Issue 1, 2006

Nucleophilic identity substitution reactions. The reaction between hydrogen fluoride and protonated alkyl fluorides

Abstract

The gas phase reactions between HF and the protonated alkyl fluorides MeFH+, EtFH+, PriFH+, and ButFH+ have been studied using ab initio methods. The potential energy profiles for both nucleophilic substitution (SN2) 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 fluorides have extreme structures which, with the exception of the Me 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.

Graphical abstract: Nucleophilic identity substitution reactions. The reaction between hydrogen fluoride and protonated alkyl fluorides

Supplementary files

Article information

Article type
Paper
Submitted
21 Sep 2005
Accepted
08 Nov 2005
First published
28 Nov 2005

Org. Biomol. Chem., 2006,4, 135-141

Nucleophilic identity substitution reactions. The reaction between hydrogen fluoride and protonated alkyl fluorides

J. K. Laerdahl, P. U. Civcir, L. Bache-Andreassen and E. Uggerud, Org. Biomol. Chem., 2006, 4, 135 DOI: 10.1039/B513315G

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