Molecular Salt Effects in the Gas Phase: Tuning the Kinetic Basicity of [HCCLiCl]− and [HCCMgCl2]− by LiCl and MgCl2

Abstract

AbstractA combination of gas‐phase ion–molecule reaction experiments and theoretical kinetic modeling is used to examine how a salt can influence the kinetic basicity of organometallates reacting with water. [HCCLiCl]− reacts with water more rapidly than [HCCMgCl2]−, consistent with the higher reactivity of organolithium versus organomagnesium reagents. Addition of LiCl to [HCCLiCl]− or [HCCMgCl2]− enhances their reactivity towards water by a factor of about 2, while addition of MgCl2 to [HCCMgCl2]− enhances its reactivity by a factor of about 4. Ab initio calculations coupled with master equation/RRKM theory kinetic modeling show that these reactions proceed via a mechanism involving f..