通过诱导旋转配对的α-化物迁移的无基铁烯复合物
Patrick W Smith1, T Don Tilley1
1Department of Chemistry , University of California, Berkeley , Berkeley , California 94720-1460 , United States.
Journal of the American Chemical Society
|March 13, 2018
概括
合成了新的铁烯复合物,并显示出独特的反应性. 这些复合物经历C-H激活,并与快速反应,在键激活反应中表现优于类型.
科学领域:
- 有机金属化学
- 化学
- 协调化学
背景情况:
- 水烯复合物是有机金属化学中的重要中间体.
- 了解无基铁复合物的反应性对于开发新的催化过程至关重要.
研究的目的:
- 合成和表征新的无基铁烯复合物.
- 研究这些铁复合物的活性,特别是在C-H激活和化反应中.
- 将铁复合物的反应性与它们的类型进行比较.
主要方法:
- 使用Cp*(iPr2MeP) FeMes作为起始材料合成铁烯复合物.
- 使用光谱技术对复合物和中间体进行表征.
- 均衡研究以了解烯和烯复合体之间的相互转换.
- 涉及CH激活和化的反应性研究.
主要成果:
- 两种新的无酸铁复合物,Cp*(iPr2MeP) Fe(H) SiHR (R = DMP,Trip) 已成功合成.
- 这些复合物与相应的铁复合物Cp*(iPr2MeP) FeSiH2R处于平衡状态.
- 具有R=DMP的铁复合物经历了分子内C-H激活,这种反应在类似的复合物中没有观察到.
- 铁复合物对具有增强的反应性,形成化产品的速度比类型更快.
结论:
- 合成的铁烯复合物代表了一类具有独特反应性的无化合物.
- 铁复合物表现出C-H键激活和高效化的倾向,在某些反应中超过类型.
- 这些发现为铁复合物在催化和合成化学中的应用开辟了新的途径.
相关概念视频
DNA Base Pairing
33.8K
Erwin Chargaff’s rules on DNA equivalence paved the way for the discovery of base pairing in DNA. Chargaff’s rules state that in a double-stranded DNA molecule,
33.8K
DNA Base Pairing
33.0K
33.0K
Base-pairing and DNA Repair
93.8K
93.8K
Relative Strengths of Conjugate Acid-Base Pairs
52.7K
Brønsted-Lowry acid-base chemistry is the transfer of protons; thus, logic suggests a relation between the relative strengths of conjugate acid-base pairs. The strength of an acid or base is quantified in its ionization constant, Ka or Kb, which represents the extent of the acid or base ionization reaction. For the conjugate acid-base pair HA / A−, the ionization equilibrium equations and ionization constant expressions are
52.7K
Factors Affecting α-Alkylation of Ketones: Choice of Base
3.6K
α-Alkylation of ketones is achieved in the presence of alkyl halides and a base. The reaction proceeds via the formation of an enolate ion followed by nucleophilic substitution. The choice of base employed is essential as it is the key factor in determining the reaction outcome.
The reaction involving bases like EtO− whose conjugate acid EtOH (pKa = 15.9) is stronger than the ketone (pKa = 19.2) results in an equilibrium mixture with higher ketone concentration. As a consequence,...
The reaction involving bases like EtO− whose conjugate acid EtOH (pKa = 15.9) is stronger than the ketone (pKa = 19.2) results in an equilibrium mixture with higher ketone concentration. As a consequence,...
3.6K
Base-Promoted α-Halogenation of Aldehydes and Ketones
4.2K
α-Halogenation of aldehydes and ketones is a reaction involving the substitution of α hydrogens with halogens in the presence of a base. The reaction begins with the abstraction of α hydrogen by the base to produce a nucleophilic enolate ion. This intermediate undergoes a subsequent nucleophilic substitution with the halogen to produce a monohalogenated carbonyl compound. If the starting substrate has more than one α hydrogen, it is difficult to stop the reaction...
4.2K


