Experimental and theoretical study on gas-phase ion/molecule reactions of silver trimer cation,Ag_3~+,with 12-crown-4

摘要

The reaction mechanisms of silver trimer cation,Ag_3~+,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 Ag_3~+ with 12C4 were observed.Metal-ligand complexes of [Ag(12C4)]~+,[Ag3(12C4)]~+ and [Ag_3(12C4)_2]~+,and of [Ag(12C4)_2]~+ and [Ag_3(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 Ag_3~+ through consecutive reactions and that neutral Ag_2 can be easily eliminated from [Ag_3(12C4)]~+.