帕拉 (II) 含有g-Keggin的解,是一种有效催化烯酸的水化
Tomohisa Hirano1, Kazuhiro Uehara, Keigo Kamata
1Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Tokyo 113-8656, Japan.
一种新型的二替代重态催化剂有效地水多种. 这种催化剂[γ-H(2) SiW(10) O(36) Pd(2)(OAc)(2)](4-),在亚酸水化反应中表现出高活性和选择性.
科学领域:
- 无机化学 无机化学
- 催化剂是一种催化剂.
- 材料科学 材料科学 材料科学
背景情况:
- 酸水化是有机合成中至关重要的转化.
- 开发高效和选择性催化剂用于烯水化仍然是一个重大挑战.
- 聚氧甲酸盐为催化应用提供可调节的结构和氧化还原特性.
研究的目的:
- 为了合成和表征一种新的二替代的γ-Keggin解状态催化剂.
- 调查这种新催化剂的催化活性和选择性,以使各种烯酸化.
- 通过动力学,机械学和计算研究来阐明催化机制.
主要方法:
- 合成 [γ-H(2)SiW(10)O(36)Pd(2)(OAc)(2)](4-) 通过 [γ-SiW(10)O(34)(H(2)O)(2)](4-) 与 Pd(OAc)(2) 的反应.
- 合成化合物的结构确定X射线晶体学.
- 用合成的催化剂或前体混合物进行各种亚烯的催化化反应.
- 动力学研究,机械学研究和密度函数理论 (DFT) 计算.
主要成果:
- 成功合成和结构性表征的单体,二替代的γ-Keggin酸解状态与双酸连接体.
- 催化剂表现出高的催化活性和选择性,用于芳香,阿利法,异芳香和不和酸的水合.
- 对于3 - 氨基胺水合,实现了860h(-1) 的周转频率和670的周转数.
- 双位点被确定为催化作用的关键,核友性对二碳的攻击是决定速度的.
结论:
- 合成的二替代酸酸是一种高效的催化剂,用于酸水化.
- 催化剂的性能与其前体的简单混合物相美,突出显示了二位点的协同效应.
- 机械学的见解证实了二部分和催化循环中决定速率的核友性攻击的重要性.
更多相关视频
11:44Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions
Published on: March 20, 2014
12:08Catalytic Reactions at Amine-Stabilized and Ligand-Free Platinum Nanoparticles Supported on Titania During Hydrogenation of Alkenes and Aldehydes
Published on: June 24, 2022
相关概念视频
Preparation of Nitriles
Aldehydes and Ketones with Water: Hydrate Formation
The formation of hydrates is a reversible reaction. Hydrate formation is influenced by steric and electronic factors accompanying the alkyl substituents on the carbonyl group: The rate of hydrate formation increases with a decrease in the number of alkyl groups attached to the carbonyl carbon. Hence,...
Alkynes to Aldehydes and Ketones: Acid-Catalyzed Hydration
Analogous to alkenes, alkynes also undergo acid-catalyzed hydration. While the addition of water to an alkene gives an alcohol, hydration of alkynes produces different products such as aldehydes and ketones.
Catalysis
Nitriles to Amines: LiAlH4 Reduction
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...
Nitriles to Ketones: Grignard Reaction
The mechanism begins with a nucleophilic attack by the Grignard reagent...
