Prediction of acid pKa values in the solvent acetone based on COSMO-RS,Journal of Computational Chemistry

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Prediction of acid pKa values in the solvent acetone based on COSMO-RS
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2022-04-22 , DOI: 10.1002/jcc.26864
Niklas Sülzner ₁ , Julia Haberhauer ₁ , Christof Hättig ₁ , Arnim Hellweg ₂

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In this contribution we extent the use of the conductor-like screening model for realistic solvation (COSMO-RS) to the prediction of pK_a values in acetone, a commonly used dipolar aprotic solvent. For this, we calculated the Gibbs free energy of dissociation of 120 organic acids (nine acrylic acids, 87 benzoic acids, nine phenols, and 15 benzenesulfonamides) using COSMO-RS at the two levels BP-TZVP and BP-TZVPD-FINE and determined the parameters for a linear free energy relation for the p𝐾a $p K_{a}$ prediction by performing linear fits to experimental values. Our results suggest that the data set dissects into two groups, with the phenols being different from the other three subsets. The acrylic and benzoic acids and the sulfonamides can be treated together and yield an excellent linear correlation (𝑟2>0.95 $r^{2} > 0.95$ ) with an RMSD of only ~0.3. The slope is found to be significantly smaller than the theoretical value (1/𝑅𝑇ln10 $1 / RT \ln 10$ ), only 45% of it, which is in accordance with findings in the literature. The phenols, however, while similarly well correlated in their own subset with an RMSD of 1.7–1.9, exhibit a slope larger than one. We discuss both a higher uncertainty in the reference values as well as physical origins as possible reasons.

中文翻译：

基于COSMO-RS的溶剂丙酮酸pKa值预测

在这篇文章中，我们将用于实际溶剂化的类导体筛选模型 (COSMO-RS) 扩展到预测丙酮（一种常用的偶极非质子溶剂）中的 p K _a值。为此，我们使用 COSMO-RS 在 BP-TZVP 和 BP-TZVPD-FINE 两个水平上计算了 120 种有机酸（9 种丙烯酸、87 种苯甲酸、9 种酚和 15 种苯磺酰胺）的吉布斯解离能，并确定了线性自由能关系的参数p𝐾一种 $p K_{a}$ 通过对实验值进行线性拟合来进行预测。我们的结果表明，数据集分为两组，酚类与其他三个子集不同。丙烯酸和苯甲酸以及磺胺类药物可以一起处理并产生出色的线性相关性（𝑟2> 0.95 $r^{2} > 0.95$ ) RMSD 仅为 ~0.3。发现斜率明显小于理论值（1 / 𝑅𝑇 ln 10 $1 / RT \ln 10$ )，只有 45%，这与文献中的发现一致。然而，酚类虽然在它们自己的子集中具有 1.7-1.9 的 RMSD 类似地很好地相关，但表现出大于 1 的斜率。我们讨论了参考值中较高的不确定性以及物理来源作为可能的原因。

更新日期：2022-04-22

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