Kostin Mikhail A, Alkhuder Omar, Xu Luhang, Krutin Danil V, Asfin Ruslan E, Tolstoy Peter M
Institute of Chemistry, St. Petersburg State University, St. Petersburg, Russia.
Department of Physics, St. Petersburg State University, St. Petersburg, Russia.
Phys Chem Chem Phys. 2024 Mar 27;26(13):10234-10242. doi: 10.1039/d3cp05817d.
In this work IR spectral characteristics of PO groups are used to evaluate the strength of OHO hydrogen bonds. Three phosphine oxides: triphenylphosphine oxide, tributylphosphine oxide and hexamethylphosphoramide are investigated as proton acceptors. The results of the experimental IR study and DFT calculation of 30 complexes formed by phosphine oxides with various substituted phenols or CFCHOH in CCl solution at room temperature are reported. We show that the PO vibrational frequency changes non-linearly upon hydrogen bond formation and strengthening and that the shift of the PO band could be used for the estimation of hydrogen bond strength in complexes with phosphine oxides. The accuracy of these estimations and the influence of solvation effects on the main characteristics of complexes are discussed.
在这项工作中，利用P=O基团的红外光谱特征来评估O—H…O氢键的强度。研究了三种氧化膦：三苯基氧化膦、三丁基氧化膦和六甲基磷酰胺作为质子受体。报道了在室温下，氧化膦与各种取代酚或CF3CH2OH在CCl4溶液中形成的30种配合物的红外实验研究结果和密度泛函理论（DFT）计算结果。我们表明，在氢键形成和增强过程中，P=O振动频率呈非线性变化，并且P=O谱带的位移可用于估计与氧化膦形成的配合物中的氢键强度。讨论了这些估计的准确性以及溶剂化效应对配合物主要特征的影响。
