在碗形π-基离子中可逆 σ-键形成:曲线和平面结构的影响
Hiroki Yokoi1, Satoru Hiroto1, Hiroshi Shinokubo1
1Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering , Nagoya University , Nagoya , Aichi 464-8603 , Japan.
Journal of the American Chemical Society
|March 16, 2018
概括
这项研究揭示了可逆的西格玛二分化在碗形的pi根酸子中,这是一个罕见的现象. 曲的结构促进了这种二元化和核性添加,与平面系统不同.
科学领域:
- 有机化学
- 超分子化学
- 材料科学
背景情况:
- 有机基的可逆西格玛键形成已得到充分研究.
- 很少报告从非局部化的pi- 基离子中形成西格玛二元体.
研究的目的:
- 为了研究一个碗形的pi根离子的可逆sigma-dimerization.
- 探索独特的曲线结构对二元化和反应性的影响.
主要方法:
- 单晶X射线衍射用于结构分析.
- 核磁共振 (NMR) 光谱学
- 通过光学光谱.
- 理论上的计算.
主要成果:
- 在水晶状态和溶液中证明了盘状pi根子的可逆sigma-dimerization.
- 在低温二元化过程中确定了C-C西格玛键的形成.
- 由于曲的结构,观察到增强的二分化和核添加 (甲氧化).
- 理论计算证实了由于减压而加速的结合形成.
结论:
- 巴基碗衍生的pi-基离子的弧形结构显著促进了西格玛二分化和核友性攻击.
- 曲系统中的结构应变缓解加速了内部碳原子的键形成.
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