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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.
The mechanism of chlorination of CuCl2 catalyzed chlorination of ethyl 2-methyloctane-2, 3-dien-4-yl phosphate was studied by using B3LYP method in density functional theory (DFT) All reactants, transition states, intermediates and products in the reaction mechanism were optimized at the 6-31 + G (d) basis set level. The rationality of intermediates and transition states was confirmed by energy and vibrational frequency analysis and IRC calculations The bonding characteristics and orbital interactions of the complexes were analyzed by using the theory of natural bond orbital (NBO) and atomic (AIM) in the molecule at the same basis set level.The reactants R and the catalyst CuCl2 could be identified by IA and IB The feasible reaction channels lead to the intermediate IM9, and the activation energies of the control steps are 129.61 and 142.10 kJ / mol, respectively. There are also two reaction paths PA and PB in the intermediate IM9 to the product P, and the activation energies of the control steps are 179.55 and 9.83 kJ / mol, respectively. The reaction channels of IA → PB and IB → PB may occur simultaneously in the whole reaction mechanism, and the lowest activation channel of reaction control step is IA → PB.