在四核铁酸复合物中通过远程氧化还原调节激活氧化
Graham de Ruiter1, Niklas B Thompson1, Davide Lionetti1
1Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
Journal of the American Chemical Society
|September 22, 2015
概括
合成的四核铁复合体与位点差异化的金属中心使选择性电子存储成为可能. 这些铁团表现出独特的氧化激活和反应性,由它们的氧化还原状态调节.
科学领域:
- 无机化学
- 协调化学
- 生物有机化学
背景情况:
- 开发具有定制电子性能的多核金属复合体.
- 了解复杂分子结构中的金属中心差异化.
- 研究用于催化剂的氧化还原活性铁集群.
研究的目的:
- 合成和描述具有位点差金属中心的新型四核铁复合物.
- 研究这些复合物的电子性质和氧化还原行为.
- 探索氧化还原状态对氧化 (NO) 激活和反应性的影响.
主要方法:
- 四核铁复合体的合成,其中包括三核核和核铁中心.
- 电化学研究 (循环电压测量) 来确定氧化还原潜力.
- 莫斯巴尔光谱和晶体分析以阐明电子结构和氧化状态.
- 与氧化 (NO) 发生反应以研究结合和激活.
主要成果:
- 成功合成位点分化的四核铁复合物.
- 电化学研究揭示了三种可逆氧化还原事件,
- 莫斯巴乌尔和晶体学数据证实了三铁核心的氧化状态变化,而不是顶层铁.
- 氧化与铁中心结合,形成一个{FeNO}{7}部分.
- 三铁芯的氧化状态调节显著影响NO拉伸频率和激活.
- 观察到差异反应性,更多的富含电子的集群促进了NO不成比例和N2O的形成.
结论:
- 合成的铁复合物提供了一种在特定金属位点储存电子和洞等价物的策略.
- 位点区分允许独立调整氧化还原特性和NO激活.
- 铁团的氧化还原状态在调节NO结合,激活和随后的反应性方面起着至关重要的作用.
相关概念视频
Nitric Oxide Signaling Pathway
6.8K
Nitric oxide (NO), an inorganic gas, acts as a potent second messenger in most animal and plant tissues. NO diffuses out of the cells that produce it and enters the neighboring cells to generate a downstream response. NO synthase (NOS) catalyzes NO production by the deamination of the amino acid arginine. There are three isoforms of NOS. Endothelial cells have endothelial NOS (eNOS), nerve and muscle cells have neuronal NOS (nNOS), and macrophages produce inducible NOS (iNOS) upon exposure...
6.8K
Electron Transport Chain: Complex III and IV
9.7K
During the electron transport chain, electrons from NADH and FADH2 are first transferred to complexes I and II, respectively. These two complexes then transfer the electrons to ubiquinol, which carries them further to complex III. Complex III passes the electrons across the intermembrane space to Cyt c, which carries them further to complex IV. Complex IV donates electrons to oxygen and reduces it to water. As electrons pass through complexes I, III, and IV, the energy released aids the pumping...
9.7K
Redox Reactions
1.4K
Redox reactions are vital biochemical processes that underpin energy metabolism in cells. These reactions involve the transfer of electrons between molecules, occurring in tandem as oxidation and reduction. Oxidation refers to the loss of electrons, while reduction denotes their gain. This coupling ensures the seamless flow of electrons through metabolic pathways. For example, in bacterial metabolism, glucose undergoes oxidation to carbon dioxide, while oxygen is simultaneously reduced to...
1.4K
Redox Reactions
59.4K
Oxidation-reduction or redox reactions involve the transfer of electrons from one molecule or atom to another. When an atom gains an electron, another atom must lose an electron, meaning oxidation and reduction must occur together. Since the redox occurs in pairs, the atom that gets oxidized is also called the reducing agent or reductant, and the atom that is reduced is also called the oxidizing agent or oxidant. A straightforward way to remember the definitions of oxidation and reduction is...
59.4K
2° Amines to N-Nitrosamines: Reaction with NaNO2
5.8K
Secondary amines react with nitrous acid to form N-nitrosamines, as depicted in Figure 1. Nitrous acid, a weak and unstable acid, is formed in situ from an aqueous solution of sodium nitrite and strong acids, such as hydrochloric acid or sulfuric acid, in cold conditions. In the presence of an acid, the nitrous acid gets protonated. The subsequent loss of water results in the formation of the electrophile known as nitrosonium ion.
5.8K
Redox Titration: Other Oxidizing and Reducing Agents
1.7K
Besides iodine, other oxidizing or reducing agents can serve as titrants in redox titrations. Common oxidizing titrants include KMnO4, cerium(IV), and K2Cr2O7. The choice of oxidizing titrants depends on factors like stability, cost, analyte strength, and reaction rate between the analyte and titrant. KMnO4 is a strong oxidizing titrant that reduces from Mn(VII) to Mn(II) in a highly acidic solution, simultaneously oxidizing the analyte to a higher oxidation state. In this case, KMnO4 acts as a...
1.7K


