离子的pi-arene和单对素协调之间的竞争?
Paola Romanato1, Simon Duttwyler, Anthony Linden
1Organic Chemistry Institute, University of Zurich, Winterthurerstrasse 190, 8057 Zurich, Switzerland.
Journal of the American Chemical Society
|July 20, 2011
概括
通过侧环相互作用,m-terphenyl支架稳定了离子. 来自化和梅西 π 面的直接协调对这种稳定有相对应的贡献.
科学领域:
- 有机化学 有机化学
- 超分子化学 超分子化学
- 计算化学是一种计算化学.
背景情况:
- 众所周知,2,6-diarylphenyl (m-terphenyl) 支架可以在固态上阻碍核友性攻击并稳定离子.
- 侧环相互作用和与的直接协调是拟议的稳定机制.
研究的目的:
- 评估直接的正极和 π 电子丰富的面部协调对 2,6-diarylphenylSiR(2) 电离子中的稳定性的相对贡献.
- 为了研究替代剂在m-terphenyl支架上的电子和硬质效应.
主要方法:
- 合成了一系列具有不同替代剂的2,6-diarylphenylSiR(2) 离子.
- 频谱分析 (NMR,UV-Vis) 来探测电子结构和粘合.
- 计算建模 (DFT) 来分析电荷分布和相互作用能量.
主要成果:
- 这种m-terphenyl支架有效地保护了中心免受核友的攻击.
- 观察到由替代的环中的正体原子直接协调.
- 还检测到来自梅西基的 π 电子丰富的面部协调.
- 计算和光谱数据表明,化协调和梅西π面相互作用的稳定贡献相似.
结论:
- 通过m-terphenyl支架稳定离子是固体保护和电子相互作用的结果.
- 整形替代剂 (如) 的直接协调和π面相互作用起着重要的,可比的作用.
- 这些发现为设计各种应用的稳定基阴离子物种提供了洞察力.
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