奇数电子结合的硫基离子:X射线结构证据表明硫-硫三电子 σ 键
Senwang Zhang1, Xingyong Wang, Yunxia Sui
1State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, and ‡Centre of Modern Analysis, Nanjing University , Nanjing 210093, China.
Journal of the American Chemical Society
|October 10, 2014
概括
持久的基离子由1,8甲甲烯形成. 这些离子体表现出三电子的西格玛键,其中一个具有硫-硫键,另一个具有罕见的异原子键.
科学领域:
- 有机化学 有机化学
- 材料科学 材料科学 材料科学
- 计算化学计算化学
背景情况:
- 1,8-甲甲是具有独特电子特性潜力的分子.
- 了解基的电子结构对于开发新材料至关重要.
研究的目的:
- 为了研究由1,8-甲纳烯衍生的基离子的形成和性质.
- 为这些基离子中三电子西格玛键提供结构证据.
主要方法:
- 一个电子的氧化1,8-甲纳.
- 电子偏磁共振 (EPR) 光谱学.电子偏磁共振 (EPR) 光谱学.
- 紫外线对吸收光谱学.
- 密度函数理论 (DFT) 的计算.
主要成果:
- 在溶液中产生了持久基离子,Nap ((SPh) 2 (1•+) 和Nap ((SPh) ((SePh) (2•+).
- 两个离子体都显示了三电子的西格玛键,由EPR,UV-vis和DFT证实.
- 阴离子1•+在固态中是稳定的,而2•+在结晶后二元化,但在溶液中改变了基离子.
结论:
- 对于1•+中的硫-硫三电子西格玛键的确的结构证据.
- 在2•+中证明了一种罕见的持久异原子三电子西格玛键.
- 突出了含有素的芳香系统独特的结合能力.
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