催化转移化过程的现实建模
Jan-Willem Handgraaf1, Evert Jan Meijer
1Van't Hoff Institute for Molecular Sciences, Universiteit van Amsterdam, Nieuwe Achtergracht 166, 1018 WV Amsterdam, The Netherlands. j.w.handgraaf@chem.leidenuniv.nl
Journal of the American Chemical Society
|February 27, 2007
概括
溶剂的影响显著改变催化转移化机制. 甲醇溶液将气相协调转移转换为一个连续的过程,降低激活障碍,并揭示了溶剂介导的途径.
科学领域:
- 计算化学的计算化学
- 催化剂是一种催化剂.
- 物理化学 物理化学
背景情况:
- 催化转移化在有机合成中至关重要.
- 了解溶剂效应对于优化催化反应至关重要.
- 之前的研究往往忽略了明确的溶剂建模.
研究的目的:
- 以计算方式研究甲的化转移与催化转移化及其反向反应.
- 为了阐明明明确的甲醇溶液中的反应机制和热力学.
- 将溶液相结果与气相计算进行比较,以量化溶剂效应.
主要方法:
- 使用ab initio分子动力学 (AIMD) 为一个完全原子化的模型.
- 在反应路径上计算热力学,机制和电子结构.
- 在气相和溶液相反应之间进行直接比较.
主要成果:
- 溶液中的能量概况与气相显著不同.
- 确定了一个明显的溶解障碍,在两个反应方向下降激活障碍.
- 在气相中协同的化物和质子转移成为溶液中的顺序机制,形成一种类似甲氧化物的中间体.
结论:
- 显式甲醇溶剂起着关键作用,改变了反应机制.
- 除了金属-联体双功能机制外,还可以使用溶剂介导的机制.
- 这项研究强调了溶剂在过渡金属催化反应中的积极作用,提供了新的机理见解.
相关概念视频
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
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...
Reduction of Alkenes: Catalytic Hydrogenation
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 surface of...
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 surface of...
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
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.
Reduction of Benzene to Cyclohexane: Catalytic Hydrogenation
Unlike the easy catalytic hydrogenation of an alkene double bond, hydrogenation of a benzene double bond under similar reaction conditions does not take place easily. For example, in the reduction of stilbene, the benzene ring remains unaffected while the alkene bond gets reduced. Hydrogenation of an alkene double bond is exothermic and a favorable process. In contrast, to hydrogenate the first unsaturated bond of benzene, an energy input is needed; that is, the process is endothermic. This is...
Heterogeneous Catalysis
Heterogeneous catalysis involves a catalyst in a different phase from the reactants. It is a process where the catalyst and the reactants are in distinct phases, typically solid and gas or liquid.Most heterogeneous catalysts are metals, metal oxides, or acids. The list includes transition metals like iron (Fe), cobalt (Co), nickel (Ni), palladium (Pd), platinum (Pt), chromium (Cr), manganese (Mn), tungsten (W), silver (Ag), and copper (Cu). These metals possess partially vacant d orbitals that...
Catalysis
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.


