  :亚锗基卡宾,抽提反应,环氧乙烷,势能面
DOI:10.1088/1674-0068/24/03/311-314
分类号: