使用二结合双金属催化剂对环氧化物进行酶选择性聚合:一项机械学研究
Syud M Ahmed1, Albert Poater, M Ian Childers
1Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University , Ithaca, New York 14853-1301, United States .
Journal of the American Chemical Society
|November 9, 2013
概括
与二结合的双金属催化剂使氧化物 (PO) 的酶选择性聚合成为可能. 催化剂结构,特别是双纳连接器,在这个关键的聚合过程中决定了立体选择性.
科学领域:
- 有机金属化学 有机金属化学
- 聚合物化学 聚合物化学
- 催化剂是一种催化剂.
背景情况:
- 氧化物 (PO) 聚合对于生产聚乙烯至关重要.
- 在PO聚合物中达到高的反抗选择性仍然是一个挑战.
- 双金属盐催化剂提供了受控聚合的潜力.
研究的目的:
- 通过使用二结合二金属 (Co) 催化剂,研究氧化物 (PO) 的酶选择性聚合.
- 阐明催化剂的结构特征,选择性,氧化状态,共催化剂作用和单体连锁机制.
- 探索结构-活动关系,以提高催化性能.
主要方法:
- 对PO聚合物的动力学和选择性的实验研究.
- 合成具有不同链接结构的新型双金属催化剂.
- 密度函数理论 (DFT) 计算用于机械洞察和结构分析.
主要成果:
- 双纳连接器的绝对立体化学对于确定酶选择性至关重要.
- 一种新的灵活的双联结催化剂显示了对PO的反选择性聚合,尽管选择性较低.
- DFT揭示了活性催化剂形式涉及外离子联体和内聚合物醇氧化物.
- 启动受益于内化联体;传播受益于两个外氧化联体.
结论:
- 双金属Cosalen催化剂与二甲结合,可有效用于对PO聚合物的酶选择性聚合.
- 催化剂的设计,特别是链接器的立体化学和灵活性,显著影响了酶选择性.
- 来自DFT的详细机制理解有助于设计更高效的催化剂.
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