氧化氧化氧化氧化酸盐Ni (I) 和Cu (I) C-有机酸盐添加物
Stefan Wiese1, Pooja Kapoor, Kamille D Williams
1Department of Chemistry, Georgetown University, Box 571227, Washington, D.C. 20057-1227, USA.
Journal of the American Chemical Society
|December 17, 2009
概括
和铜β-diketiminato复合物形成C-nitroso附加物与ArN=O,显示不同的结合和N-O键激活. 这些复合物进一步与氧化发生反应,产生新的N-aryl-N-nitrosohydroxylaminato复合物,并证明氧化化.
科学领域:
- 有机金属化学 有机金属化学
- 协调化学 协调化学
- 无机合成 无机合成
背景情况:
- 具有β-二甲基胺酸连接体的金属复合物在协调化学中具有多功能.
- 金属复合物的与有机酸盐化合物的反应是理解N-O键激活的关键.
- 具有ArN=O的单价和铜复合物的反应性尚未完全阐明.
研究的目的:
- 为了研究单价和铜β-diketiminato复合物的反应与ArN=O.
- 描述由此产生的C-nitroso添加物及其结合方式.
- 探索这些添加物与氧化 (NO) 的后续反应性.
主要方法:
- 和铜β-diketiminato复合物的合成和表征.
- 金属复合物的反应与ArN=O (Ar = 3,5-Me(2) C(6) H(3), Ph) 形成C-nitroso附加物.
- 射线晶体学和红外光谱学以确定结构和N-O键激活.
- 孤立的添加物与气态氧化 (NO) 的反应.
主要成果:
- 形成三种不同的C-酸 adducts与不同的N-O键激活:{[Me(2) NN]Ni}(2)(mu-eta(2):eta(2)-ONAr),{[Me(2) NN]Cu}(2)(mu-eta(2):eta(1)-ONAr),和[Me(2) NN]Cueta(2)-ONAr).
- X射线结构显示了ArN=O部分的对称和不对称的结合,具有显著延长的N-O结合距离 (高达1.440~4) Å).
- 红外光谱学证实了在915,1040和1113厘米−1处减少N=O激活与 adduct形成 (ν(NO) 的情况.
- 与NO的反应导致N-aryl-N-nitrosohydroxylaminato复合物[Me(2) NN]M(kappa(2) -O(2) N(2) Ar) (M = Ni,Cu) 和的尼特复合物.
结论:
- 单价和铜β-diketiminato复合物有效地与ArN=O反应,导致各种C-nitroso附加物.
- 这些添加物中N-O键激活的程度可以根据金属和结合模式进行调节.
- 这些添加物通过与NO的反应作为新型有机金属复合物的前体,包括氧化化的一种例子.
相关概念视频
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.
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...
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.
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,...
Nitrosation of Enols
The nitrosation reaction is one of the methods of preparing 1,2-diketones. The enol tautomer of the starting ketone reacts with sodium nitrite in hydrochloric acid, generating the 1,2-diketone after hydrolysis.
Electrophilic Aromatic Substitution: Nitration of Benzene
The nitration of benzene is an example of an electrophilic aromatic substitution reaction. It involves the formation of a very powerful electrophile, the nitronium ion, which is linear in shape. The reaction occurs through the interaction of two strong acids, sulfuric and nitric acid.


