流产反应导致选择性吸附剂旋转
Yi-Fang Lai1, Lydie Leung1, Matthew J Timm2
1Lash Miller Chemical Laboratories, Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, M5S 3H6, Canada. john.polanyi@utoronto.ca.
Faraday discussions
|May 29, 2024
概括
来自CF3吸附剂的电子诱导的原子充当射弹,导致基分子的旋转激发. 这种碰撞导致了失败的化学反应和铜表面的基异构.
科学领域:
- 表面科学是一门学科.
- 物理化学 物理化学
- 纳米技术纳米技术
背景情况:
- 吸附剂的电子诱导解离是表面化学中的一个关键过程.
- 了解分子-表面相互作用对于设计纳米化工过程至关重要.
- 碳化合物吸附剂在金属表面上提供独特的反应途径.
研究的目的:
- 为了研究CF3在Cu上的电子诱导解离的动态{110}.
- 为了研究高能F-原子弹和协同吸附的基分子之间的碰撞结果.
- 阐明基激发和随后的化学反应的机制.
主要方法:
- 扫描道显微镜 (STM) 在4.6K以观察解离和碰撞.
- 分子动力学 (MD) 模拟来建模碰撞动力学.
- 使用由CF3解离产生的定向能量F原子"射弹".
主要成果:
- 导向的,高能量的F原子弹弹是由CF3在Cu上的解离形成的.
- 碰撞诱导了目标基分子中的旋转激发 (时针方向/反时针方向).
- MD模拟将激发与失败反应联系起来,拉伸H-C键并促进基异构化.
结论:
- 电子诱导的解离可以为表面化学产生有针对性的反应物种.
- 碰撞几何学决定了目标分子的旋转激发.
- 这项研究揭示了一种新的途径,通过能量原子弹来诱导表面反应和异构.
相关概念视频
SN2 Reaction: Stereochemistry
9.5K
In an SN2 reaction, the nucleophilic attack on the substrate and departure of the leaving group occurs simultaneously through a transition state. As the nucleophile approaches the substrate from the back-side, the configuration of the substrate carbon changes from tetrahedral to trigonal bipyramidal and then back to tetrahedral, leading to an inversion in the configuration of the product.
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not...
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not...
9.5K
Regioselectivity and Stereochemistry of Hydroboration
8.1K
A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
8.1K
Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule
14.1K
If a set of reactants can yield multiple constitutional isomers, but one of the isomers is obtained as the major product, the reaction is said to be regioselective. In such reactions, bond formation or breaking is favored at one reaction site over others.
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
14.1K
Nucleophilic Aromatic Substitution: Addition–Elimination (SNAr)
3.8K
Nucleophilic substitution in aromatic compounds is feasible in substrates bearing strong electron-withdrawing substituents positioned ortho or para to the leaving group. The reaction proceeds via two steps: the addition of the nucleophile and the elimination of the leaving group.
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between...
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between...
3.8K
Nucleophilic Aromatic Substitution: Elimination–Addition
4.0K
Simple aryl halides do not react with nucleophiles. However, nucleophilic aromatic substitutions can be forced under certain conditions, such as high temperatures or strong bases. The mechanism of substitution under such conditions involves the highly unstable and reactive benzyne intermediate. Benzyne contains equivalent carbon centers at both ends of the triple bond, each of which is equally susceptible to nucleophilic attack. This 50–50 distribution of products is...
4.0K
meta-Directing Deactivators: –NO2, –CN, –CHO, –⁠CO2R, –COR, –CO2H
5.5K
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...
5.5K


