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.
|Journal||Journal of the Chemical Society, Faraday Transactions 2: Molecular and Chemical Physics|
|Publication status||Published - 1 Dec 1989|