Journal
RUSSIAN CHEMICAL BULLETIN
Volume 62, Issue 1, Pages 26-32Publisher
SPRINGER
DOI: 10.1007/s11172-013-0004-6
Keywords
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
Categories
Funding
- Russian Foundation for Basic Research [12-03-00912-a]
Ask authors/readers for more resources
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.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available