用二氧化碳在二氧化框架中的二裂变和功能化
Qingde Zhuo1, Jimin Yang2, Zhenbo Mo1
1Organometallic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan.
Journal of the American Chemical Society
|April 5, 2022
概括
这项研究证明了二 (N2) 与二氧化碳 (CO2) 的第一次反应,使用的是化复合物. 这一突破使N-C键形成,并为和二氧化碳的功能提供了洞察力.
科学领域:
- 无机化学
- 有机金属化学
- 催化剂
背景情况:
- (N2) 和二氧化碳 (CO2) 的激活和功能化是至关重要的,但具有挑战性的化学转化.
- 开发高效的N2和CO2利用的催化系统是可持续化学的一个关键目标.
研究的目的:
- 报告N2和CO2之间的新反应,由化复合物介导.
- 在这个系统中研究N-C键的形成和N-N和C-O键的裂变.
- 阐明反应机制并探索合成中的潜在应用.
主要方法:
- 含有二的二化物复合物的合成和特征.
- 复合物与二氧化碳在不同条件下的反应 (温度,压力,固体测量).
- 反应产品的隔离和结构确定.
- 使用同位素标记 (15N,13C) 和密度函数理论 (DFT) 计算的机制研究.
- 探索以为媒介的催化循环以合成异酸盐.
主要成果:
- 化物复合物与二氧化碳反应形成N-C键,裂解N-N和C-O键.
- 在低温下选择性形成化物/N,N-二化物复合物 (在-50°C下产量为82%)
- 在室温或加热二胺复合物时形成二酸/二复合物.
- 中间异酸/化物/氧化物复合物的分离.
- 从N2,CO2和Me3SiCl中使用H2合成三甲基西酸盐的介导循环的建立.
结论:
- 这项研究提供了第一个N2和CO2反应的例子,导致N-C键的形成.
- 可以调整反应条件以选择性地产生不同的复合物,包括化物和异化物.
- 通过同位素标记和DFT计算获得了机械洞察力,揭示了N2-CO2相互作用的前所未有的细节.
- 已经证明了从N2和CO2中合成有价值的异酸盐的可行催化循环.
相关概念视频
Preparation of Nitriles
2.2K
One of the common methods to prepare nitriles is the dehydration of amides. This method requires strong dehydrating agents like phosphorous pentoxide or boiling acetic anhydride for converting amides to nitriles. Another reagent namely, thionyl chloride also accomplishes the dehydration of amides, where amide acts as a nucleophile. The first step of the mechanism involves the nucleophilic attack by the amide on the thionyl chloride to form an intermediate. In the next step, the electron pairs...
2.2K
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism
4.1K
Nitrous acid is a relatively weak and unstable acid prepared in situ by the reaction of sodium nitrite and cold, dilute hydrochloric acid. In an acidic solution, the nitrous acid undergoes protonation when it loses water to form a nitrosonium ion—an electrophile. Nitrous acid reacts with primary amines to give diazonium salts. The reaction is called diazotization of primary amines.
4.1K
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
10.9K
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.
10.9K
Radical Formation: Homolysis
3.8K
A bond is formed between two atoms by sharing two electrons. When this bond is broken by supplying sufficient energy, either two electrons can be taken up by one atom forming ions by the cleavage called heterolysis, or the two electrons are shared by two atoms, with one each creating radicals by the cleavage called homolysis.
3.8K
Diels–Alder Reaction: Characteristics of Dienes
4.5K
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...
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...
4.5K
Aldehydes and Ketones with HCN: Cyanohydrin Formation Mechanism
3.4K
Cyanohydrins are formed when cyanide nucleophiles and carbonyl compounds like aldehydes and ketones react. A strong base, the cyanide ion, catalyzes cyanohydrin formation. The ions are generated from HCN under aqueous conditions. Once the cyanide ions are generated, the first step involves the nucleophilic attack of the cyanide ions on the electrophilic carbonyl carbon. This attack shifts the π electrons from the C=O to the oxygen atom forming the alkoxide ion intermediate. The alkoxide anion...
3.4K


