Experimental and theoretical study on gas-phase ion/molecule reactions of silver trimer cation, Ag3+, with 12-crown-4.

The reaction mechanisms of silver trimer cation, Ag₃⁺, with 12-crown-4 (12C4) were studied experimentally and theoretically. Using a cylindrical ion trap time-of-flight mass spectrometer, gas-phase ion/molecule reactions of Ag₃⁺ with 12C4 were observed. Metal-ligand complexes of [Ag(12C4)]⁺, [Ag₃(12C4)]⁺ and [Ag₃(12C4)₂]⁺, and of [Ag(12C4)₂]⁺ and [Ag₃(12C4)₃]⁺, were observed as the reaction intermediates and terminal products, respectively. The formations of the [Ag(12C4)]⁺ and [Ag(12C4)₂]⁺ complexes indicated that the neutral dimer (Ag₂) had been eliminated from the trimer cation. From the results of ab initio calculations at the HF/LanL2DZ level of theory and the experiments, it is suggested that three 12C4 molecules can attach to Ag₃⁺ through consecutive reactions and that neutral Ag₂ can be easily eliminated from [Ag₃(12C4)]⁺. [ABSTRACT FROM AUTHOR]