2-Phosphonobutane-1,2,4,-Tricarboxylic Acid (PBTC): pH-Dependent Behavior Studied by Means of Multinuclear NMR Spectroscopy

Although 2-phosphonobutane-1,2,4,-tricarboxylic acid, PBTC, has manifold industrial applications, relevant and reliable data on the protonation of PBTC are poor. However, these data are critical parameters for ascertaining PBTC speciation, especially with regard to a sound structural and thermodynamic characterization of its metal ion complexes. A rigorous evaluation of pH-dependent H-1, C-13, and P-31 chemical shifts along with accessible scalar spin-spin coupling constants (J) was performed in order to determine the pK(a) values of PBTC in 0.5 molal NaCl aqueous solution by means of nuclear magnetic resonance (NMR) spectroscopy. The phosphonate group revealed pK(a) values of 0.90 +/- 0.02 and 9.79 +/- 0.02, and the pK(a) values associated with the carboxylic groups are 3.92 +/- 0.02, 4.76 +/- 0.03, and 6.13 +/- 0.03. Supported by DFT-calculated structures revealing strong intramolecular hydrogen bonding, the sequence of deprotonation could be unambiguously determined.

Automated summary

This study rigorously evaluated the protonation of PBTC in solution using NMR spectroscopy. The pKa values of PBTC were determined, providing important data support for further understanding of its structure and thermodynamic properties.