对于N-Haloimide2-替代的里丁复合体,对素键几何学上的奥托替代效应
Shilin Yu1, J Mikko Rautiainen1, Parveen Kumar1
1Department of Chemistry, University of Jyvaskyla, P.O. Box 35, Jyvaskyla, 40014, Finland.
这项研究使用晶体学,DFT和NMR探索N-化物和化物之间的素结合. 复杂化能量和关联常数揭示了对相互作用的见解,二次相互作用影响了解决方案行为.
科学领域:
- 超分子化学 超分子化学
- 有机化学 有机化学
- 晶体学 晶体学是指结晶学.
背景情况:
- 素结合 (XB) 是一种显著的非共价相互作用.
- 胺和胺是研究XB相互作用的关键组成部分.
- 了解控制XB复合体形成的因素对于分子设计至关重要.
研究的目的:
- 为了研究 (imide) N-XN (pyridine) 素结合复合物的结构和能量特性.
- 为了将晶体学数据,DFT计算和NMR光谱学发现相关起来.
- 阐明二次相互作用对溶液中复杂稳定性的影响.
主要方法:
- 采用X射线晶体学,确定了68个晶体结构.
- 进行了密度函数理论 (DFT) 计算,得到了 86 个复合能.
- 使用NMR光谱测量90个关联常数.
主要成果:
- N-胺:皮里丁复合物表现出不同的固态度和结构特征,包括N-X键中的键曲.
- 对于N-bromoimide和iodoimide复合体,DFT复合能量范围分别在-31到-99kJ/mol之间.
- 由于二次相互作用,NMR关联常数和DFT能量在溶液中没有相关性,但关联常数与N-胺 σ-孔强度保持一致.
结论:
- 素键捐赠者的强度显著影响复杂的形成和结构.
- 二次相互作用在溶液相复杂行为中起着关键作用,影响不同实验方法之间的相关性.
- 关联常数主要取决于N-化体的电子性质 (σ-孔强度).
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