用空腔绑定客体和表面绑定阴离子在阴离子协调中的催化:抑制,激活和自催化
William Cullen1, Alexander J Metherell1, Ashley B Wragg1
1Department of Chemistry, University of Sheffield , Sheffield S3 7HF, U.K.
Journal of the American Chemical Society
|February 8, 2018
概括
协调可以催化Kemp消除反应. 其他离子的存在可以抑制这种反应,导致产品加速反应的自催化路径.
科学领域:
- 超分子化学
- 催化剂
背景情况:
- 立方M8L12协调通过客体结合和氧化物积累催化Kemp消除.
- 这种反应涉及中化和表面的离子结合.
研究的目的:
- 调查其他离子如何影响催化Kemp消除.
- 在有竞争性离子的情况下探索新的反应途径的出现.
主要方法:
- 在立方M8L12协调中研究了Kemp消除反应.
- 引入各种离子 (化物,化物,酸盐) 来观察它们对催化物的作用.
- 分析了反应动力学和形状,包括西格形行为.
主要成果:
- 和离子通过积聚在子表面来抑制氧化物介导的催化.
- 当氧化物被取代时,一个自催化途径出现,产物 (2-烯酸盐) 作为基.
- 对子表面的阳离子亲和力如下:2-烯酸盐 > 化物 > 氧化物.
- 添加的酸盐根据其基本性加速反应,证实可控制的离子影响.
结论:
- 在协调内的Kemp消除对竞争性离子的存在敏感.
- 可以通过产品在表面积累来诱导自催化,从而提供可控制的反应途径.
- 这项工作推进了对涉及空腔结合客体和表面积累的离子的双分子反应的协调的使用.
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