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采用密度泛函理论(DFT)中的B3LYP方法,研究了Cu(I)催化六氢氮杂卓衍生物偶联反应的微观反应机理.在6-31+G(d)的水平下,对反应路径中的所有反应物、中间物、过渡态和产物进行了构型优化,通过振动频率分析及内禀反应坐标(IRC)计算对过渡态进行了验证,应用自然键轨道理论(NBO)和分子中的原子理论(AIM)分析了这些物质的轨道间相互作用及成键特征.报道了可能的反应通道CuI+R1+R2→IM2→TS1→IM3→TS2→IM4→IM5→TS3→IM6→TS4→IM7→P1→P1+IM8→IM9a→TS5a→IM10a→TS6a→IM11a→IM12→TS7→IM13→TS8→IM14→TS9→IM15→P2活化能相对较低,是主要的反应通道.同时对比研究了在没有Cu(Ι)催化剂时,反应的活化能为199.01kJ/mol,而在Cu(Ι)催化下,反应活化能为176.94kJ/mol,说明了Cu(Ι)催化剂促进了反应的进行.
The B3LYP method in density functional theory (DFT) was used to study the microscopic reaction mechanism of the Cu (I) -catalyzed coupling reaction of hexahydroazepine derivatives. At 6-31 + G (d) level, All the reactants, intermediates, transition states and products in the route were optimized. The transition states were verified by the vibrational frequency analysis and the intrinsic reaction coordinate (IRC) calculations. By using the theory of natural bond orbital (NBO) and molecular (AIM) analysis of the orbital interactions and bonding characteristics of these materials reported the possible reaction channels CuI + R1 + R2 → IM2 → TS1 → IM3 → TS2 → IM4 → IM5 → TS3 → IM6 → TS4 → IM7 → P1 → P1 + IM8 → IM9a → TS5a → IM10a → TS6a → IM11a → IM12 → TS7 → IM13 → TS8 → IM14 → TS9 → IM15 → P2 The activation energy is relatively low and is the main reaction channel. In the absence of Cu (I) catalyst, the activation energy of the reaction is 199.01 kJ / mol and the activation energy is 176.94 kJ / mol under the Cu (I) catalysis, indicating that the Cu (I) catalyst promotes the reaction.