An Investigation of Gaseous α-Halogenated Carbocations and Isomeric Halonium, Halenium, and Allylhalonium Ions

Abstract

We investigated with tandem mass spectrometric methods (MS/MS) the nature and extent of stabilization of gas-phase alkyl, vinyl and 2-allyl carbenium ions caused by halogen participation of neighboring chlorine and bromine atoms. The extent of halogen atom stabilization is greatest for alkyl ions, followed closely by that for vinyl ions, and is significantly less for the 2-halosubstituted allyl ions. The data is consistent with bridged halonium ion formation in alkyl systems and bridged halenium ion formation in vinyl systems. Our results for the 2-chloro allyl system are in accord with an earlier NMR interpretation rather than with recent theory, indicating that a bridged allyl halonium ion species is involved.