一个五中心的氧化还原系统:两个非无辜的 imino-o-benzoquinonato-ruthenium 功能的分子合通过一个pi接受器桥
Atanu Kumar Das1, Biprajit Sarkar, Jan Fiedler
1Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70550 Stuttgart, Germany.
Journal of the American Chemical Society
|June 10, 2009
概括
这项研究合成并描述了一种具有氧化还原活性连接体的新型鲁复合体,揭示了金属和有机成分之间的复杂电子转移途径. 这些发现有助于更好地理解多核金属系统中非无害的连接体行为.
科学领域:
- 协调化学 协调化学
- 无机化学 无机化学
- 材料科学 材料科学 材料科学
背景情况:
- 非无害的配体在调整金属复合物的电子性质方面发挥着至关重要的作用.
- 通过介导桥梁将氧化还原活性部分合起来,可以实现复杂的电子相互作用.
研究的目的:
- 合成和表征一种新型的复合物,其中含有非无害的伊米诺诺基联体,由四基{2 - 皮里迪尔) 皮拉桥接.
- 为了研究这个多核系统内的电子转移过程和氧化还原状态.
主要方法:
- 合成的 [Cl (Q) Ru (mu-tppz) Ru (Q) Cl] (n) 复合物.
- 抗异构体的结构特征.
- 使用循环电压测量的电化学研究.
- 光谱分析包括EPR和UV对NIR光谱电化学.
- 密度函数理论 (DFT) 的计算.
主要成果:
- 该综合体表现出,伊米诺西基和桥梁酸连接体的多个可访问的氧化状态.
- 电化学和光谱数据揭示了Ru (III) - iminosemiquinone系统中的反铁磁合.
- 逐步的电子转移发生在金属中心和桥接接在减少时.
- DFT计算阐明了边界分子轨道和电子相互作用.
结论:
- 合成的复合体表现出显著的非无辜行为,具有复杂的氧化还原活性.
- 该研究提供了对多核系统中电子转移动态的详细了解,其中包含电子合的氧化还原活性成分.
- 这项工作提供了基于金属-合物合作效应的功能材料设计的见解.
相关概念视频
Oxidation of Phenols to Quinones
In the presence of oxidizing agents, phenols are oxidized to quinones. Quinones can be easily reduced back to phenols using mild reducing agents. The electron-donating hydroxyl group enhances the reactivity of the aromatic ring, enabling oxidation of the ring even in the absence of an α hydrogen.
o-hydroxy phenols are oxidized to o-quinones and p-hydroxy phenols to p-quinones. Such redox reactions involve the transfer of two electrons and two protons. The reversible redox property is crucial in...
o-hydroxy phenols are oxidized to o-quinones and p-hydroxy phenols to p-quinones. Such redox reactions involve the transfer of two electrons and two protons. The reversible redox property is crucial in...
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Electron Transport Chain: Complex I and II
The mitochondrial electron transport chain (ETC) is the main energy generation system in the eukaryotic cells. However, mitochondria also produce cytotoxic reactive oxygen species (ROS) due to the large electron flow during oxidative phosphorylation. While Complex I is one of the primary sources of superoxide radicals, ROS production by Complex II is uncommon and may only be observed in cancer cells with mutated complexes.
ROS generation is regulated and maintained at moderate levels necessary...
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Aryldiazonium Salts to Azo Dyes: Diazo Coupling
The reaction of weakly electrophilic aryldiazonium (also called arenediazonium) salts with highly activated aromatic compounds leads to the formation of products with an —N=N— link, called an azo linkage. This reaction, presented in Figure 1, is known as diazo coupling and occurs without the loss of the nitrogen atoms of the aryldiazonium salt. Highly activated aromatic compounds such as phenols or arylamines favor the diazo coupling reaction. The coupling generally occurs at the para position.
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Chain-growth or addition polymerization is successive addition reactions of monomers with a polymer chain. In radical chain-growth polymerization, the reaction proceeds via a free-radical intermediate. The free radical is formed from radical initiators, which spontaneously generate free radicals by homolytic fission. Organic peroxides (such as dibenzoyl peroxide, as shown in Figure 1) or azo compounds are popular radical initiators. A low concentration ratio of radical initiator to monomer is...
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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...

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