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Nuclear magnetic resonance study of the stoichiometry and stability of lithium ion complexes with two small size crown ethers in binary nitromethane–acetonitrile mixtures

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Abstract

Lithium-7 NMR spectrometry was used to study the complexation reaction between lithium ions and different small size crown ethers12-crown-4 (12C4), benzo-12-crown-4 (B12C4) in a number of binary nitromethane (NM)–acetonitrile (AN) mixtures. The exchange between the free and complexed lithium ion was fast on the NMR time scale and a single population average resonance was observed. Both 1:1 and 2:1 (sandwich) complexes were observed between lithium ion and 12C4 and B12C4 in pure nitromethane solution. Stepwise formation constants of the 1:1 and 2:1 (ligand/metal) complexes were evaluated from computer fitting of the NMR-mole ratio data to equations which relate the observed metal ion chemical shifts to formation constants. There is an inverse linear relationship between the logarithms of the stability constants and the mole fraction of acetonitrile in the solvent mixtures. The stability order of the 1:1 and 2:1 complexes was found to be 12C4.Li+ > B12C4.Li+. The optimized structures of the free ligands and their 1:1 and 2:1 complexes with Li+ ion were predicted by ab initio theoretical calculations using the Gausian 98 software, and the results are discussed.

Graphical Abstract

Stoichiometry and stability of the Li+ complexes with12-Crown-4 and Benzo-12-crown-4 were investigated by 7Li NMR in nitromethane-acetonitrile mixtures. The optimized structures of the free crowns and their 1:1 and 2:1 complexes with Li+ ion were predicted by ab initio theoretical calculations using the Gausian 98 software.

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Authors and Affiliations

  1. Department of Chemistry, University of Guilan, Rasht, Iran

    Nina Alizadeh

  2. Department of Chemistry, University of Razi, Kermanshah, Iran

    Mojtaba Shamsipur

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  1. Nina Alizadeh
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  2. Mojtaba Shamsipur
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Correspondence to Nina Alizadeh.

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Alizadeh, N., Shamsipur, M. Nuclear magnetic resonance study of the stoichiometry and stability of lithium ion complexes with two small size crown ethers in binary nitromethane–acetonitrile mixtures. J Incl Phenom Macrocycl Chem 68, 431–436 (2010). https://doi.org/10.1007/s10847-010-9806-4

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