非血红素铁超氧化物活化丙烯分子多态反应机理的理论研究（英文）
发布时间：2019-01-14 11:26
【摘要】：采用密度泛函DFT-B3LYP理论对非血红素铁超氧化物活化丙烯分子多态反应机理进行了探讨.研究结果表明氢原子抽取过程遵守单态反应机制,主要在基态高自旋七重态势能面进行,且具有较低活化能(ΔG~≠=65.6 k J·mol~(-1)),非血红素铁超氧化物可以作为有效氧化剂抽取氢原子。单态反应机制可能归因于近来建议的交换-加强反应原则(EER,铁中心具有较大交换稳定作用)。对于O-O键的活化,在CASSCF(10,8)/6-31+G(d)//TZVP水平下,势能面交叉区内,高自旋七重态(S1)和五重态(Q0)的自旋-轨道耦合(SOC)常数分别为2.26和2.19 cm~(-1)。轨道分析表明两条发生翻转自旋轨道具有相同空间组成(π*sub),SOC禁阻,因此通过SOC作用反应体系不可能有效地从七重态(S=3)势能面系间穿越到五重态(S=2)势能面,系间穿越可能发生在反应最后的退出阶段。
[Abstract]:Density functional DFT-B3LYP theory was used to investigate the mechanism of polymorphic reaction of propene activated by non heme iron superoxide. The results show that the extraction process of hydrogen atom obeys the single-state reaction mechanism, it is mainly carried out on the ground state high spin seven-fold potential energy surface, and has a lower activation energy (螖 G ~ 鈮，
本文编号：2408644
[Abstract]:Density functional DFT-B3LYP theory was used to investigate the mechanism of polymorphic reaction of propene activated by non heme iron superoxide. The results show that the extraction process of hydrogen atom obeys the single-state reaction mechanism, it is mainly carried out on the ground state high spin seven-fold potential energy surface, and has a lower activation energy (螖 G ~ 鈮，
本文编号：2408644
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