CAJ | 학술논문

利用密度泛函理论( DFT)研究了Rh的芳基化合物与含氮芳基卤代物交叉偶联过程催化循环的微观反应机理。在B3LYP/6-31+G(d)基组水平上(Rh、I采用了赝势基组LanL2DZ)优化了反应过程中所有化合物的几何构型并计算了频率,通过能量、频率和振动方式确定了中间体和过渡态的真实性。此外,在同等基组水平上还运用了分子中的原子理论讨论了成键临界点的电荷密度的变化,运用了自然键轨道理论讨论了键的性质与轨道间的相互作用。为了提高计算精度,在6-311++G( d,p)基组水平上计算了反应机理中所有物质在气相及溶剂化下的单点能,得到与6-31+G( d)基组计算相同的结论。结论表明Rh(Ⅰ)起到了有效的催化作用,且计算所得结论与实验结果相符合。
이용밀도범함이론( DFT)연구료Rh적방기화합물여함담방기서대물교차우련과정최화순배적미관반응궤리。재B3LYP/6-31+G(d)기조수평상(Rh、I채용료안세기조LanL2DZ)우화료반응과정중소유화합물적궤하구형병계산료빈솔,통과능량、빈솔화진동방식학정료중간체화과도태적진실성。차외,재동등기조수평상환운용료분자중적원자이론토론료성건림계점적전하밀도적변화,운용료자연건궤도이론토론료건적성질여궤도간적상호작용。위료제고계산정도,재6-311++G( d,p)기조수평상계산료반응궤리중소유물질재기상급용제화하적단점능,득도여6-31+G( d)기조계산상동적결론。결론표명Rh(Ⅰ)기도료유효적최화작용,차계산소득결론여실험결과상부합。
The cross-coupling reaction mechanism of rhodium aromatic compounds with nitrogen-containing aryl halides has been investigated by density functional theory ( DFT). The geometries and the frequencies of re-actants, intermediates, transition states, and products have been calculated at the B3LYP/6–31+G( d) lev-el, and the LanL2DZ basis has been used as the extrabasis. The vibration analysis demonstrates that the authen-ticity of transition states, and the reaction processes are confirmed by the changes of charge density at bond-forming critical point analyzed by the atoms in molecules theory. In addition, the nature bond orbital has been used to discuss the bond nature and orbital interactions at the same level. Meanwhile, the single point energies of the reaction process in gas and solvent at 6 -311 + +G(d,p) level have been individually investigated with higher precision. The results indicate that the reaction mechanism and the change trend of correspondence energy at two different levels are consistent. The result of the theory study agrees with the experimental data, it indicates that the Rh(Ⅰ) is an effective catalyst in this reaction.