在极性溶剂中增强酸合作性
Stefan Henkel1, Maria Cristina Misuraca1, Yudi Ding1
1Department of Chemistry, University of Cambridge , Lensfield Road, Cambridge CB2 1EW, U.K.
Journal of the American Chemical Society
|May 4, 2017
概括
像这样的极性溶剂与甲复合物的分子内H键相竞争. 然而,增加醇度会增强有效度 (EM),减轻这些多价值系统中的结合亲和力损失.
科学领域:
- 超分子化学
- 物理有机化学
- 光谱学
背景情况:
- 分子内键在分子识别和稳定性中起着至关重要的作用.
- 极性溶剂可以与分子内相互作用竞争并破坏,影响结合亲和力.
- 了解溶剂效应是设计具有可预测结合性质的分子的关键.
研究的目的:
- 研究极性溶剂 () 对甲-胺复合物的分子内键形成的竞争效应.
- 量化溶剂成分对分子内H键形成的有效度的影响.
- 阐明溶剂-溶液相互作用和合作结合效应之间的相互作用.
主要方法:
- 使用高通量紫外线定位来监测复杂的形成.
- 使用化学双突变周期 (DMC) 来确定有效度 (EM).
- 在不同烯-溶剂混合物中对24种甲-胺复合物进行了研究.
主要成果:
- 随着的度的增加,分子内胺H键的有效度 (EM) 显著增加 (数量级).
- 强烈溶解胺基,增加固体体积和破坏复合物的稳定性.
- 内分子H键的形成减轻了固体阻碍,增强了合作相互作用的驱动力.
结论:
- 极性溶剂的竞争性溶解可以通过增加多价值系统的有效度来抵消.
- 这项研究表明,通过增强的分子内H键形成,溶剂竞争被减弱的机制.
- 这项工作为具有可调节的结合亲缘关系的配体和复合物的设计提供了洞察力.
相关概念视频
Complexation Equilibria: The Chelate Effect
1.4K
In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
1.4K
EDTA: Chemistry and Properties
3.6K
Polydentate ligands are most widely used in complexometric titrations because they form more stable complexes with the metal ions than mono- or bidentate ligands due to the chelate effect. Examples of polydentate ligands are ethylenediaminetetraacetic acid (EDTA), crown ethers, and cryptands. The most important feature of optimal polydentate ligands is the ability to form 1:1 complexes in a single-step process. Amino carboxylic acid derivatives are frequently used as complexing agents. EDTA is...
3.6K
Molecular Shape and Polarity
76.6K
Dipole Moment of a Molecule
76.6K
Extraction: Advanced Methods
1.2K
Metal ions can be separated from one another by complexation with organic ligands–the chelating agent– to form uncharged chelates. Here, the chelating agent must contain hydrophobic groups and behave as a weak acid, losing a proton to bind with the metal. Since most organic ligands used in this process are insoluble or undergo oxidation in the aqueous phase, the chelating agent is initially added to the organic phase and extracted into the aqueous phase. The metal-ligand complex is...
1.2K
Metal-Ligand Bonds
24.9K
The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
24.9K
Solvating Effects
9.1K
An understanding of the solvating effect helps rationalize the relation between solvation and acidity of the compound. In addition, this also explains the relative stability of conjugate bases for compounds with different pKa values. This lesson details, in-depth, the principle of solvating effects. The strength of an acid and the stability of its corresponding conjugate base are determined using pKa values. This observed relationship is a consequence of solvation, which is the interaction...
9.1K


