Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 115, Issue 29, Pages 8255-8263Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp201246j
Keywords
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Funding
- National Natural Science Foundation of China [20873076, 20873075]
- Specialized Research Fund for the Doctoral Program of Higher Education [200804220009]
- Natural Science Foundation of Shandong Province [Z2008B02]
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By performing density functional theory calculations, we have studied the synthesis mechanism, electronic structure, and catalytic reactivity of a pyridinium-based ionic liquid, 1-ethylpyridinium trifluoroacetate ([epy](+) [CF3COO](-)). It is found that the synthesis of the pyridinium salt follows a S(N)2 mechanism. The electronic structural analyses show that multiple H bonds are generally involved in the pyridinium-based ionic liquid, which may play a decisive role for stabilizing the ionic liquid. The cation-anion interaction mainly involves electron transfer between the lone pair of the oxygen atom in the anion and the antibonding orbital of the C*-H bond (C* denotes the carbon atom at the ortho-position of nitrogen atom in the cation). This present work has also given clearly the catalytic mechanism of [epy](+)[CF3COO](-) toward to the Diels-Alder (D-A) reaction of acrylonitrile with 2-methyl-1, 3-butadiene. Both the cation and anion are shown to play important roles in promoting the D-A reaction. The cation [epy](+), as a Lewis acid, associates the C N group by C N center dot center dot center dot H H bond to increase the polarity of the C=C double bond in acrylonitrile, while the anion CF3COO- links with the methyl group in 2-methyl-1,3-butadiene by C-H center dot center dot center dot O H bond, which weakens the electron-donating capability of methyl and thereby lowers the energy barrier of the D-A reaction. The present results are expected to provide valuable information for the design and application of pyridinium-based ionic liquids.
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