结合铁的一氧化碳的化产生一个终端的Fe碳酸
1Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
Journal of the American Chemical Society
|March 8, 2011
概括
研究人员使用tris(phosphino) silyl连接体合成了具有氧化状态为0,+1和+2的新型单碳基铁复合体. 他们创造了一种独特的铁碳酸物种,证明了稳定的低价值铁中心.
科学领域:
- 有机金属化学 有机金属化学
- 无机化学 无机化学
- 协调化学 协调化学
背景情况:
- 四牙三 () 基连接物为金属中心提供了独特的协调环境.
- 低价值铁复合物对催化和材料科学有兴趣.
研究的目的:
- 在各种氧化状态下合成和表征单碳铁复合物.
- 为了研究一种新型铁碳酸物种的电子和结构性质.
- 为了探索一个tris ((phosphino) silyl连接体对铁复合体稳定性的影响.
主要方法:
- 铁碳基复合物的合成与一个tris(phosphino) 基连接体.
- 用X射线衍射 (XRD) 进行结构确定.
- 用Mössbauer光谱和密度函数理论 (DFT) 计算进行电子结构分析.
主要成果:
- 成功合成了氧化状态为0,+1和+2的单碳酸铁复合体.
- 一种稳定的铁碳烯物种, (SiP(iPr)(3)) FeC-OSiMe(3),由一个短的FeC键形成.
- 结构和电子分析表明,费舍尔型的卡宾连体稳定了低价值铁的中心.
结论:
- 三 () 基连接体支持铁碳基复合体中的多种氧化状态.
- 合成的铁碳酸是一种稳定,低价值的铁物种,具有独特的结合特性.
- 这些发现有助于理解低价值有机金属化合物的结合和反应性.
相关概念视频
01:13Preparation of Carboxylic Acids: Carboxylation of Grignard Reagents
Carboxylic acids can be prepared by the carboxylation of Grignard reagents (RMgX). This method is convenient for converting alkyl (primary, secondary or tertiary), vinyl, benzyl, and aryl halides to carboxylic acids with one additional carbon than the starting RMgX.
02:47Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
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.
01:19α-Hydroxy Ketones via Reductive Coupling of Esters: Acyloin Condensation Overview
The pinacol and McMurry reactions involve the reductive coupling of ketones or aldehydes. Similarly, the bimolecular reductive coupling of two ester molecules in the presence of sodium metal in an aprotic solvent yields an α-hydroxy ketone product. The α-hydroxy ketone is also called acyloin, so the reaction is referred to as ‘acyloin condensation.’
01:23Properties of Organometallic Compounds
Organometallic compounds are compounds that contain a carbon–metal bond. Carbon belongs to an organyl group like alkyl, aryl, allyl, or benzyl groups. The metal can be from Group I or Group II of the periodic table, a transition metal, or a semimetal.
01:22Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
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.
01:41Reactions of Carboxylic Acids: Introduction
Carboxylic acids possess an acidic –COOH functional group. The acidity can be attributed to the resonance stabilization of their conjugate base, wherein the negative charge is delocalized over both oxygen atoms.