Deprotonation of the amine group of Glyphosate studied by XPS and DFT

Abstract

Glyphosate (N-(phosphonomethyl)glycine, C3H8NO5P) in aqueous solutions undergoes three deprotonation re- actions generally assigned to the carboxylate oxygen (pKa1 ~ 2.2), the phosphonate oxygen (pKa2 ~ 5.5), and the amine group (pKa3 ~ 10.2). A couple of recent studies (J. Phys. Chem. A 2015, 119, 5241–5249 and J. Phys. Chem. B 2016, 120, 2132–2137), however, have put forward a new sequence in which the amine group deprotonates before the phosphonate oxygen. In this study we present experimental and theoretical data with the aim of resolving the controversy over the order of the last two deprotonations. On the experimental side, we analysed the evolution of the N1s photoemission spectrum with the pH of the aqueous solution, finding conclusive evidence that the last deprotonation occurs at the amine group. On the theoretical side, we compared the stabilities of several configurations for each glyphosate moiety, finding again that the last group that un- dergoes deprotonation is the amine group.