碳二二烯稳定型素呈现强烈的分子内电荷转移过渡
Sudipta Roy1, Peter Stollberg, Regine Herbst-Irmer
1Institut für Anorganische Chemie, Georg-August-Universität , Tammannstraße 4, 37077 Göttingen, Germany.
Journal of the American Chemical Society
|December 25, 2014
概括
研究人员使用循环氨基 (cAAC) 和N-异环 (NHC) 稳定了氨基复合体氨基,一种氨基复合体. 这些稳定的化合物呈现出鲜明的颜色,蓝色的cAAC复合体显示出较低的LUMO能量.
科学领域:
- 有机化学 有机化学
- 碳烯化学 碳烯化学
- 主群 化学 化学
背景情况:
- 作为一种不稳定的物种的二化,此前已被碳联体稳定.
- 碳联体可以通过与金属碳结合的坐标键稳定化合物.
研究的目的:
- 为了合成和表征由碳稳定的新型胺复合物.
- 研究这些新型化合物的电子结构和结合.
- 探索影响这些复合体颜色的因素.
主要方法:
- 碳稳定二西烯复合物的合成.
- 稳定的素化合物的分离和表征.
- 理论计算 (DFT) 来研究电子结构和粘合.
- 光谱分析以了解颜色的起源.
主要成果:
- 总式为碳→SiCl2→P-Ar的稳定胺基复合体是使用循环 (cAAC) 和N-异环碳 (NHC) 连接物合成的.
- 由此产生的化合物2 (cAAC) 和3 (NHC) 是可分离和可储存的,分别呈现深蓝色和红色.
- 理论计算揭示了电子结构,HOMO位于πSiP键上,LUMO位于碳素部分上.
- 与NHC相比,化合物2的强烈蓝色归因于分子内电荷转移 (ICT) 和cAAC联体中的较低的LUMO.
结论:
- 碳联体,特别是cAAC,可以有效地稳定phosphinidene物种.
- 这些复合物的电子特性和由此产生的颜色可以通过选择碳联体来调整.
- 这些发现为低价值物种的稳定性和反应性提供了新的见解.
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