有机异甲基的类同类与Cu(I) imide在侧向模式中的相互作用
Shuai-Cong Huo1, Yao Li1, Peng-Fei Ji1
1School of Chemistry and Chemical Engineering, Central South University, Lushannan Road 932, 410083 Changsha, China. yangy@csu.edu.cn.
Dalton transactions (Cambridge, England : 2003)
|July 31, 2023
概括
研究人员合成了一种新型的铜复合物,[NHC → GeN(Ar) Cu2NAr]2,通过将N-异环碳素 (NHC) 稳定基烯与铜伊米德进行反应. X射线晶体学揭示了和铜中心之间独特的侧面相互作用.
科学领域:
- 有机金属化学 有机金属化学
- 主要组化学主要组化学
- 协调化学 协调化学
背景情况:
- N-异环碳 (NHCs) 是稳定活性主群物种的多功能连接体.
- 化物代表了一个新兴的化合物类别,具有潜在的催化应用.
- 众所周知,铜伊米德能形成具有有趣结构图案的多核复合体.
研究的目的:
- 为了合成和表征一种在胺和铜胺之间形成的新型添加物.
- 为了研究化物部分与铜芯的协调模式.
- 探索将主要组元素与过渡金属相结合的结构影响.
主要方法:
- 一个N-异环碳 (NHC) 的合成稳定了非循环的细菌烯.
- 细菌烯与n-丁和一个铜 (I) 前体的反应.
- 在X射线晶体结构测定结果的添加物.
主要成果:
- 正式添加物 [NHC → GeN(Ar) Cu2NAr]2的形成,这是有机异二添加物的类似物.
- 结构阐明揭示了两个[GeNAr]单位与[Cu2NAr) 2]核心以侧向方式协调.
- 证实了NHC在稳定活性物种中的作用.
结论:
- 这项研究成功地合成和表征了一种独特的铜 adduct.
- 侧面协调模式突出了主要组和过渡金属之间的新型结合相互作用.
- 这项工作扩大了对胺胺化学及其与铜复合体的协调行为的理解.
相关概念视频
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
1.9K
Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. For instance, arenediazonium salts react with copper(I) salts of chloride, bromide, or cyanide to form corresponding aryl chlorides, bromides, and nitriles. These reactions are named Sandmeyer reactions. Although the mechanism of this reaction is complicated, as illustrated in Figure 1, they are believed to progress via an aryl copper...
1.9K
Nucleophilic Aromatic Substitution: Elimination–Addition
4.0K
Simple aryl halides do not react with nucleophiles. However, nucleophilic aromatic substitutions can be forced under certain conditions, such as high temperatures or strong bases. The mechanism of substitution under such conditions involves the highly unstable and reactive benzyne intermediate. Benzyne contains equivalent carbon centers at both ends of the triple bond, each of which is equally susceptible to nucleophilic attack. This 50–50 distribution of products is...
4.0K
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
6.1K
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...
6.1K
Acid Halides to Ketones: Gilman Reagent
3.0K
Lithium dialkyl cuprate, also known as Gilman reagents, selectively reduces acid halides to ketones. The acid chloride is treated with Gilman reagent at −78 °C in the presence of ether solution to produce a ketone in good yield.
As shown below, the mechanism proceeds in two steps. First, one of the alkyl groups of the reagent acts as a nucleophile and attacks the acyl carbon of the acid chloride to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen...
As shown below, the mechanism proceeds in two steps. First, one of the alkyl groups of the reagent acts as a nucleophile and attacks the acyl carbon of the acid chloride to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen...
3.0K
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
10.3K
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.
10.3K
Aldehydes and Ketones with Amines: Imine Formation Mechanism
5.7K
Imine formation involves the addition of carbonyl compounds to a primary amine. It begins with the generation of carbinolamine through a series of steps involving an initial nucleophilic attack and then several proton transfer reactions. The second part includes the elimination of water, as a leaving group, to give the imine.
Imines are formed under mildly acidic conditions. A pH of 4.5 is ideal for the reaction.
If the pH is low or the solution is too acidic, the reaction slows down in the...
Imines are formed under mildly acidic conditions. A pH of 4.5 is ideal for the reaction.
If the pH is low or the solution is too acidic, the reaction slows down in the...
5.7K


