Theoretical Study on Mechanism of Cycloadditional Reaction Between Dichloro-Germylidene and Formaldehyde  

二氯亚甲基锗烯与甲醛环加成反应机理的理论研究

作　　者：卢秀慧[1] 李永庆[1] 徐曰华[1] 韩军锋[1] 时乐义[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》2010年第3期287-292,I0001,共7页化学物理学报（英文）

摘　　要：Mechanism of the cycloadditional formaldehyde has been investigated reaction between singlet with MP2/6-31G^＊ method, dichloro-germylidene and including geometry optimization, vibrational analysis and energies for the involved stationary points on the potential energy surface. From the potential energy profile, we predict that the cyeloaddition reaction between singlet dichloro-germylidene and formaldehyde has two competitive dominant 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-traasfer 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.

关 键 词：Dichloro-germylidene Cycloadditional reaction Potential energy surface 

分 类 号：O[理学]