期刊
RUSSIAN CHEMICAL BULLETIN
卷 62, 期 1, 页码 26-32出版社
SPRINGER
DOI: 10.1007/s11172-013-0004-6
关键词
nucleophilic addition; reaction mechanisms; acetylene; potassium hydroxide; methanol; methanethiol; dimethyl sulfoxide; superbasic catalytic systems; quantum chemical calculations; density functional theory; B3LYP functional; MP2 perturbation theory
资金
- Russian Foundation for Basic Research [12-03-00912-a]
Cluster-continuum models (KOH center dot nDMSO, n = 1, 5) were used to model the superbasic system alkali metal hydroxide-dimethyl sulfoxide within the framework of MP2/6-311++G**/ and B3LYP/6-31G* methods. The KOH molecule surrounded by five DMSO molecules exists as solvate-loosened ion pair with elongated K-O distance. It is proposed to consider the solvate-loosened ion pair of potassium cation with hydroxide anion in the surroundings of five solvent molecules as the catalytic coordination sphere of the superbasic system KOH-DMSO. Methanol and methanethiol molecules can be incorporated with ease into the first coordination sphere of potassium cation to form methoxide and methanethiolate ions. The possibility of nucleophilic attack of methoxide and methanethiolate ions on acetylene molecule in the first coordination sphere of potassium cation was studied. The model reaction system C2H2-CH3OK-H2O with one DMSO molecule included explicitly to maintain the solvate-loosened [CH3O](-)...K+ ion pair and additional inclusion of solvent effects within the framework of the IEFPCM continuum model is the most preferable for serial calculations.
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