Abstract
The formation of complexes between crown ethers and acetonitrile, chloroform, and nitromethane were investigated in carbon tetrachloride at 25°C. A significant influence of the ring size on the selectivity of the host is evident. The host 18-crown-6 forms complexes for which the reaction enthalpy and entropy are quite high. Host molecules with benzene side groups form complexes of lower reaction enthalpy and entropy and therefore the complexes formed are less stable than that of the analogous crown ethers without aromatic groups. Solvent effects on the stability constant K, the reaction enthalpy ΔH, and the reaction entropy ΔS were studied for the complexation of malonitrile by 18-crown-6. The reaction enthalpy and entropy values change in accordance with the dielectric constant of the solvent used, but no overall effect on complex stability with change in solvent dielectric constant was observed.
Similar content being viewed by others
References
C. J. Pedersen,J. Am. Chem. Soc. 89, 7017, (1967).
C. J. Pedersen,Fed. Proc. Fed. Am. Soc. Exp. Biol. 27, 1305 (1968).
C. J. Pedersen,J. Am. Chem. Soc. 92, 386 (1970).
C. J. Pedersen and H. K. Frensdorff,Angew. Chem. 84, 16 (1972);Intern. Ed. Engl. 11, 16 (1972).
R. M. Izatt, K. Pawlak, J. S. Bradshaw, and R. L. Bruening,Chem. Rev. 91, 1721 (1991).
F. Vögtle, H. Sieger, and W. M. Müller,Top. Curr. Chem. 98, 107 (1981).
F. Vögtle and W. M. Müller,J. Incl. Phenom. 1, 369 (1983).
W. H. Watson, J. Galloy, D. A. Grossie, F. Vögtle, and W. M. Müller,J. Org. Chem. 49, 347 (1984).
E. Weber, H. P. Josel, H. Puffand, and S. Franken,J. Org. Chem. 50, 3125 (1985).
G. W. Gokel, D. J. Cram, C. L. Liotta, H. P. Harris, and F. L. Cook,J. Org. Chem. 39, 2445 (1974).
J. A. A. de Boer, D. N. Reinhoudt, S. Harkerna, and F. de Jong,J. Am. Chem. Soc. 104, 4073 (1982).
H. S. Gold and M. R. Rice,Talana 29, 637 (1982).
P. A. Mosier-Boss and A. I. Popov,J. Am. Chem. Soc. 107, 6168 (1985).
C. J. van Staveren, V. M. L. J. Aarts, P. D. J. Grootenhuis, J. van Eerden, S. Harkerna, and D. N. Reinhoudt,J. Am. Chem. Soc. 108, 5271 (1986).
D. N. Reinhoudt,J. Coord. Chem. 18, 21 (1988).
D. N. Reinhoudt and H. J. de Hertog Jr.,Bull. Soc. Chim. Belg. 97, 645 (1988).
J. N. Spencer, A. I. Zafar, T. F. Ganuis, C. H. Yoder, L. J. Fenton, J. L. Ealy, S. Gupta, C. M. Salata, I. M. Paul, W. J. Nichson, and J. E. Mihalik,J. Phys. Chem. 96, 3475 (1992).
C. Y. Zhu, J. S. Bradshaw, J. L. Oscarson, and R. M. Izatt,J. Inclusion Phenom. Mol. Recog. Chem. 12, 275 (1992).
J. J. Christensen, J. Ruckman, D. J. Eatough, and R. M. Izatt,Thermochim. Acta 3, 203 (1972).
D. J. Eatough, J. J. Christensen, and R. M. Izatt,Thermochim. Acta 3, 219, (1972).
D. J. Eatough, R. M. Izatt, and J. J. Christensen,Thermochim. Acta 3, 233 (1972).
R. M. Izatt, R. E. Terry, D. P. Nelson, Y. Chan, D. J. Eatough, J. S. Bradshaw, L. D. Hansen, and J. J. Christensen,J. Am. Chem. Soc. 98, 7626 (1976).
H.-J. Buschmann,Inorg. Chim. Acta 195, 51 (1992).
Y. Marcus,J. Solution Chem. 13, 599 (1984).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Trültzsch, R., Beger, J., Buschmann, HJ. et al. Influence of ligand structure and solvent effects on complexation of neutral guests by several crown ethers. J Solution Chem 23, 53–61 (1994). https://doi.org/10.1007/BF00972607
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF00972607