Skip to main content
Log in

A Proton NMR Study of the Stoichiometry and Stability of 18-Crown-6 Complexes with K+, Rb+ and Tl+ Ions in Binary Dimethyl Sulfoxide-Nitrobenzene Mixtures

  • Published:
Journal of Solution Chemistry Aims and scope Submit manuscript

Abstract

Proton NMR spectroscopy was used to study the complexation reaction of 18-crown-6 (18C6) with K+, Rb+ and Tl+ ions in a number of binary dimethyl sulfoxide-nitrobenzene mixtures. In all cases, the exchange between free and complexed crowns was fast on the NMR time scale and only a single population average 1H signal was observed. Formation constants of the resulting 1:1 complexes in different solvent mixtures were determined by computer fitting of the chemical shift-mole ratio data. There is an inverse relationship between the complex stability and the amount of dimethyl sulfoxide in the mixed solvent. It was found that, in all solvent mixtures used, Rb+ ion forms the most stable complex with 18-crown-6 in the series.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. Pedersen, C.J.: Cyclic polyethers and their complexes with metal salts. J. Am. Chem. Soc. 89, 7017–7036 (1967)

    Article  CAS  Google Scholar 

  2. Izatt, R.M., Bradshaw, J.S., Nielsen, S.A., Lamb, J.D., Christensen, J.J., Sen, D.: Thermodynamic and kinetic data for cation-macrocycle interactions. Chem. Rev. 85, 271–339 (1985)

    Article  CAS  Google Scholar 

  3. Izatt, R.M., Pawlak, K., Bradshaw, J.S., Bruening, R.L.: Thermodynamic and kinetic data for macrocycle interaction with cations and anions. Chem. Rev. 91, 1721–2085 (1991)

    Article  CAS  Google Scholar 

  4. Izatt, R.M., Pawlak, K., Bradshaw, J.S., Bruening, R.L.: Thermodynamic and kinetic data for macrocycle interaction with cations, anions, and neutral molecules. Chem. Rev. 95, 2529–2586 (1995)

    Article  CAS  Google Scholar 

  5. Izatt, R.M., Bradshaw, J.S., Bruening, R.L., Tarbet, B.J.: Thermodynamic and kinetic data for macrocycle interaction with neutral molecules. Chem. Rev. 92, 1261–1354 (1992)

    Article  CAS  Google Scholar 

  6. Covington, A.K., Newman, K.E.: Approaches to the problems of solvation in pure solvents and preferential solvation in mixed solvents. Pure Appl. Chem. 15, 2041–2058 (1979)

    Article  Google Scholar 

  7. Marcus, Y.: Preferential solvation of ions in mixed solvents. Part 2—the solvent composition near the ion. J. Chem. Soc. Faraday Trans. 84, 1465–1473 (1988)

    Article  CAS  Google Scholar 

  8. Saeidi, M., Shamsipur, M.: Complex formation of alkaline earth cations with 4-(2-pyridylazo) resorcinol in binary ethanol-water mixtures. J. Coord. Chem. 22, 131–137 (1990)

    Article  CAS  Google Scholar 

  9. Parham, H., Shamsipur, M.: Polarographic study of the interaction between heavy metal ions and some macrocyclic ligands in binary acetonitrile-water mixtures. J. Electroanal. Chem. 314, 71–80 (1991)

    Article  CAS  Google Scholar 

  10. Chatterjee, P., Laha, A.K., Bagchi, S.: Preferential solvation in mixed binary solvents ultraviolet-visible spectroscopy on N-alkylpyridinium iodides in mixed solvents containing cyclic ethers. J. Chem. Soc. Faraday Trans. 88, 1675–1678 (1992)

    Article  CAS  Google Scholar 

  11. Shamsipur, M., Ghasemi, J., Tamaddon, F., Sharghi, H.: Spectrophotometric determination of acidity constants of some anthraquinones and anthrones in methanol-water mixtures. Talanta 40, 697–699 (1993)

    Article  CAS  Google Scholar 

  12. Rouhollahi, A., Amini, M.K., Shamsipur, M.: NMR study of the stoichiometry stability and exchange kinetics of complexation reaction between Pb2+ ion and 18-crown-6 in binary acetonitrile-water mixtures. J. Solution Chem. 23, 63–74 (1994)

    Article  CAS  Google Scholar 

  13. Shamsipur, M., Ghasemi, J.: Conductance study of the thermodynamics of some transition and heavy metal cryptates in binary acetonitrile-imethylsulfoxide mixtures. J. Incl. Phenom. 20, 157–171 (1995)

    Article  Google Scholar 

  14. Fakhari, A., Shamsipur, M.: An NMR study of the stoichiometry and stability of lithium ion complexes with 12-crown-4 15-crown-5 and 18-crown-6 in binary acetonitrile-nitrobenzene mixtures. J. Incl. Phenom. 26, 243–251 (1996)

    Article  CAS  Google Scholar 

  15. Khajesharifi, H., Shamsipur, M.: Spectrophotometric study of the thermodynamics of complexation of lithium and sodium ions with dibenzo-24-crown-8 in binary dimethylformamide-acetonitrile mixtures using murexide as a metallohromic indicator. J. Coord. Chem. 35, 289–297 (1995)

    Article  CAS  Google Scholar 

  16. Shamsipur, M., Talebpour, Z., Alizadeh, N.: NMR study of the stoichiometry stability and ligand interchange of silver ion-hexathio-18-crown-6 complex in binary dimethyl sulfoxide solvent mixtures at 300 K. J. Solution Chem. 32, 227–338 (2003)

