【摘要】 采用密度泛函理论(DFT)中的B3LYP方法对CuCl2催化的(2-甲基辛烷-2,3-二烯-4-基)磷酸乙酯氯代环化反应机理进行了理论研究.在6-31+G(d)基组水平上对反应机理中所有反应物、过渡态、中间体和产物进行了优化,通过能量和振动频率分析以及IRC计算证实了中间体和过渡态的合理性.在相同基组水平上应用自然键轨道(NBO)理论和分子中的原子(AIM)理论分析了复合物的成键特征和轨道间相互作用.反应物R和催化剂CuCl2可通过IA和IB两条可行反应通道生成中间体IM9,控制步骤活化能分别是129.61和142.10kJ/mol.中间体IM9到产物P也有两条反应路径PA和PB,控制步骤活化能分别是179.55和9.83kJ/mol.整个反应机理中IA→PB和IB→PB反应通道可能同时发生,反应控制步骤活化能最低反应通道为IA→PB.更多还原

【Abstract】 The microcosmic mechanism of CuCl2-catalyzed chlorocyclization reaction of ethyl(2-methylocta-2,3-dien-4-yl) phosphonate was studied by density functional theory B3LYP method.The geometries of the reactants,transition states,intermediates and products were optimized at the 6-31+G(d) level.A vibration analysis and an energy calculation and IRC calculation proved the authenticities of the intermediates and the transition states.Atoms in molecules(AIM) and nature bond orbital(NBO) theories were used to discuss the bond nature and orbital interactions at the same levels.Reactant R and catalyst CuCl2 can form the intermediate IM9 through the IA and IB two possible reaction paths.The activation energies of their limiting steps are 129.61 and 142.10 kJ/mol.For the next reaction steps from the intermediate IM9 to the product P,there are two possible reaction paths PA and PB,which limiting step activation energies are 179.55 and 9.83 kJ/mol.Both paths IA→PB and IB→PB may occur simultaneously.The path IA→PB is the lowest activation energy in the whole reaction.更多还原