合成和表征一个中性三坐标有机异电子与氨基
Rei Kinjo1, Bruno Donnadieu, Mehmet Ali Celik
1UCR-CNRS Joint Research Chemistry Laboratory (UMI 2957), Department of Chemistry, University of California Riverside (UCR), Riverside, CA 92521-0403, USA.
概括
研究人员合成了一种作为易斯基的中性化合物. 这种化合物可以被氧化形成激素,为化学及其电子性质提供了新的见解.
科学领域:
- 有机金属化学 有机金属化学
- 碳烯化学 碳烯化学
- 化学 化学
背景情况:
- 氨基和玻兰分别是经典的易斯基和酸.
- 氨基的单电子氧化产生了基离子,而酸则被减少为基离子.
- 稳定的玻利和玻利离子是罕见的,并且在合成上具有挑战性.
研究的目的:
- 合成一个中性,三坐标化合物,作为一个易斯基.
- 为了研究这种新型化合物的单电子氧化.
- 描述由此产生的激素离子的电子结构.
主要方法:
- 一个中性三坐标衍生物的合成,由循环 (基) (氨基) 碳稳定.
- 合成的化合物的单电子氧化.
- Ab initio计算计算分析分子轨道的计算.
主要成果:
- 成功合成了一种表现出易斯基本性的中性三坐标化合物.
- 该化合物容易经历一电子氧化,形成稳定的基离子.
- 计算分析显示,p(π) 轨道是中性和激进离子物种电子结构的关键.
结论:
- 合成的化合物作为稳定的易斯基,可以氧化为其根子.
- 这些发现提供了对稳定母烯和烯物种的访问.
- 电子属性由p(π) 轨道控制,为基化学提供了基本的见解.
相关概念视频
Structural Isomerism
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can be...
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can be...
Preparation of Amines: Reductive Amination of Aldehydes and Ketones
Carbonyl compounds and primary amines undergo reductive amination first to produce imines, followed by secondary amines in the same reaction mixture, using selective reducing agents like sodium cyanoborohydride or sodium triacetoxyborohydride. Reductive amination produces different degrees of substitution of amines depending on the starting amine substrate.
Structure of Amines
The hybridized nitrogen atom in amines possesses a lone pair of electrons and is bound to three substituents with a bond angle of around 108°, which is less than the tetrahedral angle of 109.5°. However, the C–N–H bond angle is slightly larger at 112°, with a carbon–nitrogen bond length of 147 pm. This carbon–nitrogen bond length of of amines is longer than the carbon–oxygen bond of alcohols (143 pm) but shorter than alkanes’ carbon–carbon bond (154 pm). These aspects are illustrated in Figure...
Amines to Amides: Acylation of Amines
Various carboxylic acid derivatives (such as acid chlorides, esters, and anhydrides) can be used for the acylation of amines to yield amides. The reaction requires two equivalents of amines. The first amine molecule functions as a nucleophile and attacks the carbonyl carbon to produce a tetrahedral intermediate. This is followed by the loss of the leaving group and restoration of the C=O bond.
Next, the second equivalent of amine serves as a Brønsted base and deprotonates the quaternary amide...
Next, the second equivalent of amine serves as a Brønsted base and deprotonates the quaternary amide...
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism
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.
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Overview
Nitrous acid and nitric acids are two types of acids containing nitrogen, among which nitrous acid is weaker than nitric acid. Nitrous acid with a pKa value of 3.37 ionizes in water to give a nitrite ion and the hydronium ion.
The nitrous acid is unstable. Hence, it is formed in situ from a solution of sodium nitrite and cold aqueous acids such as hydrochloric or sulfuric acid. In an acidic solution, the –OH group of nitrous acid undergoes protonation to give oxonium ion, followed by water loss...
The nitrous acid is unstable. Hence, it is formed in situ from a solution of sodium nitrite and cold aqueous acids such as hydrochloric or sulfuric acid. In an acidic solution, the –OH group of nitrous acid undergoes protonation to give oxonium ion, followed by water loss...


