量子道效应在乌拉尼尔四氧化物的cis-trans异构化中
Yeshayahu Ben-Eliyahu1, Sebastian Kozuch2
1Chemistry Department, Nuclear Research Centre-Negev, Beer-Sheva, 84190, Israel. ybe614@gmail.com.
Dalton transactions (Cambridge, England : 2003)
|September 23, 2024
概括
量子道化显著影响了乌兰四氧化物异构化动力学. 在低温下,量子道对于质子转移至关重要,特别是水分子协助这一过程.
科学领域:
- 计算化学是一种计算化学.
- 物理化学 物理化学
- 无机化学 无机化学 无机化学
背景情况:
- 质子转移在化学反应中至关重要.
- 乌拉尼尔四氧化物 (UTH) 经历 cis-trans 异构化.
- 了解水溶液中的反应机制是很重要的.
研究的目的:
- 在UTH异构化中以计算方式调查量子道.
- 探索水分子在质子转移途径中的作用.
- 为了确定温度和水环境对反应动力学的影响.
主要方法:
- 量子力学的计算.
- 对三种不同的反应途径的分析.
- 包括气相和连续水态模型.
- 计算/动态同位素效应 (KIE).
主要成果:
- 在水溶液中,涉及两个水分子的通路在热力学和动力学上是首选的.
- 量子道是在低温下占主导地位的机制,由一个大的KIE证明.
- 在更高的温度下,经典的障碍穿越变得与道挖掘具有竞争力.
结论:
- 水分子在促进通过道在UTH异构化中进行质子转移方面发挥着关键作用.
- 量子道对于UTH低温异构化动力学是必不可少的.
- 取决于温度的机制,包括道挖掘和古典穿越,控制反应速率.
相关概念视频
Disubstituted Cyclohexanes: cis-trans Isomerism
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Depending upon the different spatial orientation of the substituents, the disubstituted cycloalkanes exhibit two types of stereoisomers. The cis isomers have the substituents on the same side of the ring, whereas the trans isomers have the substituents on the opposite sides. These stereoisomers exhibit different physical properties and cannot be interconverted without breaking the carbon-carbon bonds.
In cyclohexane, the substituents can occupy different positions generating distinct isomers....
In cyclohexane, the substituents can occupy different positions generating distinct isomers....
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Thermal and Photochemical Electrocyclic Reactions: Overview
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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.
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Stereoisomerism
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Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
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Thermal Electrocyclic Reactions: Stereochemistry
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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.
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Photochemical Electrocyclic Reactions: Stereochemistry
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The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
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Aromatic Hydrocarbon Cations: Structural Overview
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Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
Removing one hydrogen from the intervening CH2 group...
Removing one hydrogen from the intervening CH2 group...
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