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采用密度泛函方法(DFT)研究了2-甲基-1,3-顺丁二烯在Rh(Ⅰ)催化下与苯甲醛反应生成高烯丙基醇的反应机理.在B3LYP/6-31+G*水平上优化了反应过程中所有反应物、过渡态、中间体以及产物的几何构型,通过能量和振动分析确认了过渡态的真实性.并且在相同基组水平上应用自然键轨道(NBO)、前线轨道理论和分子中的原子(AIM)理论分析了这些化合物的成键特征和轨道间的相互作用.报道了可能的反应通道IA:Re→IMA1→TSA1→IMA2→IMA3→TSA2→IMA4→IMA5→TSA3→IMA6→PA;IB:Re→IMB1→TSB1→IMB2→IMB3→TSB2→IMB4→IMB5→TSB3→IMB6→PB,根据相对能量分析确定反应通道IB具有相对较低的活化能,是反应的主通道,与实验结果一致.
The reaction mechanism of 2-methyl-1,3-cis-butadiene catalyzed by Rh (Ⅰ) with benzaldehyde to produce allyl alcohol was studied by density functional theory (DFT). At B3LYP / 6-31 + G * optimization of the geometry of all reactants, transition states, intermediates and products in the reaction process, the authenticity of the transition states was confirmed by energy and vibration analysis, and the natural bond orbital (NBO), frontier orbital theory and molecular (AIM) theory, the bonding characteristics and orbital interactions of these compounds were analyzed.The possible reaction channels IA: Re → IMA1 → TSA1 → IMA2 → IMA3 → TSA2 IB → Re → IMB1 → TSB1 → IMB2 → IMB3 → TSB2 → IMB4 → IMB5 → TSB3 → IMB6 → PB, it is determined from the relative energy analysis that the reaction channel IB has a relatively low activation energy , Is the main channel of reaction, consistent with the experimental results.