八面体盐酸催化剂用于olefin聚合:替代剂和溶剂对结构和动态的影响
Anna Dall'Anese1,2, Pavel S Kulyabin3,2, Dmitry V Uborsky3,2
1Dipartimento di Chimica, Biologia e Biotecnologie, Università degli Studi di Perugia, Via dell'Elce di sotto 8, 06123 Perugia, Italy.
Inorganic chemistry
|September 19, 2023
概括
第4组金属-萨兰烯聚合催化剂表现出增强的活性,具有特定的萨兰配体修饰. 这些变化使活跃的fac-fac异构体稳定于不活跃的mer-mer异构体上,从而提高了聚合率.
科学领域:
- 有机金属化学 有机金属化学
- 聚合物科学 聚合物科学
- 催化剂是一种催化剂.
背景情况:
- 第4组金属-萨兰催化剂对于烯酸聚合是至关重要的.
- 它们的活性通常受到平衡的限制,有利于一个不活跃的mer-mer同位素.
- 活跃的面对面物种的形成需要异构化,这是一个速度限制的步骤.
研究的目的:
- 研究萨兰联体结构对催化剂活性和同位素偏好的影响.
- 阐明溶剂在稳定活性与非活性催化剂物种中的作用.
- 描述4组金属-萨兰烯聚合催化剂的活性和静止状态.
主要方法:
- 合成和激活各种4组金属-萨兰复合物与不同的整形替代剂.
- 在现场核磁共振 (NMR) 光谱学研究同位素动态和物种化.
- 用X射线晶体学来确定激活复合物的固态结构.
- 动力学研究以确定位点表皮化障碍物和反应机制.
主要成果:
- 具有大,平面替代物的萨兰联体通过稳定活性面面异构体,显著增强催化剂活性.
- 在现场的NMR和晶体结构显示,快速催化剂更喜欢面对面的同位素,而缓慢的催化剂更喜欢扭曲的mer-mer同位素.
- 溶剂协调强度和整形替代剂的体积极大地影响同位素平衡.
- 这是Zr-Salan催化剂的活性聚合基物种首次被描述.
结论:
- 第4组金属-萨兰烯聚合中的催化剂活性与活性fac-fac异构体的稳定直接相关.
- 连接体的设计,特别是正体替代剂的固态和电子性质,是控制同位素平衡和催化剂性能的关键.
- 溶剂在调节催化剂物种化和活性方面发挥着至关重要的作用.
- 这项工作为基于Salan的olefin聚合的机制提供了基本的见解.
相关概念视频
Ziegler–Natta Chain-Growth Polymerization: Overview
3.4K
Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
3.4K
Olefin Metathesis Polymerization: Overview
2.2K
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...
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists...
2.2K
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
8.5K
The rate of acid-catalyzed hydration of alkenes depends on the alkene's structure, as the presence of alkyl substituents at the double bond can significantly influence the rate.
8.5K
Polymer Classification: Stereospecificity
2.5K
Polymerization generates chiral centers along the entire backbone of a polymer chain. Accordingly, the stereochemistry of the substituent group has a significant effect on polymer properties. Polymers formed from monosubstituted alkene monomers feature chiral carbons at every alternate position in the polymer backbone. Relative to the predominant orientation of substituents at the adjacent chiral carbons, the polymer can exist in three different configurations: isotactic, syndiotactic, and...
2.5K
Stability of Substituted Cyclohexanes
12.7K
This lesson discusses the stability of substituted cyclohexanes with a focus on energies of various conformers and the effect of 1,3-diaxial interactions.
The two chair conformations of cyclohexanes undergo rapid interconversion at room temperature. Both forms have identical energies and stabilities, each comprising equal amounts of the equilibrium mixture. Replacing a hydrogen atom with a functional group makes the two conformations energetically non-equivalent.
For example, in...
The two chair conformations of cyclohexanes undergo rapid interconversion at room temperature. Both forms have identical energies and stabilities, each comprising equal amounts of the equilibrium mixture. Replacing a hydrogen atom with a functional group makes the two conformations energetically non-equivalent.
For example, in...
12.7K
Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride
1.8K
Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation...
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation...
1.8K


