通过基于Cp*M/N (M = Rh, Ir) 对的挫败的易斯对来激活CO,异化物和基
Carlos Ferrer-Bru1, Joaquina Ferrer1, Fernando J Lahoz1
1Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC─Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza, Spain.
Inorganic chemistry
|May 19, 2025
概括
和的复合物与皮里迪尼尔-阿米丁配体表现出挫败的易斯对反应性. 这些复合物与一氧化碳,异酸盐和酸盐反应,形成具有多种结合方式和结构的新有机金属化合物.
科学领域:
- 有机金属化学 有机金属化学
- 丧的易斯配对化学
- 协调化学 协调化学
背景情况:
- 挫败的易斯对 (FLP) 是由于硬质障碍而不能结合的易斯酸和,使其具有独特的反应性.
- 具有合联体的过渡金属复合物可以稳定活性物种并调节FLP类的转化.
- 皮里迪尼尔-阿米丁连接物为金属中心提供了多功能协调模式.
研究的目的:
- 为了研究和复合物的反应性,这些复合物以pyridinyl-amidine连接物作为丧的易斯对.
- 探索这些金属FLP与一氧化碳,异酸盐和酸盐等不和基质的相互作用.
- 描述由此产生的有机金属产品并阐明它们的结构特征.
主要方法:
- 新型 ((I) 和 ((I) 复合物的合成和特征与皮里迪尼尔-阿米丁配体.
- 这些复合物的与各种不和基质 (CO,异酸盐,) 的反应.
- 使用分析技术,光谱学 (NMR,IR) 和X射线衍射 (XRD) 来阐明新化合物的结构.
主要成果:
- 和复合体表现出丧的易斯对反应性,与CO,异酸盐和等基质进行接触.
- 对于含有CO的和复合物,观察到不同的反应途径,导致碳和碳衍生物.
- 复合物经历了1,1-插入和协调的异化物,并与终端基形成基复合物. 一个1,2-添加产品被观察到与二甲基乙基碳酸盐.
结论:
- 皮里迪尼尔-阿米丁支持的和复合体作为有效的丧的易斯对平台,用于小分子激活.
- 金属中心的电子和硬质性质 (Rh与Ir) 影响了与CO等基质的反应结果.
- 一系列具有独特结合安排的新有机金属复合物已被合成和特征化.
相关概念视频
02:24Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
7.6K
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
7.6K
01:11ortho–para-Directing Activators: –CH3, –OH, –NH2, –OCH3
5.7K
All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the...
5.7K
02:47Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
17.7K
Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
17.7K
01:10Aldehydes and Ketones with HCN: Cyanohydrin Formation Mechanism
2.9K
Cyanohydrins are formed when cyanide nucleophiles and carbonyl compounds like aldehydes and ketones react. A strong base, the cyanide ion, catalyzes cyanohydrin formation. The ions are generated from HCN under aqueous conditions. Once the cyanide ions are generated, the first step involves the nucleophilic attack of the cyanide ions on the electrophilic carbonyl carbon. This attack shifts the π electrons from the C=O to the oxygen atom forming the alkoxide ion intermediate. The...
2.9K
01:22Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
1.8K
The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
1.8K
01:32Aldehydes and Ketones with HCN: Cyanohydrin Formation Overview
2.6K
Cyanohydrins are compounds that contain –CN and –OH groups on the same carbon atom. They are formed by the nucleophilic addition of the cyanide ions to the carbonyl group. Cyanide ions are highly basic and nucleophilic and can be generated from HCN under aqueous conditions. However, since HCN is a weak acid, the number of cyanide ions generated is very small. Hence, a small amount of base or KCN/NaCN is added to HCN to increase the concentration of the cyanide ions in the reaction...
2.6K