对生物模拟非黑米铁复合物的O-O键裂变进行密度功能研究,证明Fe (v) -中间体
Arianna Bassan1, Margareta R A Blomberg, Per E M Siegbahn
1Contribution from the Department of Physics, Stockholm Center for Physics, Astronomy and Biotechnology, Stockholm University, S-106 91, Stockholm, Sweden. arianna@physto.se
铁复合物与三二甲基 (胺) 连接物催化碳化合物的氧化. DFT计算显示Fe(V) =O通过O-O异解与H(2) O(2) 形成,保持立体特异性.
科学领域:
- 有机金属化学 有机金属化学
- 计算化学计算化学
- 催化剂是一种催化剂.
背景情况:
- 铁复合物与三二甲基胺) (TPA) 连接体是已知的类固体碳化合物氧化的催化剂.
- 过氧化 (H2O2) 是这些催化系统中常见的氧化剂.
研究的目的:
- 通过使用H(2) O(2) 进行碳化合物氧化过程中Fe(TPA) 复合物的反应机制的研究.
- 探索催化中间体中O-O键裂解的途径.
主要方法:
- 使用B3LYP混合函数的密度函数理论 (DFT) 计算.
- 对O-O键裂变的反应路径和过渡状态的研究.
主要成果:
- 通过O-O键异解形成一种高价值的铁-氧介质 (Fe(V) = O),这与实验数据相一致.
- 与P450中间体不同的是,TPA连接体保持不氧化,主要从铁中心提取电子.
- 同解性O-O键裂变对于H(2) O(2) 来说在能量上是不可访问的,从而确保了反应的立体特异性.
- 对于酸氧化剂,O-O同解具有较低的障碍,导致立体特异性丧失.
结论:
- 该Fe(TPA) 系统通过Fe(V) = O形成通过异构的O-O裂变与H(2) O(2) 实现立体特异性氧化.
- 与基氧化物相比,H(2) O(2) 中较高的O-O键强度决定了裂变路径和立体特异性.
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