ニッケル複合体によって触媒化されたC2−O結合形成反応における窒素酸化物の活性化メカニズム
Lorenzo Baldinelli1, Paola Belanzoni1, Giovanni Bistoni1
1Dipartimento di Chimica, Biologia e Biotecnologie, Università degli Studi di Perugia, Via Elce di Sotto, 8, 06123 Perugia, Italy.
Journal of the American Chemical Society
|February 20, 2024
まとめ
ニッケル複合体は,C−O結合形成で酸素移転のために窒素酸化物 (N2O) を活性化します. リガンド・レドックス活性が触媒を可能にし,電子的および幾何学的要因が新しい触媒設計の反応経路を導く.
科学分野:
- 有機金属化学
- カタリシス
- コンピュータ化学
背景:
- ビピリジンベースのリガンドを持つニッケル複合体は,酸素伝達剤として酸化窒素 (N2O) を活性化します.
- この活性化により,温和な条件下でC ((sp2) O結合が形成されます.
研究 の 目的:
- 量子化学計算を用いて,Ni複合体によるN2O活性化の触媒機構を解明する.
- N2Oの再利用のための新しい触媒を開発するための基本的な洞察を提供すること.
主な方法:
- 量子化学計算が使われました
- コーネルラ等によるケーススタディ (Nature, 2022) でアリルハリドからフェノール合成を分析した.
主要な成果:
- Niセンターは,触媒サイクルを通してNi (II) 酸化状態にとどまります.
- 還元剤から電子を受け取るリガンド・レドックス活動は,触媒作用に不可欠である.
- 触媒経路は,リガンドの電子特性 (フィールド強度) と幾何学 (調整腕) によって影響を受けます.
結論:
- リガンドの設計は,触媒対ステキオメトリック経路の制御に不可欠です.
- リガンドを調節する特性により,N2O利用に合わせた酸化還元特性と反応性を有するNi触媒の開発が可能である.
さらに関連する動画
関連する概念動画
Catalysis
26.9K
The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
26.9K
Rate-Determining Steps
32.4K
Relating Reaction Mechanisms
In a multistep reaction mechanism, one of the elementary steps progresses significantly slower than the others. This slowest step is called the rate-limiting step (or rate-determining step). A reaction cannot proceed faster than its slowest step, and hence, the rate-determining step limits the overall reaction rate.
The concept of rate-determining step can be understood from the analogy of a 4-lane freeway with a short-stretch of traffic-bottleneck caused due to...
In a multistep reaction mechanism, one of the elementary steps progresses significantly slower than the others. This slowest step is called the rate-limiting step (or rate-determining step). A reaction cannot proceed faster than its slowest step, and hence, the rate-determining step limits the overall reaction rate.
The concept of rate-determining step can be understood from the analogy of a 4-lane freeway with a short-stretch of traffic-bottleneck caused due to...
32.4K
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism
3.8K
Nitrous acid is a relatively weak and unstable acid prepared in situ by the reaction of sodium nitrite and cold, dilute hydrochloric acid. In an acidic solution, the nitrous acid undergoes protonation when it loses water to form a nitrosonium ion—an electrophile. Nitrous acid reacts with primary amines to give diazonium salts. The reaction is called diazotization of primary amines.
3.8K
meta-Directing Deactivators: –NO2, –CN, –CHO, –⁠CO2R, –COR, –CO2H
5.6K
All meta-directing substituents are deactivating groups. These substituents withdraw electrons from the aromatic ring, making the ring less reactive toward electrophilic substitution. For example, the nitration of nitrobenzene is 100,000 times slower than that of benzene because of the deactivating effect of the nitro group. The first step in an electrophilic aromatic substitution is the addition of an electrophile to form a resonance-stabilized carbocation. The energy diagrams for...
5.6K
Nucleophilic Addition to the Carbonyl Group: General Mechanism
5.4K
The carbonyl carbon in an aldehyde or ketone is the site of a nucleophilic attack due to its electron-deficient nature. Depending on the strength of the incoming nucleophile, the reaction occurs via different mechanistic pathways.
A stronger nucleophile can directly attack the electrophilic center, the carbonyl carbon. The HOMO orbital of the nucleophile interacts with the LUMO (π* antibonding) orbital present on the carbonyl carbon. This interaction breaks the π bond and shifts the...
A stronger nucleophile can directly attack the electrophilic center, the carbonyl carbon. The HOMO orbital of the nucleophile interacts with the LUMO (π* antibonding) orbital present on the carbonyl carbon. This interaction breaks the π bond and shifts the...
5.4K
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Overview
3.3K
Nitrous acid and nitric acids are two types of acids containing nitrogen, among which nitrous acid is weaker than nitric acid. Nitrous acid with a pKa value of 3.37 ionizes in water to give a nitrite ion and the hydronium ion.
The nitrous acid is unstable. Hence, it is formed in situ from a solution of sodium nitrite and cold aqueous acids such as hydrochloric or sulfuric acid. In an acidic solution, the –OH group of nitrous acid undergoes protonation to give oxonium ion, followed by...
The nitrous acid is unstable. Hence, it is formed in situ from a solution of sodium nitrite and cold aqueous acids such as hydrochloric or sulfuric acid. In an acidic solution, the –OH group of nitrous acid undergoes protonation to give oxonium ion, followed by...
3.3K


