在Tris ((9-fluorenylidene) 甲中超过2 Å的长碳-碳结合
Takashi Kubo1,2, Yuki Suga1, Daisuke Hashizume3
1Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan.
Journal of the American Chemical Society
|August 30, 2021
概括
研究人员在烯化合物中研究了异常长的碳-碳键 (超过2.0 Å). 实验和计算方法证实了这些扩展的C-C键中的共价键相互作用.
科学领域:
- 有机化学
- 固态化学
- 计算化学
背景情况:
- 在有机化学中,碳-碳键是基本的,通常在1.5至1.54 Å之间.
- 延长的C-C键长度挑战了传统的结合理论和分子结构的理解.
研究的目的:
- 研究长于2.0 Å的C-C键的形成和特征.
- 分析具有这种扩展C-C键的烯化合物的电子结构和结合性质.
主要方法:
- 进行X射线电子密度映射以可视化电子分布.
- 固态碳-13核磁共振 (NMR) 光谱
- 完成主动空间自相一致场 (CASSCF) 的计算.
主要成果:
- 通过垂直导向的烯环形成的超过2.0 Å的C-C键.
- X射线数据揭示了最小的电子密度, 表明遥远的碳原子之间的轨道重叠.
- 最高占用分子轨道 (HOMO) 和最低不占用分子轨道 (LUMO) 的分析分别显示了相内和相外相互作用,电位间隔为2.39 eV.
- 固态13CNM显示长键碳的峰值为82.9ppm.
- 根据CASSCF (6,6) 的计算,它具有较低的激进性.
结论:
- 实验和理论数据证实了异常长的C-C键中存在共价键相互作用.
- 这项研究提供了对具有非传统键长度的分子的电子和结构性质的见解.
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