Abstract
Lithium-7 NMR studies have been carried out on lithium ion complexes with crown ethers 12C4, 15C5, and 18C6 in water and in several nonaqueous solvents. In all cases 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 in nitromethane solution. The stability of the complexes varied very significantly with the solvent. With the exception of pyridine, the stability varies inversely with the Gutmann donor number of the solvent. In general, the stability order of the complexes was found to be 15C5·Li+>12C4·Li+>18C6·Li+. Calorimetric studies on these complexes show that, in most cases, the complexes are both enthalpy and entropy stabilized.
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References
C. J. Pedersen,J. Am. Chem. Soc. 89, 7017 (1967).
B. Dietrich, J.-M. Lehn, and J.-P. Sauvage,Tetrahedron Lett., 2885, 2889 (1969).
A. I. Popov and J.-M. Lehn, Physicochemical Studies of Crown and Cryptate Complexes, inChemistry of Macrocyclic Compounds, G. A. Melson, ed. (Plenum, New York, 1979).
Y. M. Cahen, P. R. Handy, E. T. Roach, and A. I. Popov,J. Phys. Chem. 79, 80 (1975).
Y. M. Cahen, J. L. Dye, and A. I. Popov,J. Phys. Chem. 79, 1289 (1975).
Y. M. Cahen, J. L. Dye, and A. I. Popov,J. Phys. Chem. 79, 1292 (1975).
J.-M. Lehn and J.-P. Sauvage,J. Am. Chem. Soc. 97, 6700 (1975).
E. Shchori, N. Nae, and J. Jagur-Grodzinski,J. Chem. Soc. Dalton Trans., 2381 (1975).
H. K. Frensdorff,J. Am. Chem. Soc. 93, 600 (1971).
S. G. A. McLaughlin, G. Szabo, S. Ciani, and G. Eisenman,J. Membr. Biol. 9, 3 (1972).
N. Matsuura, K. Umemoto, Y. Takeda, and A. Sasaki,Bull. Chem. Soc. Jpn. 49, 1246 (1976).
J. Jagur-Grozinski,Bull. Chem. Soc. Jpn. 50, 3077 (1977).
N. Matsuura, K. Umemoto, Y. Takeda, and A. Sasaki,Bull. Chem. Soc. Jpn.,50, 3078 (1977).
E. Kauffmann, J.-M. Lehn, and J.-P. Sauvage,Helv. Chim. Acta 58, 1099 (1976).
G. W. Gokel, D. J. Cram, C. L. Liotta, H. P. Harris, and F. L. Cook,J. Org. Chem. 39, 2445 (1974).
D. Wright, Ph.D. Thesis, Michigan State University (1974).
D. H. Live and S. I. Chan,Anal. Chem. 42, 791 (1970).
J. R. Zimmerman and M. R. Foster,J. Phys. Chem. 61, 282 (1957).
C. E. Vanderzee and J. A. Swanson,J. Phys. Chem. 67, 285, 2608 (1963); J. D. Hale, R. M. Izatt, and J. J. Christensen,J. Phys. Chem. 67, 2605 (1963).
R. M. Izatt, J. D. Lamb, G. E. Maas, R. E. Asay, J. S. Bradshaw, and J. J. Christensen,J. Am. Chem. Soc. 99, 2365 (1977).
E. T. Roach, P. R. Handy, and A. I. Popov,Inorg. Nucl. Chem. Lett. 9, 359 (1973).
V. A. Nicely and J. L. Dye,J. Chem. Educ. 48, 443 (1971).
E. Mei, A. I. Popov, and J. L. Dye,J. Phys. Chem. 81, 1677 (1977).
V. Gutmann and E. Wychera,Inorg. Nucl. Chem. Lett. 2, 257 (1966)
L. M. Mukherjee and D. P. Boden,J. Phys. Chem. 73, 3965 (1969).
J. E. Prue and P. J. Sherrington,Trans. Faraday Soc. 57, 1795 (1961).
F. Accascina, G. Pistoia, and S. Schiavo,Ric. Sci. 36, 560 (1966).
F. Accascina and S. Schiavo,Ann. Chim. (Rome) 43, 695 (1953).
L. G. Savedoff,J. Am. Chem. Soc. 88, 664 (1966).
J. D. Lamb, R. M. Izatt, J. J. Christensen, and D. J. Eatough, Thermodynamics and Kinetics of Cation-Macrocycle Interaction, inChemistry of Macrocyclic Compounds, G. A. Melson, ed. (Plenum, New York, 1979).
A. J. Smetana and A. I. Popov,J. Chem. Thermodyn., in press.
M. Shamsipur and A. I. Popov,J. Am. Chem. Soc. 101, 4051 (1979).
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Smetana, A.J., Popov, A.I. Lithium-7 nuclear magnetic resonance and calorimetric study of lithium crown complexes in various solvents. J Solution Chem 9, 183–196 (1980). https://doi.org/10.1007/BF00648325
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DOI: https://doi.org/10.1007/BF00648325