环烯和环烯的C-H键解离能量
Zhixin Tian1, Alireza Fattahi, Lev Lis
1Department of Chemistry, University of Minnesota, Minneapolis, MN 55455, USA.
Journal of the American Chemical Society
|December 21, 2006
概括
这项研究测量了环丁烯中的C-H键能,为环丁烯提供了关键数据.
科学领域:
- 物理化学 物理化学
- 热化学 热化学 热化学
- 计算化学的计算化学
背景情况:
- 环丁烯的C-H键解离能 (BDE) 对于理解其反应性至关重要.
- 需要准确的循环butan热化学数据来确定循环butan形成的热量.
研究的目的:
- 为了实验性地确定循环丁烯的气相C-H键解离能.
- 为了提供循环butanadiene的形成热的实验数据.
- 评估循环和循环BDE的计算方法的准确性.
主要方法:
- 气相热力学循环使用质子亲和和和电子结合能量的测量.
- 合成和表征1和3环丁离子.
- 对环基,环基和参考化合物的高层次初始计算 (G3和W1).
主要成果:
- 测量到的环丁乙烯的基BDE为91.2±2.3千卡mol-1和维尼尔BDE为112.5±2.5千卡mol-1.
- 与cis-2-butene进行比较,发现周期性基和基的通常引用的键能有差异.
- 计算表明,文献中的环,环和环素的BDE可能被低估了3-4kcalmol-1.1.
结论:
- 循环丁烯的实验BDE为确定循环丁烯的形成热量提供了基础.
- 对于小周期性碳化合物的普遍接受的键能需要修订.
- 高级计算方法显示了准确的热化学预测的潜力,但需要验证.
相关概念视频
Bond Energies and Bond Lengths
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Combustion Energy: A Measure of Stability in Alkanes and Cycloalkanes
The low reactivity in alkanes can be attributed to the non-polar nature of C–C and C–H σ bonds. Alkanes, therefore, were initially termed as “paraffins,” derived from the Latin words: parum, meaning “too little,” and affinis, meaning “affinity.”
Alkanes undergo combustion in the presence of excess oxygen and high-temperature conditions to give carbon dioxide and water. A combustion reaction is the energy source in natural gas, liquified petroleum gas (LPG), fuel oil, gasoline, diesel fuel, and...
Alkanes undergo combustion in the presence of excess oxygen and high-temperature conditions to give carbon dioxide and water. A combustion reaction is the energy source in natural gas, liquified petroleum gas (LPG), fuel oil, gasoline, diesel fuel, and...
Thermal and Photochemical Electrocyclic Reactions: Overview
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
Thermal Electrocyclic Reactions: Stereochemistry
The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
IR Frequency Region: Alkyne and Nitrile Stretching
Both alkyne (C≡C) and nitrile (C≡N) functional groups contain triple bonds and show stretching absorptions around the wavenumber range of 2100 to 2300 cm−1 in the diagnostic region of the IR spectra.
Comparing the stretching vibrational frequency of C≡C triple bonds with that of double and single bonds, it is evident that C≡C triple bonds exhibit a higher stretching frequency than C=C double and C–C single bonds. Similarly, the C≡N triple bond exhibits higher stretching absorption than the C=N...
Comparing the stretching vibrational frequency of C≡C triple bonds with that of double and single bonds, it is evident that C≡C triple bonds exhibit a higher stretching frequency than C=C double and C–C single bonds. Similarly, the C≡N triple bond exhibits higher stretching absorption than the C=N...
Mass Spectrometry: Cycloalkane Fragmentation
In mass spectrometry, cycloalkanes exhibit distinct fragmentation patterns due to the inherent stability of their molecular ions compared to linear or branched alkanes. The ring structure of cycloalkanes provides additional stability to the molecular ions, often resulting in prominent ion peaks in the mass spectrum.
For example, cyclohexane molecular ions have a mass-to-charge ratio (m/z) of 84, which tends to produce a stronger signal than linear alkanes like hexane. This stability comes from...
For example, cyclohexane molecular ions have a mass-to-charge ratio (m/z) of 84, which tends to produce a stronger signal than linear alkanes like hexane. This stability comes from...


