的结构特征和氧化反应性 (II) 酸复合物
Jun Nakazawa1, Shota Terada, Masaki Yamada
1Department of Material and Life Chemistry, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama 221-8686, Japan. jnaka@kanagawa-u.ac.jp
Journal of the American Chemical Society
|April 16, 2013
概括
这项研究详细介绍了一种新型 (II) - 乙烯复合物,Ni (Tp) -CF3Me (κ) -mCPBA),证明其对硫化物和烯酸的电友氧化和从碳化合物中提取H原子的能力.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 无机化学 无机化学 有机化学
背景情况:
- 复合物是有机合成中的多功能催化剂.
- 乙基氧联体可以调解氧化反应.
- 了解反应机制对于催化剂设计至关重要.
研究的目的:
- 为了合成和表征一种新的 (II) - 乙烯复合物.
- 为了研究该复杂的氧化和H原子抽象能力.
- 为了阐明反应动力学和机制.
主要方法:
- (II) - 乙烯复合物的分离和完整的特征.
- 电友氧化反应与硫化物和烯酸.
- 碳化合物的原子抽象反应.
- 动力学研究 (迈凯利斯-门,二阶动力学).
主要成果:
- ((II) - 乙烯复合物[Ni ((Tp ((CF3Me)) ((κ ((2) -mCPBA)) ]已成功合成和表征.
- 该综合体表现出硫化物和烯酸的电友性氧化,与密亚尼索尔的迈凯利斯-门动力学.
- 它还显示了H原子对激活的C-H键的抽象能力,遵循二次动力学.
- 有证据表明,一种替代途径涉及O-O分裂的中间体,用于较少反应性碳化合物.
结论:
- 新型 (II) - 乙烯复合物是各种有机基质的有效氧化剂.
- 反应机制因基质的反应性而异,涉及完整复合物和O-O分裂的中间体.
- 这项工作扩大了催化氧化反应的范围.
相关概念视频
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Oxidation of aldehydes and ketones results in the formation of carboxylic acids. Aldehydes, bearing hydrogen next to the carbonyl group, are easily oxidized compared to ketones. This is because an aldehydic proton can easily be abstracted during oxidation.
Aldehydes readily undergo oxidation in strong oxidizing agents such as potassium permanganate and chromic acid. The oxidation can also be carried out using mild oxidizing agents such as silver oxide. In fact, aldehydes can be easily oxidized...
Aldehydes readily undergo oxidation in strong oxidizing agents such as potassium permanganate and chromic acid. The oxidation can also be carried out using mild oxidizing agents such as silver oxide. In fact, aldehydes can be easily oxidized...
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
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.
Alkynes to Carboxylic Acids: Oxidative Cleavage
Alkynes undergo oxidative cleavage in the presence of oxidizing reagents like potassium permanganate and ozone. The triple bond — one σ bond and two π bonds — is completely cleaved, and the alkyne is oxidized to carboxylic acids. When warm and basic aqueous potassium permanganate is used as an oxidizing agent, alkynes are first converted to carboxylate salts via an unstable α-diketone intermediate. Further, a mild acid treatment protonates the carboxylate anions generating free carboxylic acid...
Oxidation of Alcohols
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:
Oxidation of Phenols to Quinones
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 property is crucial in...
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 property is crucial in...
Acid-Catalyzed Ring-Opening of Epoxides
Epoxides that are three-membered ring systems are more reactive than other cyclic and acyclic ethers. The high reactivity of epoxides originates from the strain present in the ring. This ring strain acts as a driving force for epoxides to undergo ring-opening reactions either with halogen acids or weak nucleophiles in the presence of mild acid. The acid catalyst converts the epoxide oxygen, a poor leaving group, into an oxonium ion, a better leaving group, making the reaction feasible. The...


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