激进分子推动的石头威尔士重新安排
Roger W Alder1, Jeremy N Harvey
1School of Chemistry, University of Bristol, Cantock's Close, Bristol, UK BS8 1TS. rog.alder@bris.ac.uk
Journal of the American Chemical Society
|February 26, 2004
概括
使用计算方法研究了斯通-威尔士重排机制. 对于复杂的多环芳化合物来说,激素促进的途径比单分子途径更有可能发生.
科学领域:
- 计算化学计算化学
- 有机化学 有机化学
- 材料科学 材料科学 材料科学
背景情况:
- 斯通-威尔士重组是修改多环芳 (PAHs) 的关键反应.
- 了解这种机制对于设计新型碳材料和预测反应性至关重要.
研究的目的:
- 为了阐明石-威尔士对二乙烯到二[g,p]烯的重新排列的机制.
- 调查复杂的PAH和富勒伦的激素促进途径的可行性.
主要方法:
- 使用B3LYP/6-31G的理论水平进行密度函数计算.
- 对拟议反应途径的激活能量的分析.
主要成果:
- 一种由激素促进的机制,具有一系列的同-环基基基重组步骤,准确地解释了实验观察.
- 单分子机制表现出不切实际的高激活能量.
- 激素促进的通路仍然有利于二二[1,2,3,4-defg;1',2',3',4'-mnop]烯和C 60),尽管由于固态阻碍而增加了激活能量.
结论:
- 激进促进的机制对于理解复杂的PAHs中的Stone-Wales重排是必不可少的.
- 计算研究为碳基材料的反应途径和能量学提供了宝贵的见解.
相关概念视频
Radical Formation: Overview
A bond can be broken either by heterolytic bond cleavage to form ions or homolytic bond cleavage to yield radicals. A fishhook arrow is used to represent the motion of a single electron in homolytic bond cleavage. There are two main sources from which radicals can be formed:
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the latter, also known...
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the latter, also known...
Radical Formation: Homolysis
A bond is formed between two atoms by sharing two electrons. When this bond is broken by supplying sufficient energy, either two electrons can be taken up by one atom forming ions by the cleavage called heterolysis, or the two electrons are shared by two atoms, with one each creating radicals by the cleavage called homolysis.
Radical Formation: Abstraction
The electron of an atom can be abstracted from a compound by a relatively unstable radical to generate a new radical of relatively greater stability. For example, an initiator which forms radicals by homolysis can abstract a suitable species like a hydrogen atom or a halogen atom from a compound to generate a new radical. This ability of radicals to propagate by abstraction is a crucial feature of radical chain reactions.
Even though homolysis produces radicals, it is different from radical...
Even though homolysis produces radicals, it is different from radical...
Radical Formation: Addition
Radicals can be formed by adding a radical to a spin-paired molecule. This is typically observed with unsaturated species, where the addition of a radical across the π bond leads to the production of a new radical by dissolving the π bond. For example, the addition of a Br radical to an alkene yields a carbon-centered radical.
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an unpaired...
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an unpaired...
Radical Formation: Elimination
Another method of radical formation is the elimination process. It is the opposite of the addition route and is driven by the instability of the radical. For example, as depicted in Figure 1, dibenzoyl peroxide yields a pair of unstable radicals upon homolysis. Given its instability, this radical spontaneously undergoes elimination via a C–C bond cleavage to form a relatively more stable phenyl radical. The mechanism involves cleavage of the bond between the α and β positions with respect to...
Radical Halogenation: Stereochemistry
Stereochemistry is the study of the different spatial arrangements of atoms in a given molecule. The stereochemistry of radical halogenations can be understood from three different situations:
Halogenation to form a new chiral center:
Halogenation to form a new chiral center:


