分子结构和dinitrosylheme的构造
Jeanet Conradie1, Tebikie Wondimagegn, Abhik Ghosh
1Department of Chemistry, Faculty of Science, University of Tromsø, N-9037 Tromsø, Norway.
Journal of the American Chemical Society
|April 24, 2003
概括
作为一种反应性物种的dinitrosylheme表现出一种强烈的 cis 形状的偏好,这与之前的建议相反. 密度函数理论 (DFT) 的计算揭示了这种独特的方向偏好,这对于其生物相关性很重要.
科学领域:
- 计算化学的计算化学
- 生物有机化学 生物有机化学
背景情况:
- 丁酸是具有潜在生物学意义的独特反应物种.
- 最近报告了低温生成和光谱表征.
- 之前的红外光谱数据表明了一个跨中心对称的形状.
研究的目的:
- 通过使用计算方法来研究dinitrosylheme中首选的配体方向.
- 解决理论预测与现有的光谱数据之间的差异.
主要方法:
- 使用密度函数理论 (DFT) 的计算.
- 评估了 cis 和 trans 形态的能量优势.
主要成果:
- DFT计算强烈支持两个NO配体的cis C2v形态.
- 在能量方面,cis构造比trans导向优于大约20kcal/mol.
- 这一发现与之前从红外光谱学提出的变形相反.
结论:
- 这项研究表明,dinitrosylheme中NO配体具有显著的cis导向偏好.
- 计算结果挑战了以前对光谱数据的解释.
- 了解这种构造对于阐明dnitrosylheme的生物相关性至关重要.
相关概念视频
Structural Isomerism
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can be...
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can be...
Structure of Conjugated Dienes
Introduction
Conjugated dienes are compounds characterized by the presence of alternating double and single bonds. In a conjugated system like 1,3-butadiene, the unhybridized 2p orbital on each carbon overlaps continuously, allowing the π electrons to be delocalized across the entire molecule. In contrast, this type of overlap does not occur in cumulated and isolated dienes, such as 2,3-pentadiene and 1,4-pentadiene, respectively. Instead, the π electrons remain localized between the double...
Conjugated dienes are compounds characterized by the presence of alternating double and single bonds. In a conjugated system like 1,3-butadiene, the unhybridized 2p orbital on each carbon overlaps continuously, allowing the π electrons to be delocalized across the entire molecule. In contrast, this type of overlap does not occur in cumulated and isolated dienes, such as 2,3-pentadiene and 1,4-pentadiene, respectively. Instead, the π electrons remain localized between the double...
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.
Structure of Benzene: Kekulé Model
In 1865, August Kekule suggested the structure of benzene according to the structural theory of organic chemistry based on the three assertions—formula of benzene is C6H6, all the hydrogens of benzene are equivalent, and each carbon must have four bonds due to its tetravalency.
He proposed that benzene has a cyclic structure of six carbon atoms attached to one hydrogen atom each, with three alternating pi bonds.
He proposed that benzene has a cyclic structure of six carbon atoms attached to one hydrogen atom each, with three alternating pi bonds.
Structure of Amines
The hybridized nitrogen atom in amines possesses a lone pair of electrons and is bound to three substituents with a bond angle of around 108°, which is less than the tetrahedral angle of 109.5°. However, the C–N–H bond angle is slightly larger at 112°, with a carbon–nitrogen bond length of 147 pm. This carbon–nitrogen bond length of of amines is longer than the carbon–oxygen bond of alcohols (143 pm) but shorter than alkanes’ carbon–carbon bond (154 pm). These aspects are illustrated in Figure...
Aromatic Hydrocarbon Cations: Structural Overview
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 with both...
Removing one hydrogen from the intervening CH2 group with both...


