コ ((サロフェン) -p-ヒドロキノンの催化性エアロビック酸化:エアロビック酸化触媒のメカニズムと影響
Colin W Anson1, Soumya Ghosh2, Sharon Hammes-Schiffer2
1Department of Chemistry, University of Wisconsin-Madison , 1101 University Avenue, Madison, Wisconsin 53706, United States.
Journal of the American Chemical Society
|March 1, 2016
まとめ
コバルト (塩) 複合体とp-ベンゾキノンは,有酸素酸化における酸化還元媒介体として作用する. この研究により,効率的な触媒化のために,陽子結合電子移転と水酸化物中間物質を含むシナジスティックメカニズムが明らかになった.
科学分野:
- カタリシス
- 有機化学
- 生物化学
背景:
- マクロサイクル金属複合体とp-ベンゾキノンは,有酸素酸化における重要な共触媒的還元媒介体である.
- その反応機構とエネルギー効率を理解することは,新しい触媒プロセスを開発する上で極めて重要です.
研究 の 目的:
- コバルト (塩) (コ) (サロフェン) によるp-ヒドロキノンの有酸素酸化のメカニズムとエネルギー効率を調査する.
- 酸素減少を媒介する触媒と共触媒の作用を明らかにする.
主な方法:
- 反応を研究するために,動力学的およびスペクトル学的分析が用いられました.
- 密度関数理論 (DFT) の計算は,反応経路と中間物質をモデル化するために使用された.
- 触媒サイクルを理解するために実験データと計算データを統合した.
主要な成果:
- 触媒の静止状態は,Co (II) (サロフェン),Co (III) 超酸化添加物,および水素結合添加物の均衡を伴う.
- 速度を制限するステップは,半ヒドロキノンからCo (III) -ヒドロペロキシド中間体への陽子結合電子移転です.
- 調整された過酸化水素の中間体は,第2のヒドロキノン分子を酸化する.
結論:
- Co ((salophen) とp-ヒドロキノンはエアロビック酸化において相乗効果を示す.
- このメカニズムは複雑な酸化還元プロセスと中間生成を含み,効率的なO2減量と共触媒再生につながります.
関連する概念動画
Oxidation of Phenols to Quinones
5.2K
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...
5.2K
Oxidation of Alcohols
18.1K
In this lesson, the oxidation of alcohols is discussed in depth. The various reagents used for oxidation of primary and secondary alcohols are detailed, and their mechanism of action is provided.
The process of oxidation in a chemical reaction is observed in any of the three forms:
The process of oxidation in a chemical reaction is observed in any of the three forms:
18.1K
Radical Autoxidation
3.4K
The oxidation of an organic compound in the presence of air or oxygen is called autoxidation. For example, cumene reacts with oxygen to form hydroperoxide. Autoxidation involves initiation, propagation, and termination steps. Many organic compounds are susceptible to autoxidation—especially ethers in the presence of oxygen, which form hydroperoxides. Even though this reaction is slow, old ether bottles contain small amounts of peroxide, which leads to laboratory explosions during ether...
3.4K
Phase I Reactions: Oxidation of Aliphatic and Aromatic Carbon-Containing Systems
878
Phase I biotransformation reactions are integral to drug metabolism, predominantly involving oxidative, reductive, and hydrolytic transformations. Chief among these are oxidative reactions, which enhance the hydrophilicity of xenobiotics and introduce polar functional groups to facilitate their elimination from the body.
Oxidation reactions are fundamental in aromatic carbon-containing systems. An example is the hydroxylation of phenobarbital, a process that transforms it into...
Oxidation reactions are fundamental in aromatic carbon-containing systems. An example is the hydroxylation of phenobarbital, a process that transforms it into...
878
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
13.4K
Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
13.4K
Drug Metabolism: Phase I Reactions
5.6K
A phase I reaction is a biochemical process that introduces a functionally reactive polar group to a substance. This transformation predominantly occurs in the liver, facilitated by the cytochrome P450 system of hemoproteins situated in the lipophilic endoplasmic reticulum of cells. The metabolite generated through this process can have varying polarities. If it is sufficiently polar, it can be easily excreted in the urine due to its water compatibility. However, if the metabolite is nonpolar,...
5.6K


![Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F60786.jpg&w=3840&q=50)