在异化物的催化转化中,与之间显著的合作性
Mark C Lipke1, Allegra L Liberman-Martin1, T Don Tilley1
1Department of Chemistry, University of California , Berkeley, California 94720, United States.
Journal of the American Chemical Society
|July 8, 2016
概括
具有多个金属--键的鲁复合物介导着异化物转换. 这些反应展示了
科学领域:
- 有机金属化学
- 催化剂
- 化学
背景情况:
- 有M-H-Si键的鲁复合物是已知的催化剂.
- 异化物是有机合成中的多功能不和基质.
研究的目的:
- 研究具有多重M-H-Si键的鲁复合物的对异酸盐的反应性.
- 阐明由这些复合物介导的异化物转换机制.
- 探索在过渡金属催化反应中的作用.
主要方法:
- - 复合物的合成和特征.
- 在受控条件下与异化物发生反应.
- 标签,动态同位素效应 (KIE) 研究和NMR光谱学.
主要成果:
- 从复合物和异化物中形成碳复合物.
- 通过水化,化和C-H激活,复合物2a产生了一种西拉环印林产物.
- 复杂的1c催化异化物降解合形成基.
- 机理研究显示了各种协调物种的参与.
结论:
- -复合物可以调解复杂的异化物转换,包括伪催化和催化反应.
- 具有复杂的作用,通过多种协调模式和M-H-Si键参与.
- 这些发现扩大了对在过渡金属催化中的有用性的理解.
相关概念视频
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
4.0K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
4.0K
Heterogeneous Catalysis
75
Heterogeneous catalysis involves a catalyst in a different phase from the reactants. It is a process where the catalyst and the reactants are in distinct phases, typically solid and gas or liquid.Most heterogeneous catalysts are metals, metal oxides, or acids. The list includes transition metals like iron (Fe), cobalt (Co), nickel (Ni), palladium (Pd), platinum (Pt), chromium (Cr), manganese (Mn), tungsten (W), silver (Ag), and copper (Cu). These metals possess partially vacant d orbitals that...
75
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
9.3K
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
9.3K
Radical Reactivity: Concentration Effects
1.9K
In a radical reaction, the concentration of starting materials governs the selectivity of a radical. For example, the reaction between an alkyl halide and an alkene, in the presence of tin hydride and AIBN, begins with the generation of a tin radical. The generated radical then abstracts halogen from the alkyl halide, producing an alkyl radical. This alkyl radical can either react with tin hydride, yielding an alkane, or add to an alkene, generating a nitrile-stabilized radical, eventually...
1.9K
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
7.9K
All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...
7.9K
Catalysis
31.8K
The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
31.8K


