Correlations and predictions of pKa values of fluorophenols and bromophenols using hydrogen-bonded complexes with ammonia
Correlations and predictions of pKa values of fluorophenols and bromophenols using hydrogen-bonded complexes with ammonia
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DOI：
10.1021/jp052824e
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发表时间：
2006-01-12
影响因子：
2.9
通讯作者：
Tao, FM
中科院分区：
文献类型：
--
作者：
Han, J;Tao, FM
对一系列氢键氟苯酚-氨和溴苯酚-氨配合物进行了密度泛函理论计算。分子间和分子内的性质，特别是与氢键有关的性质，已经被仔细地分析了。一些性质，如羟基的键长和拉伸频率，氢键长和结合能，被证明是高度相关的，并且与已知的实验pK(a)值线性相关。线性相关性已用于预测该系列中所有氟苯酚和溴苯酚的pK(a)值。不同分子性质的预测pK(a)值是一致的，并且与现有的实验值很好地吻合。该研究表明，计算出的氢键配合物的分子性质可以利用已建立的线性相关性有效和系统地预测大范围有机酸的pK(a)值。
Density functional theory calculations have been preformed on a series of the hydrogen-bonded fluorophenol-ammonia and bromophenol-ammonia complexes. Intermolecular and intramolecular properties, particularly those related to hydrogen bonding, have been carefully analyzed. Several properties, such as the bond length and stretching frequency of the hydroxyl group, the hydrogen bond length and binding energy, are shown to be highly correlated with each other and are linearly correlated with known experimental pK(a) values of the halogenated phenols. The linear correlations have been used to predict the pK(a) values of all fluorophenols and bromophenols in the series. The predicted pK(a) values are shown to be consistent from different molecular properties and are in good agreement with available experimental values. This study suggests that calculated molecular properties of hydrogen-bonded complexes allow the effective and systematic prediction of pK(a) values for a large range of organic acids using the established linear correlations.