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Carl N Iverson1, Charles A G Carter, R Tom Baker
1Los Alamos Catalysis Initiative, Chemistry Division, MS J514, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA. bakertom@lanl.gov
Journal of the American Chemical Society
|October 16, 2003
概括
甲基复合物与罗化离子产生 cis 和 trans 异构体. 转变异构体迅速激活C-H键,而化溶剂则揭示了对催化反应的机制性见解.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 合成化学 合成化学
背景情况:
- 复合物在催化过程中至关重要.
- 了解连接体对反应性的影响是关键.
- 激活C-H键是一种基本的转变.
研究的目的:
- 为了合成和表征中性甲基复合物.
- 为了研究异构体对C-H激活反应性的影响.
- 使用同位素标记阐明反应机制.
主要方法:
- 通过与N- ((arylimino) pyrrolide离子的反应合成甲基复合物.
- 对C-H激活中cis和trans同位素活性进行比较研究.
- 在C6D6中进行标记实验,以追踪甲基组的起源.
主要成果:
- 成功合成了 cis 和 trans 中性甲基复合物.
- 与cis异构体相比,转异构体在C-H激活中表现出明显更高的活性 (>80x).
- 同位素标记揭示了不同的甲基组转移途径,这取决于替代剂的批量.
结论:
- 甲基复合物的立体化学有着深刻的影响C-H激活效率.
- N- ((arylimino) pyrrolide配体的立体和电子因素影响反应结果.
- 机理学研究为催化C-H功能化提供了宝贵的见解.
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...
¹H NMR: Complex Splitting
A proton M that is coupled to a proton X results in doublet signals for M. However, NMR-active nuclei can be simultaneously coupled to more than one nonequivalent nucleus. When M is coupled to a second proton A, such as in styrene oxide, each peak in the doublet is split into another doublet.
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied first.
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied first.
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...
Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)
Two NMR-active nuclei bonded to a central atom can be involved in geminal or two-bond coupling. Geminal coupling is commonly seen between diastereotopic protons in chiral molecules and unsymmetrical alkenes, among others.
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
¹H NMR: Long-Range Coupling
The coupling interactions of nuclei across four or more bonds are usually weak, with J values less than 1 Hz. While these are usually not observed in spectra, the presence of multiple bonds along the coupling pathway can result in observable long-range coupling.
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene π orbitals.
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene π orbitals.
C–C Bond Cleavage: Retro-Aldol Reaction
The reverse of the aldol addition reaction is called the retro-aldol reaction. Here, the carbon–carbon bond in the aldol product is cleaved under acidic or basic conditions to form two molecules of carbonyl compounds. The mechanism of the reaction consists of three steps.
In the first step, as depicted in Figure 1, the base deprotonates the β-hydroxy ketone at the hydroxyl group to form an alkoxide ion.
In the first step, as depicted in Figure 1, the base deprotonates the β-hydroxy ketone at the hydroxyl group to form an alkoxide ion.


