一个反应性 (IV) - 氧化复合物:一个缺失的中间体在通过高金属-氧甲类化合物转移的原子
Jan Paulo T Zaragoza1, Maxime A Siegler1, David P Goldberg1
1Department of Chemistry , The Johns Hopkins University , 3400 North Charles Street , Baltimore , Maryland 21218 , United States.
Journal of the American Chemical Society
|March 16, 2018
概括
这项研究合成了一种罕见的 ((IV) 氧化复合物,证明了其强大的原子抽象能力. 这种 (IV) 氧化物是一种比 (V) 氧化物复合体更强的H原子抽取器.
科学领域:
- 无机化学 无机化学
- 生物有机化学 生物有机化学
- 催化剂是一种催化剂.
背景情况:
- 高价值的金属氧化物物种是O2激活和生产中的关键中间体.
- 具有良好的特征的单核M ((IV)) ((OH)) 复合体很少,这限制了机理学的理解.
研究的目的:
- 为了合成和表征一种新的单核 ((IV) 氧化复合物.
- 与相关的物种相比,研究这个复合物的反应性和H原子抽象能力.
主要方法:
- 复合物的合成和X射线衍射 (XRD) 特性.
- 使用UV-Vis光谱学从醇中提取H原子的动态研究.
- 动态同位素效应 (KIE) 的测量.
主要成果:
- 通过使用硬质要求高的冠状体连接体,成功合成和结构性表征了Mn(IV) ((OH) ((ttppc).
- 在H原子抽象中,Mn () 呈现出明显更高的反应性 (k2 ≈ 2.73 × 10^4 M^-1 s^-1),比Mn () V () O () 呈现出更高的反应性 (k2 ≈ 2.73 × 10^4 M^-1 s^-1).
- 来自替代和KIE数据的相关性证实了协调的原子转移 (HAT) 机制.
结论:
- 固态阻碍的Mn{\displaystyle Mn}{\displaystyle Mn}{\text{IV}{\text{OH}}}}复合体是一种罕见且强大的H原子抽取器.
- 在H原子抽象中, (IV) (OH) 复合物表现优于高价值 (V) (O) 和一些Fe (IV) (O) 复合物.
- 这项工作为通过高价值金属复合体介导的OH键裂解机制提供了关键的见解.
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