尼克尔的Eta2-有机化物复合物及其通过二挤出转化为终端的imido复合物
Rory Waterman1, Gregory L Hillhouse
1Gordon Center for Integrative Science, Department of Chemistry, The University of Chicago, 929 East 57th Street, Chicago, Illinois 60637, USA.
Journal of the American Chemical Society
|August 30, 2008
概括
有机亚的催化反应产生稳定的亚添加物. 这些中间体在加热后通过二挤出容易转化为终端的imido复合物.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂 催化剂
- 亚化物化学 亚化物化学
背景情况:
- 有机复合物是有机合成中的有价值的催化剂.
- 有机亚酸是含化合物的多功能前体.
研究的目的:
- 为了合成和表征新的酸添加物.
- 为了研究这些添加物对 imido 复合体形成的反应性.
主要方法:
- [{dtbpe) Ni]2{eta2-mu-C6H6) 与1-阿达曼提拉和梅西泰拉的反应.
- 分离和结晶学表征由此产生的亚酸添加物.
- 热解研究以确定分解途径.
主要成果:
- 稳定的eta2-有机亚酸添加物 (dtbpe) Ni(eta2-N3R) 已成功合成并对R=亚达曼和梅西进行了表征.
- 这些添加物被确定为终端形态复合物的形成中的关键中间体.
- 观察到在轻度热解亚添加物时会出现分子内二损失.
结论:
- 这项研究表明,通过阿齐德 adducts,结终端imido复合体的新途径.
- 这些发现提供了关于有机金属系统中二挤出机制的见解.
相关概念视频
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.
2° Amines to N-Nitrosamines: Reaction with NaNO2
Secondary amines react with nitrous acid to form N-nitrosamines, as depicted in Figure 1. Nitrous acid, a weak and unstable acid, is formed in situ from an aqueous solution of sodium nitrite and strong acids, such as hydrochloric acid or sulfuric acid, in cold conditions. In the presence of an acid, the nitrous acid gets protonated. The subsequent loss of water results in the formation of the electrophile known as nitrosonium ion.
Preparation of Amines: Reduction of Oximes and Nitro Compounds
Oximes can be reduced to primary amines using catalytic hydrogenation, hydride reduction, or sodium metal reduction. The reduction of aliphatic and aromatic nitro compounds to primary amines takes place by either catalytic hydrogenation or by using active metals like Fe, Zn, and Sn in the presence of an acid.
Though catalytic hydrogenation can reduce nitrobenzenes, the reduction is nonselective in the presence of other functional groups. For instance, if nitrobenzene contains an aldehyde group,...
Though catalytic hydrogenation can reduce nitrobenzenes, the reduction is nonselective in the presence of other functional groups. For instance, if nitrobenzene contains an aldehyde group,...
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...
Catalysis
The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
Nitriles to Amines: LiAlH4 Reduction
Nitriles are reduced to amines in the presence of strong reducing agents like lithium aluminum hydride through a typical nucleophilic acyl substitution. The reaction requires two equivalents of the reducing agent. The reducing agent acts as a source of hydride ions.
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...


