在 imido-bridged dirhodium (III) 和 amido-bridged dirhodium (II) 复合物之间,由和氧驱动的相互转换
Koji Ishiwata1, Shigeki Kuwata, Takao Ikariya
1Department of Applied Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152-8552, Japan.
Journal of the American Chemical Society
|March 18, 2009
概括
本研究详细介绍了二 (III) 硫胺化合物复合物的合成和反应性. 这些复合物经历氧化还原相互转换,可以催化有氧氧化反应,展示了它们在催化中的潜力.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 协调化学 协调化学
背景情况:
- 具有桥接连体的迪罗复合体对催化有兴趣.
- 硫胺联体具有独特的电子和硬质性质.
- 了解氧化还原行为的理解对于催化应用至关重要.
研究的目的:
- 为了合成和表征新的硫利米多桥接二 (III) 复合物.
- 为了研究这些复合体与捐赠者和氧的反应性.
- 探索它们作为有氧氧化反应中的催化剂的潜力.
主要方法:
- 通过与p-toluenesulfonamide的反应合成二 (III) 硫烯胺复合物.
- 研究与捐赠者 (H2,2-propanol) 和氧的反应性.
- DFT计算和实验研究以阐明反应机制.
- 催化测试H2和酒精的有氧氧化.
主要成果:
- 形成硫利米多桥接的二 (III) 复合物[Cp*Rh) ] (1a).
- 在二 (III) 胺基复合物和二 (II) 胺基复合物之间进行氧互转换.
- 复合物1a在H2和酒精的有氧氧化中表现出催化活性,与相关的或非桥接复合物不同.
结论:
- 合成的迪罗复合物表现出有趣的氧化还原特性和反应性.
- 硫胺连接体在这些迪罗复合物的催化活性中起着关键作用.
- 这些发现突出了双核复合物的潜力,作为有氧氧化催化剂.
相关概念视频
Structural Isomerism
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 be...
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 be...
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
Diazonium Group Substitution: –OH and –H
Nitrous acid, a weak acid, is prepared in situ via the reaction of sodium nitrite with a strong acid under cold conditions. This nitrous acid prepared in situ reacts with primary arylamines to form arenediazonium salts. Such reactions are known as diazotization reactions. As shown in Figure 1, the formation of arenediazonium salts begins with the decomposition of nitrous acid in an acidic solution to give nitrosonium ions.
Valence Bond Theory
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...
Colors and Magnetism
Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human eye.
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human eye.
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.


