合成动力稳定的1,2-二二二二二二
Tomohiro Agou1, Yusuke Sugiyama, Takahiro Sasamori
1Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan.
Journal of the American Chemical Society
|February 24, 2012
概括
研究人员使用重的基组合成了稳定的1,2-二二基. 这些化合物表现出独特的-双键特性,在加热时经历异构化为三基.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
- 频谱学是一种光谱学.
背景情况:
- 1,2-二二基烯是基烯的类型.
- 稳定低坐标物种是一个挑战.
- 了解Si=Si结合提供了对化学的洞察.
研究的目的:
- 为了合成和表征动态稳定1,2-二二二烯.
- 为了研究Si=Si双键的电子特性.
- 为了研究这些disilene的热反应性.
主要方法:
- 1,2-二二基烯的合成,使用固态体积大的基.
- 溶液和固态特性 (例如,NMR,X射线晶体学).
- 在溶液中进行热异构化研究.
主要成果:
- 成功分离了动态稳定的1,2-二二基.
- 在溶液和固体状态中都有显著的Si=Si双键性质的证据.
- 与水素相比,Si-H键具有更高的s特性.
- 在中度加热后观察到对三基的异构化,以分子内迁移作为速度限制的步骤.
结论:
- 绝缘保护是有效的隔离反应性1,2-二二基.
- 合成的化合物由于Si=Si键而具有独特的电子特性.
- 热异构化为新的化结构提供了一条途径.
相关概念视频
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
Diels–Alder Reaction: Characteristics of Dienes
The Diels–Alder reaction brings together a diene and a dienophile to form a six-membered ring. Both components have unique characteristics that influence the rate of the reaction.
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is more stable, the...
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is more stable, the...
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.
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.
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.
Structure of Conjugated Dienes
Introduction
Conjugated dienes are compounds characterized by the presence of alternating double and single bonds. In a conjugated system like 1,3-butadiene, the unhybridized 2p orbital on each carbon overlaps continuously, allowing the π electrons to be delocalized across the entire molecule. In contrast, this type of overlap does not occur in cumulated and isolated dienes, such as 2,3-pentadiene and 1,4-pentadiene, respectively. Instead, the π electrons remain localized between the double...
Conjugated dienes are compounds characterized by the presence of alternating double and single bonds. In a conjugated system like 1,3-butadiene, the unhybridized 2p orbital on each carbon overlaps continuously, allowing the π electrons to be delocalized across the entire molecule. In contrast, this type of overlap does not occur in cumulated and isolated dienes, such as 2,3-pentadiene and 1,4-pentadiene, respectively. Instead, the π electrons remain localized between the double...


