一种终端Ni (III) - 胺,具有多种反应途径
Elzbieta Kogut1, Heather L Wiencko, Libei Zhang
1Department of Chemistry, Georgetown University, Box 571227, Washington, DC 20057-1227, USA.
Journal of the American Chemical Society
|August 11, 2005
概括
(I) β-二甲胺酸复合物被合成并发生反应,形成-胺酸复合物. 这些复合物表现出独特的结合和反应性,包括imido组转移和基质特征.
科学领域:
- 有机金属化学 有机金属化学
- 无机化学 无机化学 有机化学
- 协调化学 协调化学
背景情况:
- 复合物与β-二甲基酸连接体是合成中的多功能构建块.
- 13电子碎片是形成新的金属-连接体键的反应性中间体.
研究的目的:
- 为了合成和表征新的β-二甲基胺Ni (I) 丁添加物.
- 为了探索这些添加物作为"裸体"碎片的合成子的反应性.
- 为了研究-伊米多复合物的形成和性质.
主要方法:
- 合成Ni (I) 露提丁添加物.
- 与N3Ad发生反应,形成Ni-imido复合体.
- 用于结构确定的X射线晶体学.
- 电子偏磁共振 (EPR) 光谱仪用于电子结构分析.
主要成果:
- 合成Ni (I) lutidine添加物及其作为合成剂的使用.
- 形成一个单个桥梁的 imide 短的 Ni-Ni 和 Ni-N ((imido) 距离.
- 隔离一个具有合约的Ni-N(imido) 债券和显著的多重债券性质的Ni(III) 终端 imide.
- 经过EPR研究,发现了体环境和高精度合与imido的关系.
- 证明了imido组转移反应和imido的激进性质.
结论:
- β-二甲基酸 (Ni) 复合物是反应性碎片的有效前体.
- 由此产生的-伊米多复合体表现出独特的结构和电子特性.
- 这些复合体表现出多样化的反应性,包括imido组转移和基于基的转化.
相关概念视频
Metal-Ligand Bonds
The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
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...
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...
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
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° 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.
Redox Titration: Other Oxidizing and Reducing Agents
Besides iodine, other oxidizing or reducing agents can serve as titrants in redox titrations. Common oxidizing titrants include KMnO4, cerium(IV), and K2Cr2O7. The choice of oxidizing titrants depends on factors like stability, cost, analyte strength, and reaction rate between the analyte and titrant. KMnO4 is a strong oxidizing titrant that reduces from Mn(VII) to Mn(II) in a highly acidic solution, simultaneously oxidizing the analyte to a higher oxidation state. In this case, KMnO4 acts as a...


