溶液中素结合的热力学:替代剂,结构和溶剂效应
Mohammed G Sarwar1, Bojan Dragisic, Lee J Salsberg
1Department of Chemistry, Lash Miller Chemical Laboratories, University of Toronto, Toronto, Ontario M5S 3H6, Canada.
Journal of the American Chemical Society
|January 19, 2010
概括
这项研究用NMR定位量化溶液中的素结合热力学. 静电模型显示了局限性,突出了溶剂效应和与结合的差异.
科学领域:
- 物理化学 物理化学
- 有机化学 有机化学
- 超分子化学 超分子化学
背景情况:
- 素结合是一种显著的非共价相互作用.
- 了解溶液中的热力学对于化学应用至关重要.
- 现有的模型通常依赖于简化的静电描述.
研究的目的:
- 在有机溶液中进行素结合的详细热力学研究.
- 调查替代剂对素键供体能力的影响.
- 将静电模型的局限性与计算和溶剂效应数据进行比较.
主要方法:
- 使用了 (19) F NMR 定位来确定关联常量.
- 雇佣了替代的甲作为素键捐赠者.
- 分析了使用替代常数和静电电位的线性自由能量关系.
- 评估计算衍生的结合能量和溶剂效应.
主要成果:
- 对各种易斯基-相互作用的量化关联常数.
- 建立了素键捐赠者的线性自由能量关系.
- 纯电静电模型对于全面的素结合数据的已证明的局限性.
- 与键相比,确定了重要的溶剂效应和差异.
结论:
- 溶液中的素结合热力学可以使用NMR定位准确地确定.
- 静电模型对于复杂的素结合场景是有用的,但不足.
- 溶剂效应起着至关重要的作用,区分素结合与气结合.
相关概念视频
Radical Halogenation: Thermodynamics
The thermodynamic favorability of a reaction is determined by the change in Gibbs free energy (ΔG). ΔG has two components- enthalpy (ΔH) and entropy (ΔS). The entropy component is negligible for alkane halogenation because the number of reactants and product molecules are equal. In this case, the ΔG is governed only by the enthalpy component. The most crucial factor that determines ΔH is the strength of the bonds. ΔH can be determined by comparing the energy between bonds broken and bonds...
Alkyl Halides
Structural Properties
Alkyl halides are halogen-substituted alkanes wherein one or more hydrogen atoms of an alkane is replaced by a halogen atom such as fluorine, chlorine, bromine, or iodine. The carbon atom in an alkyl halide is bonded to the halogen atom, which is sp3-hybridized and exhibits a tetrahedral shape.
Unlike alkyl halides, compounds in which a halogen atom is bonded to an sp2 -hybridized carbon atom of a carbon-carbon double bond (C=C) are called vinyl halides. Whereas aryl...
Alkyl halides are halogen-substituted alkanes wherein one or more hydrogen atoms of an alkane is replaced by a halogen atom such as fluorine, chlorine, bromine, or iodine. The carbon atom in an alkyl halide is bonded to the halogen atom, which is sp3-hybridized and exhibits a tetrahedral shape.
Unlike alkyl halides, compounds in which a halogen atom is bonded to an sp2 -hybridized carbon atom of a carbon-carbon double bond (C=C) are called vinyl halides. Whereas aryl...
Halogenation of Alkenes
Halogenation is the addition of chlorine or bromine across the double bond in an alkene to yield a vicinal dihalide. The reaction occurs in the presence of inert and non-nucleophilic solvents, such as methylene chloride, chloroform, or carbon tetrachloride.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
Reactions at the Benzylic Position: Halogenation
Benzylic halogenation takes place under conditions that favor radical reactions such as heat, light, or a free radical initiator like peroxide.
Formation of Halohydrin from Alkenes
An alkene, such as propene, reacts with bromine in the presence of water to yield a halohydrin. Halohydrins contain a halogen and a hydroxyl group attached to adjacent carbons. When the halogen is bromine, it is called a bromohydrin, while a chlorohydrin has chlorine as the halogen.
Comparing Intermolecular Forces: Melting Point, Boiling Point, and Miscibility
Intermolecular forces are attractive forces that exist between molecules. They dictate several bulk properties, such as melting points, boiling points, and solubilities (miscibilities) of substances. Molar mass, molecular shape, and polarity affect the strength of different intermolecular forces, which influence the magnitude of physical properties across a family of molecules.
Temporary attractive forces like dispersion are present in all molecules, whether they are polar or nonpolar. They...
Temporary attractive forces like dispersion are present in all molecules, whether they are polar or nonpolar. They...


![The Synthesis of [Sn10(Si(SiMe3)3)4]2- Using a Metastable Sn(I) Halide Solution Synthesized via a Co-condensation Technique](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F54498.jpg&w=3840&q=50)