Akademik Veri Yönetim Sistemi
ORGANIC & BIOMOLECULAR CHEMISTRY, cilt.4, sa.1, ss.135-141, 2006 (SCI-Expanded)
The gas phase reactions between HF and the protonated alkyl. uorides MeFH+, EtFH+, PriFH(+), and (BuFH+)-F-t have been studied using ab initio methods. The potential energy profiles for both nucleophilic substitution ( S(N)2) and elimination (E2) pathways have been investigated. Both backside Walden inversion and frontside nucleophilic substitution reaction profiles have been generated. Backside substitution is very favourable, but shows relatively little variation with the alkyl group. Frontside substitution reaction barriers are only slightly higher than the barrier for backside substitution for HF + MeFH+, and the difference in barrier heights for frontside and backside displacement seems negligible for the larger alkyl groups. Reaction barrier trends have been analysed and compared with the results of similar studies of the H2O/ROH2 + and NH3/RNH3 + systems (R = Me, Et, Pri, and But). Compared to the two other classes, protonated. uorides have extreme structures which, with the exception of theMe substrate, are weakly bound complexes between an alkyl cation and HF. The results nourish the idea that nucleophilic substitution reactions are better understood in view of competition between frontside and backside substitution than from the traditional SN1/SN2 perspective.