相关实验视频
Updated: Aug 29, 2025

09:58
Light-driven Enzymatic Decarboxylation
Published on: May 22, 2016
11.8K
在Redox-Inactive稀土中O2的过氧选择性降低产生两性过氧化物
Matthew J Lueckheide1, Mehmed Z Ertem2, Michael A Michon1
1Department of Chemistry, Brown University, Providence, Rhode Island02912, United States.
Journal of the American Chemical Society
|September 9, 2022
概括
研究人员合成了第一个分子氧化物,使选择性氧化减少成为可能. 这一发现为在催化和化学合成中利用氧化还原无活性金属离子提供了新的途径.
科学领域:
- 无机化学
- 有机金属化学
- 催化剂
背景情况:
- 金属过氧化物在生物和合成过程中至关重要.
- 稀土过氧化物参与催化,但研究不足.
- 对于孤立的,特征化的稀土过氧化物存在有限的反应性研究.
研究的目的:
- 报告使用稀土三酸盐选择性降解二氧化.
- 为了分离和描述第一个分子氧化物.
- 研究稀土过氧化物的反应性和机械路径.
主要方法:
- 使用甲基甲基铁素 (Fc*) 和稀土三酸盐在甲醇中选择性减少氧化物.
- 通过单晶X射线衍射,拉曼和NMR光谱学对氧化物 (2-Pr) 的分离和表征.
- 质子化研究和反应性评估 (电友和核友).
主要成果:
- 在二氧化物降解中达到高过氧选择性 (93-99% O2^2-).
- 成功分离和表征了第一个分子氧化物,[PrIII2 ((O2^2-) ((18C6) 2 ((EG) 2)) [OTf]4 (2-Pr).
- 证明了2-Pr的高热稳定性及其在氧原子转移和酸裂解中的反应性.
结论:
- 氧气的减少速度是由金属离子的可达性决定的,而不是易斯的酸度.
- 在电子转移之前的弱金属联体相互作用可以使氧化还原无活性金属离子具有差异反应性.
- 开辟了利用稀土金属中心的催化和合成的新途径.
相关概念视频
Regioselectivity of Electrophilic Additions-Peroxide Effect
8.8K
In the presence of organic peroxides, the addition of hydrogen bromide to an alkene yields the isomer that is not predicted by Markovnikov’s rule. For example, the addition of hydrogen bromide to 2-methylpropene in the presence of peroxides gives 1-bromo-2-methylpropane. This addition reaction proceeds via a free radical mechanism, which reverses the regioselectivity. The free radical reaction mechanism involves three stages: initiation, propagation, and termination.
8.8K
Oxidation of Phenols to Quinones
3.4K
In the presence of oxidizing agents, phenols are oxidized to quinones. Quinones can be easily reduced back to phenols using mild reducing agents. The electron-donating hydroxyl group enhances the reactivity of the aromatic ring, enabling oxidation of the ring even in the absence of an α hydrogen.
o-hydroxy phenols are oxidized to o-quinones and p-hydroxy phenols to p-quinones. Such redox reactions involve the transfer of two electrons and two protons. The reversible redox...
o-hydroxy phenols are oxidized to o-quinones and p-hydroxy phenols to p-quinones. Such redox reactions involve the transfer of two electrons and two protons. The reversible redox...
3.4K
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
6.1K
Diols are compounds with two hydroxyl groups. In addition to syn dihydroxylation, diols can also be synthesized through the process of anti dihydroxylation. The process involves treating an alkene with a peroxycarboxylic acid to form an epoxide. Epoxides are highly strained three-membered rings with oxygen and two carbons occupying the corners of an equilateral triangle. This step is followed by ring-opening of the epoxide in the presence of an aqueous acid to give a trans diol.
6.1K
Radical Oxidation of Allylic and Benzylic Alcohols
2.1K
Activated manganese(IV) oxide can selectively oxidize allylic and benzylic alcohols via a radical intermediate mechanism. Primary allylic alcohols are oxidized to aldehydes, while secondary allylic alcohols yield ketones. The redox reaction of potassium permanganate with an Mn(II) salt such as manganese sulfate (under either alkaline or acidic conditions), followed by thorough drying, yields the oxidizing agent: activated MnO2. While MnO2 is insoluble in the solvents used for the reaction, the...
2.1K
Redox Titration: Other Oxidizing and Reducing Agents
376
Besides iodine, other oxidizing or reducing agents can serve as titrants in redox titrations. Common oxidizing titrants include KMnO4, cerium(IV), and K2Cr2O7. The choice of oxidizing titrants depends on factors like stability, cost, analyte strength, and reaction rate between the analyte and titrant. KMnO4 is a strong oxidizing titrant that reduces from Mn(VII) to Mn(II) in a highly acidic solution, simultaneously oxidizing the analyte to a higher oxidation state. In this case, KMnO4 acts as a...
376
Sharpless Epoxidation
4.2K
The conversion of allylic alcohols into epoxides using the chiral catalyst was discovered by K. Barry Sharpless and is known as Sharpless epoxidation. The use of a chiral catalyst enables the formation of one enantiomer of the product in excess. This chiral catalyst is mainly a chiral complex of titanium tetraisopropoxide and tartrate ester (specific stereoisomer). The stereoisomer used in the chiral catalyst dictates the formation of the enantiomer of the product. In other words, the use of...
4.2K

