Abstract
Ab initio molecular orbital calculations at the MP2/6-31G*//MP2/6-31G* + ZPE level have been performed in order to explore the reaction between CH3OH2+ and CH3OH. The detailed mechanism of proton transfer, CH3OH2+ + CH3OH → CH3OH + CH3OH2+, and of cationic nucleophilic substitution, CH3OH2+ + CH3OH → (CH3)2OH+ + H2O has been investigated. The former reaction involves a symmetric proton bound dimer, I, [CH3OHa---Hb---HcOCH3]+, in which exchange of the three hydrogens Ha,b,c is allowed (critical energy ca. 50 kJ mol−1. The nucleophilic substitution process involves two ion neutral complexes II, [CH3O(H)---CH3OH2]+, and III, [CH3OHC(H3)---OH2]+, only weakly stable toward isomerization. The methyl cation transfer II → III is calculated to require 28 kJ mol−1. The proposed reaction profile supports and completes the previous theoretical and experimental studies on this system. © 1997 John Wiley & Sons, Ltd.
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