Computational Study on the Nature of Bonding between Silver Ions and Nitrogen Ligands

Abstract

In this paper, the nature of silver ion-nitrogen atom bonding in the complexation with ammonia, azomethine, pyridine, and hydrogen cyanide from one to four coordinations is studied at the B97-1 level of density functional theory. The results indicate that the two-coordinated complex of the silver ion with different nitrogen ligands representing sp, sp², and sp³ orbital hybridizations is the most stable form having the shortest Ag⁺-N bond distance, highest vibrational frequencies, largest bond order, and favorable Gibbs free energy of formation. Natural bond orbital analyses further show that σ-donation from the nitrogen lone pair to the silver empty 5s orbital is dominant in the dative metal-ligand bonding character with N-sp³ having the largest contribution among the different N atomic orbital hybridizations. Natural energy decomposition analyses further show that the two-coordinated complexes have enhanced electrostatic interaction and charge transfer energies over other coordination types leading them to be more stable. For this reason, the two-coordinated complexes would be a better representation for studying bonding and interaction in silver ion complexes.