Experimental and DFT Studies on the Identity Exchange Reactions between Phenyl Chalcogen Iranium Ions and Alkenes

Abstract

The gas-phase ion–molecule identity exchange reactions of phenyl chalcogen iranium ions with alkenes have been examined experimentally in a linear ion trap mass spectrometer by isotope labeling experiments. The nature of both the alkene and the chalcogen play crucial roles, with the bimolecular rates for π-ligand exchange following the order: [PhTe(c-C6H10)]+ + c-C6D10 > [PhTe(C2D4)]+ + C2H4 > [PhSe(c-C6H10)]+ + c-C6D10, with no reaction being observed for [PhSe(C2D4)]+ + C2H4, [PhS(C2D4)]+ + C2H4, and [PhS(c-C6H10)]+ + c-C6D10. The experimental results correlate with RRKM modeling and density functional theory (DFT) calculations, which also demonstrates that these reactions proceed via asso..