"反向电子需求"连接体替代:实验和计算的洞察力在的olefin 交换在 ((0))
Brian V Popp1, Joseph L Thorman, Christine M Morales
1Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI 53706, USA.
Journal of the American Chemical Society
|November 13, 2004
概括
在(0) 复合体中发生的olefin 替代是通过一种关联机制发生的. 缺电子的烯反应更快,表明 ((0) 在这种反向电子需求反应中充当核友.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 反应机制 反应机制
背景情况:
- 了解富含电子的晚期过渡金属的反应性在催化过程中至关重要.
- ((0) 复合物是广泛使用的催化剂,但它们的替代机制需要进一步阐明.
研究的目的:
- 为了研究中烯酸替代的机制(0).
- 为了深入了解的基本反应性(0) 与olefins.
- 将观察到的烯酸替代物归类为一种特定类型的配体替代反应.
主要方法:
- 合成和表征巴托库普罗因-(0) 复合物与不同的酸铁烯配体.
- 对氨酸替代反应的动力学研究.
- 密度函数理论 (DFT) 计算以建模反应路径.
主要成果:
- 氨酸替代反应通过一种关联机制进行.
- 更缺乏电子的烯具有更快的反应速率.
- DFT的计算显示(0) 作为核爱好者,攻击烯酸的空PI轨道.
结论:
- 在中烯酸替代 (((0) 是一种"反向电子需求"的配体替代反应.
- 中心的核性特征决定了反应的选择性.
- 这项研究为晚期过渡金属的反应性提供了新的视角.
相关概念视频
Free-Radical Chain Reaction and Polymerization of Alkenes
The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.
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.
Olefin Metathesis Polymerization: Overview
Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
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Ion exchange chromatography separates charged molecules from a solution by reversibly exchanging them with mobile, or 'active', ions associated with the oppositely charged stationary phase. This method can be used to separate ions, soften and deionize water, and purify solutions. The polymers comprising the ion-exchange column are high-molecular-weight and chemically stable polymers, crosslinked to be porous and essentially insoluble. They are also functionalized with either acidic or basic...


