2013年6月24日
Intermolecular interactions in Li+-glyme and Li +-glyme-TFSA- complexes: Relationship with physicochemical properties of [Li(glyme)][TFSA] ionic liquids
ChemPhysChem
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- 巻
- 14
- 号
- 9
- 開始ページ
- 1993
- 終了ページ
- 2001
- 記述言語
- 英語
- 掲載種別
- 研究論文(学術雑誌)
- DOI
- 10.1002/cphc.201200843
The stabilization energies (ΔEform) calculated for the formation of the Li+ complexes with mono-, di- tri- and tetra-glyme (G1, G2, G3 and G4) at the MP2/6-311G* level were -61.0, -79.5, -95.6 and -107.7 kcal mol-1, respectively. The electrostatic and induction interactions are the major sources of the attraction in the complexes. Although the ΔEform increases by the increase of the number of the O⋯Li contact, the ΔEform per oxygen atom decreases. The negative charge on the oxygen atom that has contact with the Li+ weakens the attractive electrostatic and induction interactions of other oxygen atoms with the Li+. The binding energies calculated for the [Li(glyme)]+ complexes with TFSA- anion (glyme=G1, G2, G3, and G4) were -106.5, -93.7, -82.8, and -70.0 kcal mol-1, respectively. The binding energies for the complexes are significantly smaller than that for the Li+ with the TFSA- anion. The binding energy decreases by the increase of the glyme chain length. The weak attraction between the [Li(glyme)]+ complex (glyme=G3 and G4) and TFSA - anion is one of the causes of the fast diffusion of the [Li(glyme)]+ complex in the mixture of the glyme and the Li salt in spite of the large size of the [Li(glyme)]+ complex. The HOMO energy level of glyme in the [Li(glyme)]+ complex is significantly lower than that of isolated glyme, which shows that the interaction of the Li + with the oxygen atoms of glyme increases the oxidative stability of the glyme. The interactions in Li+-glymes-TFSA- complexes: The interactions of Li+ with glymes (tri- and tetra-glyme) are strong (-96 and -108 kcal mol-1), while the interactions of the [Li(glyme)]+ complexes with TFSA- (-82 and -70 kcal mol-1) are weaker than that between Li+ and TFSA - (-137 kcal mol-1). Copyright © 2013 WILEY-VCH Verlag GmbH &
Co. KGaA, Weinheim.
Co. KGaA, Weinheim.
- リンク情報
- ID情報
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- DOI : 10.1002/cphc.201200843
- ISSN : 1439-4235
- ISSN : 1439-7641
- SCOPUS ID : 84879183337
- Web of Science ID : WOS:000320383300031