Ligation Kinetics as a Probe for Non-Covalent Electrostatic Bonding and Electron Solvation of Alkali and Alkaline Earth Cations with Ammonia
AbstractMono-ligation kinetics were measured for ammonia reacting with atomic cations in the first two groups of the periodic table (K+, Rb+, Cs+ and Ca+, Sr+, Ba+). Also, mono-ligation energies were computed using density functional theory (DFT) in an attempt to assess the role of non-covalent electrostatic interactions in these chemical reactions. The measurements were performed at room temperature in helium bath gas at 0.35 Torr using an inductively coupled plasma/selected-ion flow tube (ICP/SIFT) tandem mass spectrometer. Rate coefficients are reported for ammonia addition, the only reaction channel that was observed with all these cations. A systematic decrease in the rate of addition of NH3 was observed for both group 1 and 2 cations going down the periodic table. The computational studies predict a decrease in the adduct binding energy and an increase in the bond separation going down groups 1 and 2 of the periodic table and provide some insight into the role of the extra selectron in the group 2 radical cations in ligand bonding. A correlation is seen between the efficiency of ligation and the binding energy of the adduct ion and attributed to the lifetime of the intermediate encounter complex against back dissociation which is dependent on its well depth. Higher-order additions of ammonia were also observed. Remarkable differences in the extent and kinetics were seen between the group 1 and 2 cations, and these were attributed to the occurrence of ammonia solvation of the extra s electron in the higher-order adducts of the alkaline earth cations.
