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采用密度泛函理论(DFT)研究了钯催化苯乙烯与N-氟代双苯磺酰胺反应机理.在B3LYP/6-311+G*基组水平上对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进行了优化,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)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.研究发现了两条可能的反应通道IA与IB,其控制步骤活化能分别为17.81 k J.mol-1、56.04k J.mol-1,由以上比较结果可以看出,IA通道具有较低的活化能,即IA通道为整个反应的最优反应通道,与实验结果一致.此外我们还研究了溶剂对反应的影响.
The reaction mechanism of palladium catalyzed by styrene and N-fluorobisbenzenesulfonamide was studied by density functional theory (DFT). The reaction of all reactants, transition states, The geometry of the intermediate and the product was optimized. The transition state was confirmed by energy and vibration analysis. And the atomic bond (AIM) theory of natural bond orbital (NBO) The bonding characteristics and orbital interactions of these compounds were studied.The two possible reaction channels, IA and IB, were found to have activation energies of 17.81 k J. mol-1, 56.04 k J. mol-1 The above results show that the IA channel has a lower activation energy, that is, the IA channel is the optimal reaction channel for the entire reaction, which is consistent with the experimental results.In addition, we also study the impact of solvent on the reaction.