Substituent effect on the interaction of aromatic primary amines and diamines with supercritical CO(2) from infrared spectroscopy and quantum calculations.

The nature and the strength of the interactions occurring between aromatic primary amines and CO(2) have been investigated by combining infrared spectroscopy with molecular modelling. A series of infrared absorption experiments on various aromatic mono- and diamines in supercritical CO(2) have been performed at constant temperature (T = 40 degrees C) for various CO(2) pressures varying from 6 to 30 MPa. Then, we carried out a theoretical analysis based on quantum calculations using both density functional (B3LYP) and ab initio (MP2) computational methods. Whatever the amine considered, CO(2) is found to be on average above the nitrogen atom of the NH(2) group for which the donating lone pair interacts with the carbon atom of CO(2). Several types of interactions have been identified, namely, electron donor-acceptor (EDA), hydrogen bonds as well as dispersion forces. Contrary to aliphatic amines, the dispersion interaction is significant in the aromatic amine-CO(2) complexes because of the presence of the aromatic ring. The substituents are found to influence the stability and structure of the amine-CO(2) complexes, directly by electrostatic and steric effects of the substituent, and indirectly through the change in the partial charge on the nitrogen atom. Finally, a good correlation has been put in evidence between the partial charge on the nitrogen atom and the EDA interaction occurring between the aromatic amines and CO(2).