三氧化衍生物支持三环:产生一个反应性 (III) 中心,具有单个反应性口袋
Ingrid Castro-Rodriguez1, Kristian Olsen, Peter Gantzel
1Department of Chemistry and Biochemistry, University of California-San Diego, 9500 Gilman Drive MC 0358, La Jolla, CA 92093-0358, USA.
Journal of the American Chemical Society
|April 10, 2003
概括
这项研究报告了具有独特反应性的新复合物. (III) 与亚化物反应,形成 (IV) 和 (V) 复合物,揭示了结合和电子结构的洞察力.
科学领域:
- 有机金属化学 有机金属化学
- 无机化学 无机化学
- 化学 的化学
背景情况:
- 复合物由于其独特的电子特性而引起人们的兴趣.
- 开发新的配体对于控制的反应性至关重要.
- 了解复合物的电子结构,可以了解它们的潜在应用.
研究的目的:
- 为了合成和表征新的单核复合体.
- 研究 (III) 复合物与有机亚酸盐的反应性.
- 阐明 (III), (IV) 和 (V) 复合体中的电子结构和结合.
主要方法:
- 单核复合物的合成.
- 谱学表征 (例如,UV-Vis,NMR) 进行.
- 单晶X射线衍射. 单晶X射线衍射.
- 密度函数理论 (DFT) 的计算.
主要成果:
- 成功合成和表征了 (III), (IV) 和 (V) 复合物,其中包含一个由三旋旋子支持的三-氧化物联体.
- 观察到 (III) 复合物与有机亚酸盐形成 (IV) 亚酸盐和 (V) 胺酸盐复合物的反应性.
- DFT研究显示, (III) 和 (V) 种类中的pi键稳定,与 (IV) 复合体中的离子键形成鲜明对比.
结论:
- 六酸连接体使协调不和反应性中心成为可能.
- 电子结构和结合方式随着的氧化状态 (+III, +IV, +V) 显著变化.
- 的f-轨道相互作用在稳定不同氧化状态和影响复杂性质方面发挥着关键作用.
更多相关视频
相关概念视频
Molecules with Multiple Chiral Centers
Molecules that possess multiple chiral centers can afford a large number of stereoisomers. For instance, while some molecules like 2-butanol have one chiral center, defined as a tetrahedral carbon atom with four different substituents attached, several molecules like butane-2,3-diol have multiple chiral centers. A simple formula to predict the number of stereoisomers possible for a molecule with n chiral centers is 2n. However, there can be a lower number where some of the stereoisomers are...
Thermal and Photochemical Electrocyclic Reactions: Overview
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
Photochemical Electrocyclic Reactions: Stereochemistry
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
Radical Reactivity: Overview
Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired molecule. These three...
Radical Reactivity: Steric Effects
The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
Along with electronic factors, steric factors also account...
Along with electronic factors, steric factors also account...
Pericyclic Reactions: Introduction
Pericyclic reactions are organic reactions that occur via a concerted mechanism without generating any intermediates. The reactions proceed through the movement of electrons in a closed loop to form a cyclic transition state, where rearrangement of the σ and π bonds yields specific products.
Pericyclic reactions can be classified into three categories: electrocyclic reactions, cycloaddition reactions, and sigmatropic rearrangements. Electrocyclic reactions and sigmatropic rearrangements are...
Pericyclic reactions can be classified into three categories: electrocyclic reactions, cycloaddition reactions, and sigmatropic rearrangements. Electrocyclic reactions and sigmatropic rearrangements are...
![Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F51444.jpg&w=3840&q=50)

