【摘要】：采用密度泛函DFT-B3LYP理論對(duì)非血紅素鐵超氧化物活化丙烯分子多態(tài)反應(yīng)機(jī)理進(jìn)行了探討.研究結(jié)果表明氫原子抽取過(guò)程遵守單態(tài)反應(yīng)機(jī)制,主要在基態(tài)高自旋七重態(tài)勢(shì)能面進(jìn)行,且具有較低活化能(ΔG~≠=65.6 k J·mol~(-1)),非血紅素鐵超氧化物可以作為有效氧化劑抽取氫原子。單態(tài)反應(yīng)機(jī)制可能歸因于近來(lái)建議的交換-加強(qiáng)反應(yīng)原則(EER,鐵中心具有較大交換穩(wěn)定作用)。對(duì)于O-O鍵的活化,在CASSCF(10,8)/6-31+G(d)//TZVP水平下,勢(shì)能面交叉區(qū)內(nèi),高自旋七重態(tài)(S1)和五重態(tài)(Q0)的自旋-軌道耦合(SOC)常數(shù)分別為2.26和2.19 cm~(-1)。軌道分析表明兩條發(fā)生翻轉(zhuǎn)自旋軌道具有相同空間組成(π*sub),SOC禁阻,因此通過(guò)SOC作用反應(yīng)體系不可能有效地從七重態(tài)(S=3)勢(shì)能面系間穿越到五重態(tài)(S=2)勢(shì)能面,系間穿越可能發(fā)生在反應(yīng)最后的退出階段。
[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，

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