尿素键供体强度:更大并不总是更好
Celine Nieuwland1, Angelina N van Dam1, F Matthias Bickelhaupt1,2,3
1Department of Chemistry and Pharmaceutical Sciences, Amsterdam Institute of Molecular and Life Sciences (AIMMS), Vrije Universiteit Amsterdam, De Boelelaan 1108, 1081 HZ Amsterdam, The Netherlands. c.fonsecaguerra@vu.nl.
Physical chemistry chemical physics : PCCP
|December 11, 2024
概括
尿素衍生物是催化和分子识别的关键. 氨酸中的固体效应意外地增强了键强度,为更强键的捐赠者提供了新的设计策略.
科学领域:
- 有机化学 有机化学
- 超分子化学 超分子化学
背景情况:
- 尿素在催化,分子识别和自我组装中是至关重要的,这是由于它们的键捐赠能力.
- 键捐赠体强度通常通过增加石化物大小 (O到S到Se) 或取电子组来增强,从而增加NH组的正电荷.
研究的目的:
- 为了研究固体效应对1,3-diaryl X-urea 的键供体强度的影响.
- 探索优化尿素衍生物中键供体强度的策略.
主要方法:
- 量子化学分析被用来研究影响键供体强度的电子和硬质因素.
- 对含有不同素元素 (O,S,Se) 和替代物的尿素衍生物进行比较分析.
主要成果:
- 在1,3-diaryl X-urea中确定了一种固体机制,它破坏了电子调因子的预期附加性.
- 尽管NH酸度较低,但1,3-二urea与它们的S-和Se-类似物相比,显示出增强的键供体强度.
- 为了克服固体限制,提出了一项涉及14组元素的预扭曲尿素类型捐赠者的策略.
结论:
- 绝缘阻碍在调节结捐赠体强度在尿素尿酸中起着至关重要的作用.
- 这些发现为设计和合成各种应用的增强键供体分子提供了一种新的方法.
相关概念视频
Basicity of Aliphatic Amines
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Amines can behave as Brønsted–Lowry bases by accepting a proton from the acid to form corresponding conjugate acids. Due to a lone pair of nonbonding electrons, aliphatic amines can also act as Lewis bases by forming a covalent bond with an electrophile.
To measure the basicity of amines, two conventions are generally used. The first defines Kb as the basicity constant for the deprotonation reaction of water by the amine, as presented in Figure 1. Conventionally, lower Kb indicates...
To measure the basicity of amines, two conventions are generally used. The first defines Kb as the basicity constant for the deprotonation reaction of water by the amine, as presented in Figure 1. Conventionally, lower Kb indicates...
5.7K
Hydrogen Bonds
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A hydrogen bond is formed when a weakly positive hydrogen atom already bonded to one electronegative atom (for example, the oxygen in the water molecule) is attracted to another electronegative atom from another polar molecule, such as water (H2O), hydrogen fluoride (HF), or ammonia (NH3). The huge electronegativity difference between the H atom (2.1) and the atom to which it is bonded (4.0 for an F atom, 3.5 for an O atom, or 3.0 for an N atom), combined with the very small size of an H atom...
8.0K
Basicity of Heterocyclic Aromatic Amines
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Heterocyclic amines, where the N atom is a part of an alicyclic system, are similar in basicity to alkylamines. Interestingly, the heterocyclic amine having a nitrogen atom as part of an aromatic ring has much less basicity than its corresponding alicyclic counterpart. For this reason, as presented in Figure 1, piperidine (pKb = 2.8) is significantly more basic than pyridine (pKb = 8.8).
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Weak Base Solutions
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Some compounds produce hydroxide ions when dissolved by chemically reacting with water molecules. In all cases, these compounds react only partially and so are classified as weak bases. These types of compounds are also abundant in nature and important commodities in various technologies. For example, global production of the weak base ammonia is typically well over 100 metric tons annually, being widely used as an agricultural fertilizer, a raw material for chemical synthesis of other...
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Titration of a Weak Base with a Strong Acid
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The titration curve of a weak base like ammonia with a strong acid like hydrochloric acid is the mirror image of the titration curve of a weak acid with a strong base.
Using the ICE table and substituting the Kb value, we calculate the initial pH of 50 mL of 0.1 M ammonia to be 11.11. Addition of 25 mL of 0.1 M hydrochloric acid to this solution of ammonia results in a buffer with an equal concentration of ammonia and ammonium ions. The pH of this buffer can be calculated by substituting these...
Using the ICE table and substituting the Kb value, we calculate the initial pH of 50 mL of 0.1 M ammonia to be 11.11. Addition of 25 mL of 0.1 M hydrochloric acid to this solution of ammonia results in a buffer with an equal concentration of ammonia and ammonium ions. The pH of this buffer can be calculated by substituting these...
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Relative Strengths of Conjugate Acid-Base Pairs
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Brønsted-Lowry acid-base chemistry is the transfer of protons; thus, logic suggests a relation between the relative strengths of conjugate acid-base pairs. The strength of an acid or base is quantified in its ionization constant, Ka or Kb, which represents the extent of the acid or base ionization reaction. For the conjugate acid-base pair HA / A−, the ionization equilibrium equations and ionization constant expressions are
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