Abstract
The alkylation processes of the reactions X- + CH3F → XCH3 + F-, where X = OH, CH3 and H2CCHO, have been studied theoretically by means of 3-21 + G ab initio calculations. Transition states have been directly located. The use of a diffuse function-augmented basis set allows kinetically (O-alkylation) and thermodynamically (C-alkylation) controlled reactions of acetaldehyde enolate to be clearly separated. The changes of potential surfaces by the use of the 3-21 + G basis set instead of the 3-21G one are discussed, with special attention to the relevant modifications of transition structures. The influences of thermal corrections and electron correlation have also been considered.
Original language | English |
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Pages (from-to) | 1531-1538 |
Journal | Journal of the Chemical Society, Faraday Transactions 2: Molecular and Chemical Physics |
Volume | 85 |
Issue number | 9 |
DOIs | |
Publication status | Published - 1 Dec 1989 |