使用Co (III) /K (I) 异质核催化剂的二氧化碳和氧化物环开放共聚化机制的洞察
Arron C Deacy1, Andreas Phanopoulos2, Wouter Lindeboom1
1Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Oxford OX1 3TA, U.K.
Journal of the American Chemical Society
|September 21, 2022
概括
这项研究揭示了-催化剂如何促进二氧化碳和二氧化的共聚化. 会激活单体,而会启动环开放,指导未来的催化剂设计.
科学领域:
- 催化剂
- 聚合物化学
- 计算化学
背景情况:
- 二氧化碳和氧化物的环开放共聚化对于生产有价值的聚合物至关重要.
- 了解催化机制是提高催化剂效率和选择性的关键.
- 双核催化剂具有独特的反应性,但它们的机制往往未得到充分研究.
研究的目的:
- 通过使用Co (III) K (I) 异核复合物来阐明二氧化碳和氧化物的催化循环开环共聚.
- 确定和在激活单体和稳定中间体中的作用.
- 为了合理设计催化剂,研究产品和副产品形成的机制.
主要方法:
- 结合实验和计算 (密度函数理论) 的研究.
- 在不同的条件下分析催化活性和选择性.
- 关键反应步骤的热力学和动力学障碍计算.
主要成果:
- 会激活氧化物并稳定中间体;为环开放提供核爱素.
- 对环氧化物开放和碳酸形成的计算激活障碍具有竞争力.
- 实验结果证实了二氧化碳和碳酸盐中间体之间的平衡,可通过二氧化碳压力和温度进行控制.
结论:
- Co (III) K (I) 复合物有效催化共聚合物,每个金属中心都有不同的作用.
- 确定速率的步骤是氧化物环开放,选择性受中间平衡的影响.
- 这种机制的理解为设计改进的二氧化碳利用催化剂提供了基础.
相关概念视频
Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)
2.7K
Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
2.7K
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
Cationic Chain-Growth Polymerization: Mechanism
2.4K
The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the...
2.4K
Base-Catalyzed Ring-Opening of Epoxides
8.8K
Due to their highly strained structures, epoxides can readily undergo ring-opening reactions through nucleophilic substitution, either in the presence of an acid or a base. The nucleophilic substitution reactions in the presence of acid are called acid-catalyzed ring-opening reactions, and nucleophilic substitution reactions in the presence of a base are called base-catalyzed ring-opening reactions. Epoxides undergo base-catalyzed ring-opening reactions in the presence of a strong nucleophile...
8.8K
Acid-Catalyzed Ring-Opening of Epoxides
7.6K
Epoxides that are three-membered ring systems are more reactive than other cyclic and acyclic ethers. The high reactivity of epoxides originates from the strain present in the ring. This ring strain acts as a driving force for epoxides to undergo ring-opening reactions either with halogen acids or weak nucleophiles in the presence of mild acid. The acid catalyst converts the epoxide oxygen, a poor leaving group, into an oxonium ion, a better leaving group, making the reaction feasible. The...
7.6K
Vicinal Diols via Reductive Coupling of Aldehydes or Ketones: Pinacol Coupling Overview
1.8K
Wilhelm Rudolph Fittig discovered the pinacol coupling reaction in 1859. It is a radical dimerization reaction and involves the reductive coupling of aldehydes or ketones in the presence of hydrocarbon solvent to yield vicinal diols.
1.8K


