变化在pnictogen-oxygen结合解锁大大增强的Bronsted基本性为单体氧化物stibine氧化物的变化
John S Wenger1, Addis Getahun1, Timothy C Johnstone1
1Department of Chemistry and Biochemistry, University of California Santa Cruz, Santa Cruz, California 95064, USA. johnstone@ucsc.edu.
Dalton transactions (Cambridge, England : 2003)
|August 2, 2023
概括
像stibine氧化物这样的更重的pnictine氧化物由于电子结构的变化而显著增强了布伦斯特基本性. 这种增加的基本性提高了它们在转化等反应中的催化效率.
科学领域:
- 有机金属化学 有机金属化学
- 无机化学 无机化学 有机化学
- 物理化学 物理化学
背景情况:
- 单质素氧化物和素氧化物通过O中心的单一对作为布伦斯特德基.
- 在pnictoryl结合的周期性趋势被扩展到与Dipp3SbO.的合成.
- 计算研究表明,较重的菌素增强了孤独对的破坏稳定性和捐赠能力.
研究的目的:
- 为了评估单质酸氧化物 (Dipp3PnO; Pn = P, As, Sb) 的布伦斯特德基本性.
- 为了研究核素原子原子号对电子结构和基本性的影响.
- 探索增强的氧化基本性的催化应用.
主要方法:
- 用各种酸的固体测量反应性研究.
- 计算研究包括异体反应和质子亲和力.
- H NMR光谱定位用于pKaH,MeCN的确定.
主要成果:
- 与较轻的同类相比,SbO显示出大大增强的质子接受.
- 从Dipp3AsO到Dipp3SbO.观察到布伦斯特德基本度增加了10倍.
- 在Bronsted基催化转化中,SbO显著提高了催化效率.
结论:
- 布伦斯特基本性从Dipp3PO
3AsO 3SbO.大幅增加 - 这种趋势是由于随着原子数的增加而发生的pnictoryl键电子结构变化的直接结果.
- 提升Dipp3SbO的基本性为改善催化应用提供了潜力.
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