硫离子在π-酸催化剂的服务中
Ruiping Li1, Mohammad Zafar1, David Danovich1
1Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem, 9190401, Israel.
Angewandte Chemie (International ed. in English)
|November 27, 2023
概括
研究人员为催化开发了刚性硫钉联体. 这些配体增强金属的电友性,使高反应性三酸 () 复合物可用于均催化.
科学领域:
- 有机金属化学 有机金属化学
- 一致性催化剂的同质性
- 连接体设计 连接体设计
背景情况:
- 阴离子配体对于π-酸催化是有价值的,因为它具有可调节的电子吸收特性.
- 之前已经引入了型硫酸,但由于具有不稳定的金属硫键,限制了催化使用.
研究的目的:
- 为了克服硫结合金属复合物的可变性问题.
- 为了证明硬化硫钉联体与的催化潜力.
主要方法:
- 合成和X射线晶体分析一种新的刚性硫钉-Pt (II) 复合物的合成和X射线分析.
- 密度函数理论 (DFT) 计算以探测电子结构和金属电友性.
- 使用新复合物和乙烯类似物进行循环异构化反应的动力学研究.
主要成果:
- 一个硬的硫钉脚手架成功地稳定了Pt (II) 复合体中的金属硫键.
- 射线分析证实了尽管有正电荷,但硫的协调.
- 由于硫协调,DFT的计算显示了Pt (II) 中心的增强电友性.
- 动力学研究显示,与其乙烯类似物相比,三酸盐硫-Pt(II) 复合物的反应性显著更高.
结论:
- 增加硫刀脚手架的刚性可以克服MS债券可变性问题.
- 这项研究展示了硫基联体在同质催化中的首次成功应用.
- 开发出的三酸硫-Pt(II) 复合体是循环异构反应的高度反应性催化剂.
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