同位素效应揭示了"离子"催化的一种替代机制
Joseph A Izzo1, Pernille H Poulsen2, Jeremy A Intrator1
1Department of Chemistry , Binghamton University , Binghamton , New York 13902 , United States.
Journal of the American Chemical Society
|June 26, 2018
概括
这项研究揭示了使用过氧化的新环氧化机制. 实验数据和计算支持传统的iminium-ion机制上的syn-SN2'替代途径.
科学领域:
- 有机化学
- 反应机制
- 催化剂
背景情况:
- 乙醇的氧化是有机合成中的关键转化.
- 利醇乙烯是各种有机反应的有效催化剂.
- 了解反应机制是优化合成路径的关键.
研究的目的:
- 通过使用过氧化催化二烯乙烯的氧化机制.
- 研究特定碳原子在速度决定步骤中的作用.
- 将拟议的 syn-SN2' 机制与已确定的 iminium-ion 途径进行比较.
主要方法:
- 在和β-碳原子的C动态同位素效应 (KIEs) 的实验性确定.
- 密度函数理论 (DFT) 计算以建模反应路径并预测KIE.
- 实验KIE与不同机制的理论预测值的比较.
主要成果:
- 对碳和β-碳原子均观察到正常的CKE,表明它们参与了速率决定的步骤.
- DFT的计算表明,传统的离子机制无法解释所观察到的KIE.
- 一个syn-SN2'替代机制,绕过一个离散的iminium-ion中间体,与实验数据有很强的一致性.
结论:
- 这项研究提出了一种新型的SN2'机制,用于用过氧化催化.
- 这种机制比以前接受的离子通路更好地解释了实验中的动态同位素效应.
- 这些发现提供了对催化循环的更深入的理解,并可以指导开发更有效的环氧化策略.
相关概念视频
Intermolecular vs Intramolecular Forces
91.5K
Intermolecular forces (IMF) are electrostatic attractions arising from charge-charge interactions between molecules. The strength of the intermolecular force is influenced by the distance of separation between molecules. The forces significantly affect the interactions in solids and liquids, where the molecules are close together. In gases, IMFs become important only under high-pressure conditions (due to the proximity of gas molecules). Intermolecular forces dictate the physical properties of...
91.5K
Common Ion Effect
34.1K
Compared with pure water, the solubility of an ionic compound is less in aqueous solutions containing a common ion (one also produced by dissolution of the ionic compound). This is an example of a phenomenon known as the common ion effect, which is a consequence of the law of mass action that may be explained using Le Châtelier’s principle. Consider the dissolution of silver iodide:
34.1K
Ionic Strength: Effects on Chemical Equilibria
2.9K
The addition of an inert ionic compound increases the solubility of a sparingly soluble salt. For example, adding potassium nitrate to a saturated solution of calcium sulfate significantly enhances the solubility of calcium sulfate. Le Châtelier's principle cannot predict this shift in the equilibrium. Instead, this could be explained in terms of changes in the effective concentration of the ions in solution in the presence of added inert salt.
In this solution, the primary...
In this solution, the primary...
2.9K
Ion Exchange
1.6K
Ion exchange chromatography separates charged molecules from a solution by reversibly exchanging them with mobile, or 'active', ions associated with the oppositely charged stationary phase. This method can be used to separate ions, soften and deionize water, and purify solutions. The polymers comprising the ion-exchange column are high-molecular-weight and chemically stable polymers, crosslinked to be porous and essentially insoluble. They are also functionalized with either acidic or...
1.6K
Inductively Coupled Plasma-Mass Spectrometry (ICP-MS): Interferences
1.7K
Inductively coupled plasma–mass spectrometry (ICP–MS) is a highly selective and sensitive technique for accurate elemental analysis. Though the analysis of ICP–MS mass spectra is comparatively straightforward, it is affected by spectroscopic and non-spectroscopic interferences. Spectroscopic interferences arise when the plasma contains ionic species with an m/z value the same as the analyte ion. Spectroscopic interference can be categorized as isobaric, polyatomic ions, and...
1.7K
Insensitive Nuclei Enhanced by Polarization Transfer (INEPT)
1.2K
Insensitive Nuclei Enhanced by Polarization Transfer (INEPT) is an advanced Nuclear Magnetic Resonance (NMR) technique specifically designed to detect and enhance the signals of low-abundance nuclei, such as carbon-13 and nitrogen-15, in small molecules. The fundamental principle behind INEPT is the transfer of polarization from a more abundant and highly polarizable nucleus, typically hydrogen-1, to the low-abundance nucleus of interest. This process effectively boosts the NMR signal of the...
1.2K


