电场辅助的阴离子π催化
Masaaki Akamatsu1, Naomi Sakai1, Stefan Matile1
1Department of Organic Chemistry, University of Geneva , 1211 Geneva, Switzerland.
Journal of the American Chemical Society
|May 9, 2017
概括
电场远程控制子-π催化,增强反应速度和选择性. 这种电场辅助的催化对控制化学反应具有前景.
科学领域:
- 催化剂
- 物理化学
- 材料科学
背景情况:
- 阴离子-π催化利用电子缺陷 π 系统的催化剂与阴离子相互作用.
- 远程控制催化活性和选择性是化学合成的一个重大挑战.
研究的目的:
- 通过电场对子-π催化物的远程控制进行研究.
- 探索电场对固定离子-π催化剂的活性和选择性的影响.
主要方法:
- 在导电性氧化物表面上合成和固定-π催化剂.
- 在不同电场下研究马龙酸半与酸受体的添加反应.
- 研究酸盐添加对催化剂对电场的反应效应.
主要成果:
- 离子-π催化剂的活性和选择性由应用的电场调节.
- 对于一个不利的反应途径,观察到的速率增长超过100倍.
- 过渡状态识别的选择性提高了高达 -14.8 kJ mol-1
- 添加酸盐 (IC50=2.2 mM) 取消了电场的响应.
结论:
- 电场可以使离子催化剂的 π 酸表面两极化,增强介质和过渡状态的识别.
- 这证明了电场辅助子-π催化物的存在和实际意义.
- 这些发现为触媒过程的远程控制开辟了新的途径.
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