Ab initio and density functional study of substituent effects in halogenated cations of alkenes

Abstract

A theoretical study of the halogenated cations of mono-, di-, tri- and tetramethyl-substituted ethylenes, C3H6X+, C4H8X+, C5H10X + and C6H12X+, X=F, Cl, Br, have been studied at the ab initio MP2 and density functional B3LYP levels of theory implementing 6-311++G(d,p) basis set. The potential energy surfaces of all molecules under investigation have been scanned and the 13C and 1H NMR chemical shifts for all the bridged halonium ions studied have been calculated using the GIAO method at the B3LYP level. The calculated halogen binding energies in the halonium ions have been correlated with the experimental rates of chlorination and bromination of the corresponding alkenes. The computed hydride affinities and the NICS values for the bridged cations show that the bromo cations are more stable than the analogous chloro and fluoro cations. © 2005 Elsevier Ltd. All rights reserved.