The Reactions of Alkoxide-Alkanol Negative Ions with Ketene. An ab initio and Ion Cyclotron Resonance Study

Abstract

Alkanol-alkoxide negative ions [RO^----HOR] react with ketene to form stable species H-C≡C-O^----HOR. The initial intermediate in the reaction sequence is produced by the formation of a hydrogen bond between the negatively charged oxygen of [RO^----HOR] and a hydrogen of ketene. This intermediate decomposes by competing reactions, viz. ( i ) a minor pathway involving direct elimination of ROH, and (ii) a major pathway involving a rearrangement sequence. Intermediates and product ions have been defined by using ab initio calculations at the 4-31G level. The differences between the reactions of [RO^----HOR]/ketene and [RO^---- HOR]/acetaldehyde systems are discussed.