一个前所未有的α-olefin分布,由一个均的乙烯寡合化催化剂产生的
Atanas K Tomov1, Juan J Chirinos, Richard J Long
1Imperial College London, South Kensington Campus, London SW7 2AY, UK.
Journal of the American Chemical Society
|June 15, 2006
概括
一种新型的催化剂有效地氧化乙烯,产生独特的α-olefins分布. 这种不寻常的产品选择性是由一个涉及双催化站点的金属环链生长机制解释的.
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:
- 复合物是烯寡合化的已知催化剂.
- 控制olefin寡合化中的产品分布仍然是一个重大挑战.
研究的目的:
- 为了研究 bis(benzimidazolyl) 胺复合物的催化活性和产品选择性.
- 阐明所观察到的不寻常产品分布背后的机制.
主要方法:
- 使用复合物和甲基氨 (MAO) 的乙烯寡合化.
- 乳标记研究探测反应途径.
- 对1-烯产品分布的分析.
主要成果:
- 催化剂表现出异常高的乙烯寡合化活性.
- 观察到前所未有的产品分布,C4n系列的烯酸比C4n+2系列丰富得多.
- 标签支持一个金属环链生长机制.
结论:
- 双 () 胺复合物是一种高度活性和选择性的寡合化催化剂.
- 这种不寻常的产品分布源于一个金属循环机制内的两个不同的催化位点的相互作用.
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.
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
Anionic Chain-Growth Polymerization: Mechanism
The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael acceptor.
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...
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)
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...
Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)
Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...


