Two series of 1:1 complexes with strong OHN hydrogen bonds formed by dimethylphosphinic and phenylphosphinic acids with 10 substituted pyridines were studied experimentally by liquid state NMR spectroscopy at 100 K in solution in a low-freezing polar aprotic solvent mixture CDF 3 /CDClF 2 . The hydrogen bond geometries were estimated using previously established correlations linking 1 H NMR chemical shifts of bridging protons with the O···H and H···N interatomic distances. A new correlation is proposed allowing one to estimate the interatomic distance within the OHN bridge from the displacement of 31 P NMR signal upon complexation. We show that the values of 31 P NMR chemical shifts are affected by an additional CH···O hydrogen bond formed between the P?O group of the acid and ortho-CH proton of the substituted pyridines. Breaking of this bond in the case of 2,6-disubstituted bases shifts the 31 P NMR signal by ca. 1.5 ppm to the high field.
CITATION STYLE
Giba, I. S., Mulloyarova, V. V., Denisov, G. S., & Tolstoy, P. M. (2019). Influence of Hydrogen Bonds in 1:1 Complexes of Phosphinic Acids with Substituted Pyridines on 1 H and 31 P NMR Chemical Shifts. Journal of Physical Chemistry A, 123(11), 2252–2260. https://doi.org/10.1021/acs.jpca.9b00625
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