Fascinating interaction of the ammonium cation with [2.2.2]paracyclophane: experimental and theoretical study

Abstract

ABSTRACTBy means of electrospray ionisation mass spectrometry, it was evidenced experimentally that the ammonium cation (NH4+) reacts with the electroneutral [2.2.2]paracyclophane ligand (C24H24) to form the cationic complex [NH4(C24H24)]+. Moreover, applying quantum chemical calculations, the most probable conformation of the proven [NH4(C24H24)]+ complex was solved. In the complex [NH4(C24H24)]+ having a symmetry very close to C3, the ‘central’ cation NH4+ is coordinated by three strong bifurcated intramolecular hydrogen bonds to the corresponding six carbon atoms from the three benzene rings of [2.2.2]paracyclophane via cation–π interaction. Finally, the interaction energy, E(int), of the considered complex [NH4(C24H24)]+ was evaluated as −625.8 kJ/mol, confirming the formation of this fascinating complex species as well. It means that the [2.2.2]paracyclophane ligand can be considered as an effective receptor for the ammonium cation in the gas phase.