NMR Quantification of Hydrogen-Bond-Accepting Ability for Organic Molecules

2021/04/21 by Mira Milic, Karina Targos, Magda Tellez Chavez +3 · 28 citations
Chemistry · #Catalysis #Chemical Reaction Mechanisms #Chemical shift #Chemistry #Computational chemistry #Crystallography and molecular interactions #Electronic effect #Fluorine-19 NMR #Hydrogen bond #Ion #Molecular spectroscopy and chirality #Molecule #Nuclear magnetic resonance spectroscopy #Organic chemistry #Organic molecules #Physical chemistry #Proton #Proton NMR #Protonation

paper · doi:10.1021/acs.joc.0c02876

published in The Journal of Organic Chemistry 86(9), 6031-6043 (American Chemical Society)

openalex publication_date 2021/04/21 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/30

Abstract

The hydrogen-bond-accepting abilities for more than 100 organic molecules are quantified using 19 F and 31 P NMR spectroscopy with pentafluorobenzoic acid (PFBA) and phenylphosphinic acid (PPA) as commercially available, inexpensive probes. Analysis of pyridines and anilines with a variety of electronic modifications demonstrates that changes in NMR shifts can predict the secondary effects that contribute to H-bond-accepting ability, establishing the ability of PFBA and PPA binding to predict electronic trends. The H-bond-accepting abilities of various metal-chelating ligands and organocatalysts are also quantified. The measured Δδ( 31 P) and Δδ p ( 19 F) values correlate strongly with Hammett parameters, p K a of the protonated HBA, and proton-transfer basicity (p K BH+ ).

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