伊米达佐[1,5-a]二烯:一种适用于稳定的N-异环碳酸盐的多功能结构
Manuel Alcarazo1, Stephen J Roseblade, Andrew R Cowley
1Instituto de Investigaciones Químicas (CSIC-US), Américo Vespucio 49, E-41092 Seville, Spain.
Journal of the American Chemical Society
|March 10, 2005
概括
研究人员使用imidazo[1,5-a]pyridine框架开发了新的N-异环碳. 这些稳定的碳化合物,包括Rh (I) 单碳化合物和二碳化合物,在催化和材料科学中提供了新的可能性.
科学领域:
- 有机化学 有机化学
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
背景情况:
- 伊米达佐[1,5-a]里丁支架因其在开发新型碳联体方面的潜力而得到认可.
- 由于其独特的电子和硬质性质,N-异环碳 (NHC) 在催化和材料科学中至关重要.
研究的目的:
- 为了合成和表征新的稳定的N-异环碳从imidazo[1,5-a]pyridine骨架衍生.
- 探索这些新型碳作为有机金属化学中的配体的实用性.
主要方法:
- 合成伊米达佐[1,5-a]氨酸-3-烯酸 (ImPy) 和它们的衍生物.
- 制备和表征Rh (I) 单和双碳化合物复合物.
- 描述技术可能包括NMR光谱学,质谱学和潜在的X射线晶体学.
主要成果:
- 成功合成稳定的以皮里丁为基础的imidazo[1,5-a] N-异环碳.
- 形成Rh(I) 单碳和双碳复合物 (6和7),以及一个半离子碳衍生物 (13).
- 描述的碳化合物综合体证明了 imidazo[1,5-a]pyridine 平台的多功能性.
结论:
- 伊米达佐[1,5-a]里丁骨架是一种可行的和多功能平台,用于产生新型和稳定的N-异环碳.
- 合成的碳及其Rh (I) 复合物对催化和协调化学的应用有望.
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...
Carbocations
Carbocations are one of the reaction intermediates formed during several nucleophilic substitutions or elimination reactions. A carbocation is an electron-deficient species with the central carbon atom having six electrons and three bonded atoms. The central carbon in a carbocation is sp2 hybridized with trigonal planar geometry. It has an empty p orbital perpendicular to the plane of the structure that can accept electrons. Thus, carbocations act as strong electrophiles and may react with any...
Structures of Carboxylic Acid Derivatives
Structure of Carboxylic Acid Derivatives
Carboxylic acid derivatives contain an acyl group attached to a heteroatom such as chlorine, oxygen, or nitrogen. The carbonyl carbon and oxygen are both sp2-hybridized with an unhybridized p orbital.
The three sp2 orbitals of the carbonyl carbon form three σ bonds, one each with the carbonyl oxygen, the α carbon, and the heteroatom, whereas the other two sp2 orbitals of the carbonyl oxygen are occupied by the lone pairs. Further, the unhybridized p...
Carboxylic acid derivatives contain an acyl group attached to a heteroatom such as chlorine, oxygen, or nitrogen. The carbonyl carbon and oxygen are both sp2-hybridized with an unhybridized p orbital.
The three sp2 orbitals of the carbonyl carbon form three σ bonds, one each with the carbonyl oxygen, the α carbon, and the heteroatom, whereas the other two sp2 orbitals of the carbonyl oxygen are occupied by the lone pairs. Further, the unhybridized p...
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...
Basicity of Heterocyclic Aromatic Amines
Heterocyclic amines, where the N atom is a part of an alicyclic system, are similar in basicity to alkylamines. Interestingly, the heterocyclic amine having a nitrogen atom as part of an aromatic ring has much less basicity than its corresponding alicyclic counterpart. For this reason, as presented in Figure 1, piperidine (pKb = 2.8) is significantly more basic than pyridine (pKb = 8.8).
Nomenclature of Carboxylic Acid Derivatives: Amides and Nitriles
Naming Amides
The IUPAC and common names of amides are derived from the parent carboxylic acid, by replacing the suffix “oic acid” and “ic acid,” respectively, with “amide.” In the following example, the IUPAC name ethanamide is derived from ethanoic acid, and the common name, acetamide, is obtained from acetic acid.
The IUPAC and common names of amides are derived from the parent carboxylic acid, by replacing the suffix “oic acid” and “ic acid,” respectively, with “amide.” In the following example, the IUPAC name ethanamide is derived from ethanoic acid, and the common name, acetamide, is obtained from acetic acid.


