Molecular salt effects in the gas phase: Tuning the kinetic basicity of [HCCLiCl]- and [HCCMgCl2]- by LiCl and MgCl2

Abstract

A 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≡CMgCl 2 ] - , consistent with the higher reactivity of organolithium versus organomagnesium reagents. Addition of LiCl to [HC≡CLiCl] - or [HC≡CMgCl 2 ] - enhances their reactivity towards water by a factor of about 2, while addition of MgCl 2 to [HC≡CMgCl 2 ] - 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 i..