乙到乙烯的室温脱
Vincent N Cavaliere1, Marco G Crestani, Balazs Pinter
1Department of Chemistry and Molecular Structure Center, Indiana University, Bloomington, Indiana 47405, USA.
Journal of the American Chemical Society
|June 18, 2011
概括
一个基复合物在室温下激活乙C-H键,形成乙烯 adduct. 随后的氧化产生了化物复合物,证明了对有机化合物的新反应性.
科学领域:
- 有机金属化学 有机金属化学
- 化学 的化学
- 在C-H激活激活.
背景情况:
- 类基胺是反应性中间体.
- -键激活是化学中的一个关键转换.
- 了解早期过渡金属基胺的反应性至关重要.
研究的目的:
- 为了研究一个短暂的基基复合物的反应性.
- 为了探索对乙的C-H键激活.
- 描述由此产生的联体复合物及其转化.
主要方法:
- 合成基化的前体.
- 在室温下,基与乙的反应.
- 使用光谱方法对中间体和产品进行表征.
- 使用有机亚化物进行的氧化研究.
主要成果:
- 类基, (PNP) TiC(t) Bu,在室温下激活乙C-H键.
- 发生β-转移,形成一个-乙烯添加物.
- 与有机亚酸盐的氧化导致乙烯挤出和单核模态复合物.
结论:
- 过渡性类基利丁素能够进行C-H激活和随后的连接体重组.
- 这项研究揭示了产生化物复合物的新途径.
- 这些发现有助于理解早期过渡金属的反应性.
相关概念视频
Reduction of Alkenes: Catalytic Hydrogenation
Alkenes undergo reduction by the addition of molecular hydrogen to give alkanes. Because the process generally occurs in the presence of a transition-metal catalyst, the reaction is called catalytic hydrogenation.
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the surface of...
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the surface of...
Electrophilic Addition of HX to 1,3-Butadiene: Thermodynamic vs Kinetic Control
The addition of a hydrogen halide to 1,3-butadiene gives a mixture of 1,2- and 1,4-adducts. Since more substituted alkenes are more stable, the 1,4-adduct is expected to be the major product. However, the product distribution is strongly influenced by temperature; low temperature favors the 1,2-adduct, whereas the 1,4-adduct is predominant at high temperature.
Stability of Conjugated Dienes
Introduction
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
Acid-Catalyzed Hydration of Alkenes
Alkenes react with water in the presence of an acid to form an alcohol. In the absence of acid, hydration of alkenes does not occur at a significant rate, and the acid is not consumed in the reaction. Therefore, alkene hydration is an acid-catalyzed reaction.
Carboxylic Acids to Methylesters: Alkylation using Diazomethane
Carboxylic acids react with diazomethane in an ether solvent via alkylation at the carboxylate oxygen atom to give methyl esters of the corresponding acid with excellent yields.
Reduction of Benzene to Cyclohexane: Catalytic Hydrogenation
Unlike the easy catalytic hydrogenation of an alkene double bond, hydrogenation of a benzene double bond under similar reaction conditions does not take place easily. For example, in the reduction of stilbene, the benzene ring remains unaffected while the alkene bond gets reduced. Hydrogenation of an alkene double bond is exothermic and a favorable process. In contrast, to hydrogenate the first unsaturated bond of benzene, an energy input is needed; that is, the process is endothermic. This is...


