Gas-Phase Basicity and Acidity Trends in α,β-Unsaturated Amines, Phosphines, and Arsines
作者:Otilia Mó、Manuel Yáñez、Michèle Decouzon、Jean-François Gal、Pierre-Charles Maria、Jean-Claude Guillemin
DOI:10.1021/ja982657e
日期:1999.5.1
The acidity and basicity trends in the series of α,β-unsaturated amines, phosphines, and arsines were analyzed through the use of G2 ab initio calculations and the examination of experimental data obtained by means of FT-ICR techniques. The α,β-unsaturated amines, phosphines, and arsines are less basic but significantly more acidic than the corresponding saturated analogues. However, while both vinyl-
通过使用 G2 ab initio 计算和检查通过 FT-ICR 技术获得的实验数据,分析了一系列 α,β-不饱和胺、膦和胂的酸度和碱度趋势。与相应的饱和类似物相比,α,β-不饱和胺、膦和胂的碱性较低,但酸性明显更强。然而,虽然乙烯基和乙炔胺都优先在 β-碳原子上质子化,但乙烯基和乙炔基膦在气相中是磷碱。胂与相应的膦非常相似,尽管 Cα 原子的质子化与杂原子的质子化竞争。由于 XH- 基团与 C-C 多重键的有利相互作用,不饱和化合物的酸性增强主要归因于阴离子的稳定化。这种稳定作用对胺类最大,对胂类最小。这些不饱和化合物的低相对碱性是由于不稳定...