鉄に結合した一酸化炭素のシリレーションにより,終端のFeカルビネが得られる
1Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
Journal of the American Chemical Society
|March 8, 2011
まとめ
研究者らは,トリス (((フォスフィノ)) シリルリガンドを使用して,酸化状態0,+1および+2を持つ新しいモノカルボニル鉄複合体を合成しました. 彼らはユニークな鉄カルビネ種を作り,安定した低価鉄の中心を示した.
科学分野:
- 有機金属化学 有機金属化学
- 無機化学 無機化学とは
- 協調化化学について
背景:
- テトラデントートトリス・ポスフィノ・シリル・リガンドは,金属の中心部にユニークな調整環境を提供します.
- 低価鉄複合体は,触媒と材料科学に興味があります.
研究 の 目的:
- 様々な酸化状態のモノカルボニル鉄複合体を合成し,特徴づけること.
- 鉄カルビンの新種の電子的および構造的性質を調査する.
- 鉄複合体の安定性に対するトリス (((フォスフィノ)) シリルリガンドの影響を調査する.
主な方法:
- 鉄カルボニル複合体の合成にトリス・ポスフィノ・シリルリンガンドを用いる.
- 構造的決定のためのX線微分法 (XRD).
- 電子構造分析のためのモースバウアー光譜と密度関数理論 (DFT) 計算.
主要な成果:
- 酸化状態0,+1,+2のモノカルボニル鉄複合体を成功裏に合成した.
- 安定した鉄カルビネ種 (SiP ((iPr) ((3)) FeC-OSiMe ((3)) は,短いFeC結合で形成された.
- 構造と電子分析は,低価鉄を安定させるフィッシャー型カルビネリガンドを示した.
結論:
- トリス ((phosphino) シリルリガンドは,鉄カルボニル複合体における多様な酸化状態をサポートする.
- 合成された鉄カルビンは,ユニークな結合特性を持つ安定した低価鉄種を表しています.
- これらの発見は,低値の有機金属化合物の結合と反応性の理解に貢献します.
関連する概念動画
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.