介导质子合电子转移:量化非常弱的N-H和O-H同质键强度和控制它们的因素
Emily A Boyd1, Jonas C Peters1
1Division of Chemistry and Chemical Engineering, California Institute of Technology (Caltech), Pasadena, California 91125, United States.
Journal of the American Chemical Society
|November 8, 2022
概括
这项研究引入了一种明确的三 (II) 复合物,作为一种强大的质子合电子转移 (PCET) 试剂,可准确测量异常弱的N-H和O-H键,以提高反应性.
科学领域:
- 有机金属化学
- 减氧化学
背景情况:
- 二氧化物 (SmI2) 是一种单电子还原剂,用于质子合电子转移 (PCET) 反应.
- 由于常见的溶剂混合物如四基 (THF) /酒精的物种化定义不佳,SmI2的反应性受到限制.
- 准确的热力学数据,如键解离自由能量 (BDFE),对于理解和预测Sm介导的PCET反应性至关重要.
研究的目的:
- 开发一个明确的模型系统来研究基于SmII的PCET反应性.
- 准确确定具有功能化的宏环连体的复合体中的N-H和O-H键的BDFE值.
- 将该模型系统的反应性与传统的SmI2/THF系统进行比较.
主要方法:
- 合成大量的化宏环联体 ((ArOH) 2Me2cyclam),以确保溶解性并防止二元化.
- 使用宏循环连接体对SmII复合物的电化学表征.
- 直接测量热力学参数,以计算2-pyrrolidone和MeOH复合物的BDFEs.
- 扩展热化学循环的分析,以阐明结合减弱的起源.
主要成果:
- 该复合物具有清洁的电化学行为,并保持可溶性.
- 特别弱的N-H和O-H BDFEs分别测量了2- pyrrolidone (< 27. 2 kcal mol-1) 和MeOH (< 24. 1 kcal mol-1) 复合物.
- 结合的弱化归因于强烈减少的SmII中心和强烈的SmIII-pyrrolidonate/alkoxide相互作用.
结论:
- 开发的模型系统为基于SmII的PCET提供可靠的热力学数据.
- 获得的BDFE值明显低于在THF中通常观察到的SmI2.
- 这项工作为设计基于SmII的高效 (电) 催化系统铺平了道路.
更多相关视频
相关概念视频
Spin–Spin Coupling: One-Bond Coupling
1.0K
Coupling interactions are strongest between NMR-active nuclei bonded to each other, where spin information can be transmitted directly through the pair of bonding electrons. While nuclei polarize their electrons to the opposite spins, the bonding electron pair has opposite spins. Configurations with antiparallel nuclear spins are expected to be lower in energy. When coupling makes antiparallel states more favorable, J is considered to have a positive value. The one-bond coupling constant, 1J,...
1.0K
Spin–Spin Coupling Constant: Overview
988
In bromoethane, the three methyl protons are coupled to the two methylene protons that are three bonds away. In accordance with the n+1 rule, the signal from the methyl protons is split into three peaks with 1:2:1 relative intensities. The methylene protons appear as a quartet, with the relative intensities of 1:3:3:1.
Qualitatively, any spin plus-half nucleus polarizes the spins of its electrons to the minus-half state. Consequently, the paired electron in the hydrogen–carbon bond must...
Qualitatively, any spin plus-half nucleus polarizes the spins of its electrons to the minus-half state. Consequently, the paired electron in the hydrogen–carbon bond must...
988
¹H NMR: Long-Range Coupling
1.9K
The coupling interactions of nuclei across four or more bonds are usually weak, with J values less than 1 Hz. While these are usually not observed in spectra, the presence of multiple bonds along the coupling pathway can result in observable long-range coupling.
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene...
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene...
1.9K
Radical Formation: Homolysis
3.6K
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.
3.6K
Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)
1.1K
Two NMR-active nuclei bonded to a central atom can be involved in geminal or two-bond coupling. Geminal coupling is commonly seen between diastereotopic protons in chiral molecules and unsymmetrical alkenes, among others.
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
1.1K
Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)
1.1K
Vicinal or three-bond coupling is commonly observed between protons attached to adjacent carbons. Here, nuclear spin information is primarily transferred via electron spin interactions between adjacent C‑H bond orbitals. This generally favors the antiparallel arrangement of spins, so 3J values are usually positive.
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the...
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the...
1.1K


![Protein Film Infrared Electrochemistry Demonstrated for Study of H2 Oxidation by a [NiFe] Hydrogenase](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F55858.jpg&w=3840&q=50)