相关实验视频
Updated: May 28, 2026

10:44
Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
Published on: April 19, 2019
通过d0复合体与α-二胺连接体,通过以连接体为中心的氧化还原过程产生碳基
Hayato Tsurugi1, Teruhiko Saito, Hiromasa Tanahashi
1Department of Chemistry, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan.
Journal of the American Chemical Society
|October 11, 2011
概括
合成了新的高价值复合物与氧化还原活性α-二胺配体. 这些复合物通过涉及连接体的独特电子转移机制促进了C-Cl键裂解和四乙酸盐分解.
科学领域:
- 有机金属化学 有机金属化学
- 协调化学 协调化学
- 降解氧化化学 降解氧化化学
背景情况:
- 高价值复合物在催化中具有价值.
- 反氧活性干提供可调节的电子性质.
- 了解电子转移机制对于反应性至关重要.
研究的目的:
- 合成和表征高价值复合物与氧化还原活性α-二胺联体.
- 调查这些复合物的作用在减少性C-Cl键裂解和氧化性四乙酸盐分解.
- 阐明二胺系统的氧化还原行为和电子结构.
主要方法:
- 合成 (α-二胺) TaCl (n) 复合物 (n=3,4) 使用TaCl (n5),α-二胺联体和一个有机还原剂.
- 涉及聚烯和四烯酸盐的反应,以研究反应性.
- 化学氧化和还原复合物的分离和表征.
- 电子偏磁共振 (EPR) 谱学用于研究基质物种.
主要成果:
- 成功制备高价值复合物与氧化还原活性α-二胺联体.
- 通过联体电子转移证明了三罗坦复合物的降解性C-Cl键裂解.
- 通过联体电子转移观察氧化四甲酸盐分解的四 хлоротантал复合物.
- 结合体中心的氧化还原产品的隔离,表示可调节的氧化还原状态.
- 通过EPR.识别溶液中的中心和配体局部化的基因异构体.
结论:
- 具有氧化还原活性α-二胺配体的高价值复合物表现出多样性的反应性.
- α-二胺联体在调节和氧化转换的电子转移中起着至关重要的作用.
- 这些复合物作为了解有机金属化学中的电子转移过程的有价值模型.
- 不同的氧化还原异构体的存在凸显了这些系统内的复杂电子相互作用.
相关概念视频
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 Formation: Addition
Radicals can be formed by adding a radical to a spin-paired molecule. This is typically observed with unsaturated species, where the addition of a radical across the π bond leads to the production of a new radical by dissolving the π bond. For example, the addition of a Br radical to an alkene yields a carbon-centered radical.
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an unpaired...
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an unpaired...
Radical Reactivity: Nucleophilic Radicals
Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For instance, consider...
Radical Formation: Elimination
Another method of radical formation is the elimination process. It is the opposite of the addition route and is driven by the instability of the radical. For example, as depicted in Figure 1, dibenzoyl peroxide yields a pair of unstable radicals upon homolysis. Given its instability, this radical spontaneously undergoes elimination via a C–C bond cleavage to form a relatively more stable phenyl radical. The mechanism involves cleavage of the bond between the α and β positions with respect to...
Radical Reactivity: Intramolecular vs Intermolecular
Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an electrophilic alkene or vice versa. In such reactions, the radical and generally the alkene, which is also called the radical trap, are two different molecules. Additionally, for such intermolecular reactions to occur, the radical trap must be active, present in an excess concentration, and the radical starting material must have a weak carbon–halogen...
Radical Formation: Overview
A bond can be broken either by heterolytic bond cleavage to form ions or homolytic bond cleavage to yield radicals. A fishhook arrow is used to represent the motion of a single electron in homolytic bond cleavage. There are two main sources from which radicals can be formed:
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the latter, also known...
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the latter, also known...

