选择性B3) -H激活提供多核Ir3) -III) 复合体与 (o-Carboranyl) 二联体
Yong-Xiao Zhu1, Run-Ze Yuan1, Hai-Ning Zhang1
1Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, State Key Laboratory of Molecular Engineering of Polymers, Department of Chemistry, Fudan University, Shanghai, 200433, P. R. China.
Chemistry (Weinheim an der Bergstrasse, Germany)
|April 16, 2024
概括
研究人员开发了用于直接激活B-H的新型卡博拉尼尔二乙联体. 这种方法成功地形成了无银或的二金属和三金属复合物. 在B(3) 位置确认了选择性激活.
科学领域:
- 有机金属化学 有机金属化学
- 化学 化学
- 协调化学 协调化学
背景情况:
- 碳烯是多功能含集群,具有独特的电子特性.
- 开发有效的方法来使碳酸具有功能,并将其纳入金属复合体至关重要.
- 直接的C-H或B-H激活为复杂的有机金属结构提供了原子经济的途径.
研究的目的:
- 为了合成新型的卡博拉尼尔迪埃斯特桥接联体.
- 为了实现这些配体的直接B-H激活,使用 (III) 前体.
- 为了描述由此产生的双金属或三金属复合物,并确认选择性激活.
主要方法:
- 通过在位置换反应合成卡博拉尼尔二乙联体.
- 直接B-H激活使用半三明治的 (III) 复合物 ([Cp*IrCl2]2).
- 使用单晶X射线衍射和其他光谱技术对产品进行表征.
主要成果:
- 一系列连接两个或三个o-carborane单元的carboranyl dithioester配体已经成功合成.
- 通过[Cp*IrCl2]2实现了这些配体的直接B-H激活,而不需要白银或金属.
- 证实了双金属和三金属 (III) 复合物的形成,具有选择性的B (III) -H激活.
- 插入SnCl2的衍生物进一步支持了选择性的B(3) -H激活.
结论:
- 新型卡博拉尼尔二乙配体使有效的直接B-H激活通路成为可能.
- 这种方法为各种双金属和三金属碳-复合物提供了一条简单的途径.
- 在B(3) 位置的选择性激活突出了这些碳酸系统的受控反应性.
相关概念视频
02:51Metal-Ligand Bonds
20.7K
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...
20.7K
02:42Valence Bond Theory
8.5K
Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
8.5K
02:34Structural Isomerism
19.2K
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
19.2K
01:19Complexation Equilibria: The Chelate Effect
513
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...
513
00:43Complexometric Titration: Ligands
948
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...
948
01:22EDTA: Chemistry and Properties
1.9K
Polydentate ligands are most widely used in complexometric titrations because they form more stable complexes with the metal ions than mono- or bidentate ligands due to the chelate effect. Examples of polydentate ligands are ethylenediaminetetraacetic acid (EDTA), crown ethers, and cryptands. The most important feature of optimal polydentate ligands is the ability to form 1:1 complexes in a single-step process. Amino carboxylic acid derivatives are frequently used as complexing agents. EDTA is...
1.9K