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Theoretical Study on Mechanism of Cycloadditional Reaction Between Dichloro-Germylidene and Formaldehyde
Xiu-hui Lu*,Yong-qing Li,Yue-hua Xu,Jun-feng Han,Le-yi Shi
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  
Yue-hua Xu School of Chemistry and Chemical Engineering, University of Ji'nan, Ji'nan 250022, China  
Jun-feng Han School of Chemistry and Chemical Engineering, University of Ji'nan, Ji'nan 250022, China  
Le-yi Shi School of Chemistry and Chemical Engineering, University of Ji'nan, Ji'nan 250022, China  
Abstract:
Mechanism of the cycloadditional reaction between singlet dichloro-germylidene and formaldehyde has been investigated with MP2/6-31G* method, including geometry opti-mization, vibrational analysis and energies for the involved stationary points on the poten-tial energy surface. From the potential energy profile, we predict that the cycloaddition reaction between singlet dichloro-germylidene and formaldehyde has two competitive dom-inant reaction pathways, going with the formation of two side products (INT3 and INT4), simultaneously. Both of the two competitive reactions consist of two steps, two reactants firstly form a three-membered ring intermediate INT1 and a twisted four-membered ring intermediate INT2, respectively, both of which are barrier-free exothermic reactions of 41.5 and 72.3 kJ/mol; then INT1 isomerizes to a four-membered ring product P1 via transition state TS1, and INT2 isomerizes to a chlorine-transfer product P2 via transition state TS2, with the barriers of 2.9 and 0.3 kJ/mol, respectively. Simultaneously, P1 and INT2 further react with formaldehyde to form INT3 and INT4, respectively, which are also barrier-free exothermic reaction of 74.9 and 88.1 kJ/mol.
Key words:  Dichloro-germylidene, Cycloadditional reaction, Potential energy surface
FundProject:
Theoretical Study on Mechanism of Cycloadditional Reaction Between Dichloro-Germylidene and Formaldehyde
卢秀慧*,李永庆,徐曰华,韩军锋,时乐义
摘要:
用MP2/6-31G*方法研究了单线态二氯亚甲基锗烯与甲醛环加成反应的反应机理,该反应有两条相互竞争的主反应通道,同时伴随着两中间体(INT3和INT4)副产物的生成. 第一条主反应通道所生成的物种为三员环中间体(INT1)和Ge-O顺位的四员环产物(P1);第二条主反应通道所生成的物种为Ge-O对位的扭曲四员环中间体(INT2)和氯迁移产物(P2);P1和INT2分别与甲醛(R2)的进一步作用而导致了两副产物的生成.
关键词:  二氯亚甲基锗烯,环加成反应,势能面
DOI:10.1088/1674-0068/23/03/287-292
分类号: