On the existence of the elusive monomethyl ester of carbonic acid [CH 3OC(O)OH] at 300 K: 1H- and 13C NMR measurements and DFT calculations

• Published in: European Journal of Inorganic Chemistry
• Main Authors: Dibenedetto A., Aresta M., Giannoccaro P., Pastore C., Papai I., Schubert G.
• Other Authors: Dibenedetto, A., Aresta, M., Giannoccaro, P., Pastore, C., Papai, I., Schubert, G.
• Format: Article in Journal/Newspaper
• Language: English
• Published: 2006
• Subjects: Carbon dioxide; Density functional calculation; Methylation; NMR spectroscopy; Carbonic acid
• Online Access: https://hdl.handle.net/11586/413670; https://doi.org/10.1002/ejic.200500622

The elusive monomethyl ester of carbonic acid [CH3OC(O)-OH] has been prepared at 300 K by protonation of the sodium salt NaOC(O)OCH3 with anhydrous HCl or water and characterized by 1H- and 13C NMR spectroscopy. The stability of the acid and its reactivity towards hydroxo ions and methylating agents under ambient conditions are discussed. The energetics and the mechanism of the investigated reactions are examined on the basis of density functional calculations. For kinetic and thermodynamic reasons CH3OC(O)OH is unlikely to be formed by insertion of CO2 into the O-H bond of methanol. © Wiley-VCH Verlag GmbH & Co. KGaA, 2006.