在的调反应性通过异质金属替代在一个氧化还原活性聚合物金属中
Leyla R Valerio1, Claire M Dopp1, William W Brennessel1
1Department of Chemistry, University of Rochester Rochester NY 14627 USA matson@chem.rochester.edu.
Chemical science
|March 2, 2026
概括
在与结合的硫基聚中,异金属的替代调整了电子特性,使控制的多电子反应和新型高价值复合物的合成成为可能,用于小分子激活.
科学领域:
- 无机化学 无机化学 有机化学
- 有机金属化学 有机金属化学
- 动因化物化学 动因化物化学
背景情况:
- 氧化还原活性金属体作为多电子转换的电子储库.
- 调整这些连接体的电子性质及其对金属中心反应性的影响还未得到充分研究,特别是在活性化物化学中.
研究的目的:
- 为了合成和研究异金属替代结合的聚基聚合物组件.
- 探索异金属替代如何调节中心的电子结构和反应性.
- 在小分子激活中比较异金属和同金属硫基聚的反应性.
主要方法:
- 从预先组装的UMo2复合物中合成一种异金属替代的-硫酸复合物, (Cp*3ZrMo2S4) Cp*UCl2.
- 减少到完全减少的集群, (Cp*3ZrMo2S4) Cp*U.
- 与同金属类型的小分子激活研究进行比较, (Cp*3Mo3S4)Cp*U.
- 使用亚博和元素硫的反应性研究.
主要成果:
- 在中心用基局部氧化替代异金属,形成一个U(VI) -bis(imido) 物种, (Cp*3ZrMo2S4)Cp*U(NPh) 2.2.
- 与元素硫的反应产生了一个独特的二硫化物桥接产品, (Cp*3ZrMo2S4) Cp*U(μ2-S2) 2.2.
- 与其全模拟物相比,异金属集群表现出明显的反应性,这有利于分解.
结论:
- 在氧化还原活性聚酸金属体中进行异金属替代是一种有效的策略,用于调整电子结构.
- 这种调调节了中心的多电子反应.
- 合成的复合物为探索化学和催化提供了新的途径.
更多相关视频
04:51Author Spotlight: Functionalizing Metal-Organic Frameworks: Advancements, Challenges, and the Power of Post-Synthetic Ligand Exchange
Published on: June 23, 2023
4.3K
10:10Application of Elemental Lanthanides in the Selective C-F Activation of Trifluoromethylated Benzofulvenes Providing Access to Various Difluoroalkenes
Published on: July 28, 2018
6.9K
相关概念视频
01:26Redox Titration: Other Oxidizing and Reducing Agents
1.5K
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...
1.5K
02:51Metal-Ligand Bonds
24.9K
The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
24.9K
01:26EDTA: Auxiliary Complexing Reagents
1.4K
EDTA titrations are usually carried out in highly basic conditions, where the fully deprotonated form of EDTA, Y4−, actively complexes with the free metal ions in the solution. Several metal ions precipitate as hydrous oxide (hydroxides, oxides, or oxyhydroxides) under these conditions, lowering the concentration of free metal ions in the solution. For this reason, auxiliary complexing agents or ligands such as ammonia, tartrate, citrate, or triethanolamine are used in EDTA titrations to...
1.4K
00:43Complexometric Titration: Ligands
2.4K
Different monodentate and polydentate ligands are used as complexing agents in complexometric titration reactions. The formation of complexes by mono- and bidentate ligands involves two or more intermediate steps, limiting their use as complexing agents. In comparison, polydentate ligands can form complexes with metal ions in a single-step process, facilitating sharper end points. This means polydentate ligands, such as amino carboxylic acid derivatives, are most commonly employed in...
2.4K
02:58Properties of Transition Metals
30.3K
Transition metals are defined as those elements that have partially filled d orbitals. As shown in Figure 1, the d-block elements in groups 3–12 are transition elements. The f-block elements, also called inner transition metals (the lanthanides and actinides), also meet this criterion because the d orbital is partially occupied before the f orbitals.
30.3K
01:19Complexation Equilibria: The Chelate Effect
1.4K
In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
1.4K