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A comparative ab initio quantum chemical study of methanol interaction with potassium and rubidium hydroxides surrounded by DMSO molecules is performed. The reaction profiles of the formation of a nucleophilic particle in the direct interaction of methanol with an undissociated molecule of alkali metal hydroxide are considered. The levels of the description of the reacting system by different cluster continuum models are compared. [ABSTRACT FROM AUTHOR]

An ab initio quantum chemical study of the reaction profiles of the nucleophile particle formation in the interaction of methanol, methanthiol, and acetoxime with an undissociated molecule of alkali metal hydroxide is performed for the gas phase and also with the explicit inclusion of a dimethyl sulfoxide molecule into the calculation and with allowance made for solvation effects within the continuum model. [ABSTRACT FROM AUTHOR]

The reaction mechanism of the formation of alkali metal ethynides C2H2 + MOH → C2HM + H2O (M = Li, Na, K) is studied for the gas phase (MP2/6-311++G**//RHF/6-31+G*) and also with regard to the solvent effect of dimethyl sulfoxide (DMSO) included within the continuum model. Among all acetylene complexes with alkali metal hydroxides considered (C2H2·MOH (M = Li, Na, K)), only the complex with KOH is thermodynamically stable in DMSO solution. The formation of this structure results in activation of the acetylene molecule towards electrophilic attack. The formation of alkali metal ethynide in solution is also thermodynamically favorable only in the system with potassium hydroxide of a whole series of metals considered. Further, the ethynide ion can interact in KCCK·HOH systems. [ABSTRACT FROM AUTHOR]