通过C5Me4SiMe3-结合的二核和三核水合物激活和化
Takanori Shima1,2, Jimin Yang3, Gen Luo3
1Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan.
Journal of the American Chemical Society
|April 18, 2020
概括
这项研究首次使用明确的化复合物进行了二 (N2) 裂变和化. 研究人员通过与多化合物的新反应实现了N2激活和随后的化.
科学领域:
- 有机金属化学
- 无机化学
- 催化剂
背景情况:
- 通过金属化物激活 (N2) 对于固定至关重要,但仍然具有挑战性.
- 对精确定义的金属复合物的N2激活研究是有限的.
- 聚化合物具有N2激活的潜力.
研究的目的:
- 通过C5Me4SiMe3结合的二核和三核聚化物复合物进行N2激活和化.
- 探索N2裂变和化所涉及的反应途径和中间体.
- 提供第一个由精确定义的化复合物的N2裂变和化示例.
主要方法:
- 二核和三核聚化物复合物的合成和表征
- 在不同条件下的解反应 (稀释剂与缩溶液).
- 在不同温度下与二 (N2) 发生反应.
- 用密度函数理论 (DFT) 计算来研究反应机制.
主要成果:
- 通过解形成二二和三核四化合物.
- N2激活和化导致四核二胺/二和二胺/二/二复合物.
- 一种二化物中间体的鉴定及其转化为二化物/二化物复合物
- 观察可逆立体同质化和化形成二胺/二化合物.
- 三核复合物与N2的反应产生二胺复合物.
- DFT计算支持将N2纳入为确定利率的步骤.
结论:
- 精确定义的聚化合物可以有效地分裂和化二 (N2).
- 这项研究首次成功证明了化复合物的N2裂变和化.
- 反应机制包括N-N键裂变,N-H键形成和C-H键激活.
相关概念视频
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.8K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
3.8K
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
8.8K
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.
8.8K
Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride
2.2K
Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...
2.2K
Catalysis
29.9K
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.
29.9K
Reduction of Alkenes: Catalytic Hydrogenation
13.8K
Alkenes undergo reduction by the addition of molecular hydrogen to give alkanes. Because the process generally occurs in the presence of a transition-metal catalyst, the reaction is called catalytic hydrogenation.
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
13.8K
Aldehydes and Ketones with HCN: Cyanohydrin Formation Mechanism
4.1K
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 alkoxide anion...
4.1K


