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| 1 | Quantum chemical and topological study on the insertion reaction of dichlorcarbene with acetaldehyde显示文摘The insertion reaction mechanisms of siglet and striglet CCl2 with CH3CHO have been studied by using the DFT, NBO, CCSD(T) and AIM method. The geometries of reactions, transition state and products were completely optimized by B3LYP/6-31G(d). All the energy of the species was obtained at the CCSD(T)/6-31G(d,p) level. The calculated results indicated that all the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CCl2 can not only insert the Cα—H (reaction I) but also can react with Cβ—H (reaction Ⅱ). There are three main existing pathways and the products are P1 (CH3COHCCl2), P2 (CH2COHCHCl2) and P4[CHCl2CHCHOH] respectively. Reaction Ⅱ happens more easily according to the energy changes and the barrier in rate-controlling step. In addi-tion, the important geometries in domain pathways have been studied by AIM theory. And also, the en-ergy changes of H in the inserted C—H bond have been investigated. | LI ZhiFeng ZHU YuanCheng YANG Sheng LU XiaoQuan | 2008 | Chinese Science Bulletin2008，53，15： | 1 |
| 2 | Quantum chemical study on insertion and abstraction reaction of dichlorocarbene with methyl alcohol and methyl mercaptan显示文摘The insertion and abstraction reaction mechanisms of singlet and triplet CCl2 with CH3MH (M=O, S) have been studied by using the DFT, NBO and AIM methods. The geometries of reactions, the transition state and products were completely optimized by B3LYP/6-311G(d, p). All the energy of the species was obtained at the CCSD(T)/6-311G(d, p) level. The calculated results indicated that the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CCl2 can not only trigger the insertion reaction with C-H and M-H in four pathways, by which the products P1 [CH3OCHCl2, reactionⅠ(1)], P3[Cl2HCCH2OH, reactionⅠ(2)], P5[CH3SCHCl2, reactionⅡ(1)] and P7[Cl2HCCH2SH, reac-tion Ⅱ(2)] are produced respectively, but also abstract M-H, resulting P4 [CH2O+CH2Cl2, reactionⅠ(3)] and P8[CH2S+CH2Cl2, reactionⅡ(3)]. In addition, the important geometries in domain pathways have been studied by AIM and NBO theories. | LI ZhiFeng ZHU YuanCheng LI HuiXue LIU XinWen LU XiaoQuan | 2009 | Science China Chemistry2009，52，3： | 1 |
| 3 | 二氯卡宾与甲醇及甲硫醇反应的拓扑积分和热力学与动力学性质显示文摘在b3lyp/6—311g(d,p)水平上运用经Wigner校正的Eyring过渡态理论和统计热力学方法,对CCI,与CHaMH(M=O,S)中C—H键、M—H键插入反应的热力学与动力学性质及其拓扑积分性质进行了研究。计算结果表明,在250~850K的温度范围内,更有利于CCl2插入甲醇O-H键生成产物P1[CH3OCHCl2]的反应I(1)的发生.而在850-2200K的温度范围内,反应I(1)及I(2)[插入C—H键,生成P3:Cl2HCCH2OH]没有明显的选择优势;CCl2插入甲硫醇O-H[反应II(1)]及C—H[反应II(2)]的适宜温度为400-1600K,低温下有利于生成CH3SCHCl2,而在高温下,反应II(1)及II(2)的选择性优势也不明显。最后,讨论了被插入C—H键、O—H键及S—H键中H原子的能量变化. | 李志锋 李红玉 何文静 | 2009 | 天水师范学院学报2009，29，2： | 0 |
| 4 | 二溴卡宾与CH_3OH多通道反应的理论计算显示文摘对单、三重态CBr_2与CH_3OH的多通道反应进行了理论计算.在B3LYP/6-311G*水平上优化了势能面上构型并进行了构型确认.计算了各物种经零点能校正的CCSD(T)能量.结果表明,单重态CBr_2既可以与O—H键插入生成1,1-二溴代甲醚P1(CH_3OCHBr_2),也可以与C—H键插入生成2,2-二溴代乙醇P3(Br_2HCCH_2OH).同时,存在单重态CBr_2与CH_3OH抽提双氢生成P_(abs)(CH_2O+CH_2Br_2)的反应.采用统计热力学及Wigner校正的Erying理论研究了主反应通道的热力学及动力学性质,并对反应通道上的关键点进行了NBO和AIM分析. | 李志锋 何文静 唐慧安 朱元成 | 2009 | 原子与分子物理学报2009，26，6： | 0 |
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