对N,C,N'-arylruthenium (II) 和 (III) 2,2':6',2''-terpyridine离子进行选择性的准化和二聚化
Sipke H Wadman1, Remco W A Havenith, Martin Lutz
1Chemical Biology & Organic Chemistry, Debije Institute for Nanomaterials Science, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands.
Journal of the American Chemical Society
|January 22, 2010
概括
含有N,C,N结合联体的鲁复合物通过铜 (II) 氧化经历轻度化和二聚化. DFT计算揭示了没有配对的电子.
科学领域:
- 有机金属化学 有机金属化学
- 协调化学 协调化学
- 合成化学 合成化学
背景情况:
- 与N,C,N'-结合联体的鲁复合体因其独特的电子性质而引起人们的兴趣.
- 了解这些复合物的反应性对于开发新的合成方法至关重要.
研究的目的:
- 为了研究N,C,N'-结合的阿里卢特皮里丁复合物的化和二聚化反应.
- 阐明反应机制和氧化状态的作用.
主要方法:
- 鲁 (II) 复合物的氧化与铜 (II) 素盐.
- 动力学研究以确定反应顺序.
- 密度函数理论 (DFT) 计算来分析电子结构.
- 氧化还原数据和电子吸收光谱学.
主要成果:
- 实现了复合物的轻微化 (C-X合) 和二极化 (C-C合).
- 化发生在循环金属化联结体的位上.
- 反应动力学与氧化剂与复杂物比率有所不同,表明不同的反应途径.
- DFT的计算显示, (III) 种中的未配对电子定位在 para 位置.
结论:
- (III) 复合物作为持久的有机金属基,促进C-X和C-C合反应.
- 循环金属联结体的电子特性在指导反应性方面发挥着关键作用.
- 建立了二复合体功能化的温和条件.
更多相关视频
相关概念视频
Aromatic Hydrocarbon Cations: Structural Overview
Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
Removing one hydrogen from the intervening CH2 group with both...
Removing one hydrogen from the intervening CH2 group with both...
Electrophilic Addition to Alkynes: Halogenation
Introduction
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Halogenation of Alkenes
Halogenation is the addition of chlorine or bromine across the double bond in an alkene to yield a vicinal dihalide. The reaction occurs in the presence of inert and non-nucleophilic solvents, such as methylene chloride, chloroform, or carbon tetrachloride.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...
Nucleophilic Aromatic Substitution: Addition–Elimination (SNAr)
Nucleophilic substitution in aromatic compounds is feasible in substrates bearing strong electron-withdrawing substituents positioned ortho or para to the leaving group. The reaction proceeds via two steps: the addition of the nucleophile and the elimination of the leaving group.
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between the...
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between the...
Nucleophilic Aromatic Substitution: Elimination–Addition
Simple aryl halides do not react with nucleophiles. However, nucleophilic aromatic substitutions can be forced under certain conditions, such as high temperatures or strong bases. The mechanism of substitution under such conditions involves the highly unstable and reactive benzyne intermediate. Benzyne contains equivalent carbon centers at both ends of the triple bond, each of which is equally susceptible to nucleophilic attack. This 50–50 distribution of products is confirmed through isotopic...


![[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)