    Article  CAS  Google Scholar 

  17. Izatt, R.M., Clark, G.A., Bradshaw, J.S., Lamb, J.D., Christensen, J.J.: Sep. Purif. Methods 15, 21 (1986)

    Article  CAS  Google Scholar 

  18. Lindoy, L.F., Baldwin, D.S.: Ligand design for selective metal-ion transport through liquid membranes. Pure Appl. Chem. 61, 909–914 (1989)

    Article  CAS  Google Scholar 

  19. Cecille, L., Casaraci, M., Pietrelli, L. (eds.): New Separation Chemistry Techniques for Radioactive Waste and Other Specific Applications. Elsevier, Amsterdam (1991)

    Google Scholar 

  20. Buhlmann, P., Pretsch, E., Bakker, E.: Carrier based ion-selective electrodes and the bulk optodes. 2. Ionophores for potentiometric and optical sensors. Chem. Rev. 98, 1593–1687 (1998)

    Article  Google Scholar 

  21. Lippolis, V., Shamsipur, M.: Coordination properties and analytical applications of mixed donor macrocycles containing the 1,10-phenanthroline sub-unit. J. Iran Chem. Soc. 3, 105–127 (2006)

    CAS  Google Scholar 

  22. Stover, H.D.H., Maurice, L.J., Delville, A., Detellier, C.: Sodium: dibenzo-30-crown-10 aggregates in solution: Na-23 NMR study. Polyhedron 4, 1091–1094 (1985)

    Article  CAS  Google Scholar 

  23. Shamsipur, M., Popov, A.I.: Multinuclear NMR study of dibenzo-30-crown-10 complexes with sodium potassium and cesium ions in nonaqueous solvents. J. Am. Chem. Soc. 101, 4051–4055 (1979)

    Article  CAS  Google Scholar 

  24. Kim, J., Shamsipur, M., Huang, S.Z., Huang, R.H., Dye, J.L.: Sandwich and mixed sandwich complexes of the cesium ion with crown ethers in nitromethane. J. Phys. Chem. A 103, 5615–5620 (1999)

    Article  CAS  Google Scholar 

  25. Karkhaneei, E.A., Zebarjadian, M.H., Shamsipur, M.: 23Na NMR studies of stoichiometry and stability of sodium ion complexes with several crown ethers in binary acetonitrile-dimethylsulfoxide mixtures. J. Incl. Phenom. 54, 309–313 (2006)

    Article  CAS  Google Scholar 

  26. Schmidt, E., Popov, A.I.: Potassium-39 NMR study of the complexation kinetics of potassium(+) ion by 18-crown-6 in some nonaqueous solvents. J. Am. Chem. Soc. 105, 1873–1878 (1983)

    Article  CAS  Google Scholar 

  27. Strasser, B.O., Shamsipur, M., Popov, A.I.: Kinetics of complexation of the cesium ion with large crown ethers in acetone and in methanol solutions. J. Phys. Chem. 89, 4822–4824 (1985)

    Article  CAS  Google Scholar 

  28. Shamsipur, M., Popov, A.I.: Study of the complexation kinetics of Cs+ ion with dibenzo-30-crown-6 in some nonaqueous solvents by 133Cs NMR. J. Phys. Chem. 92, 147–151 (1988)

    Article  CAS  Google Scholar 

  29. Briere, K.M., Detellier, C.: Solvent effects in the metal interchange of crown-ether alkali-metal cation complexes—transition from an associate exchange in nitromethane to a dissociative exchange in acetonitrile studied by Na-23 nuclear-magnetic-resonance. J. Phys. Chem. 96, 2185–2189 (1992)

    Article  CAS  Google Scholar 

  30. Shamsipur, M., Karkhaneei, E., Afkhami, A.: Lithium-7 NMR study of the exchange kinetics of the lithium ion with cryptand C221 in methanol solution. Temperature dependence of the exchange mechanism. Polyhedron 17, 3809–3815 (1998)

    Article  CAS  Google Scholar 

  31. Amini, M.K., Shamsipur, M.: NMR study of the stoichiometry stability, ad exchange kinetics of alkaline earth complexes with 18-crown-6 in some nonaqueous solutions. J. Phys. Chem. 95, 9601–9604 (1991)

    Article  CAS  Google Scholar 

  32. Alizadeh, N., Shamsipur, M.: NMR study of the ligand interchange of 18-crown-6 complexes with La3+, Ca2+, Pb2+ and Ba2+ ions in 70% methanol solution. J. Chem. Soc. Faraday Trans. 92, 4391–4394 (1996)

    Article  CAS  Google Scholar 

  33. Shamsipur, M., Alizadeh, N.: NMR study of the ligand interchange of hexacyclen and hexamethylhexacyclen complexes with Tl+ ion in 70% methanol solution. J. Chin. Chem. Soc. 45, 241–247 (1998)

    CAS  Google Scholar 

  34. Bordbar, M., Shamsipur, M.: 1H NMR studies of homo and mixed ligand complexes of Tl+ ion with several polyazamacrocycles. Bioorg. Med. Chem. 13, 2253–2262 (2005)

    Article  CAS  Google Scholar 

  35. Alizadeh, N., Bordbar, M., Shamsipur, M.: Proton NMR investigation of the stoichiometry stability, and exchange kinetics of Tl+ complexes with hexacyclen and methylhexacyclen in N, N-dimethylformamide solutions. Observation of a three-site exchange process. Bull. Chem. Soc. Jpn. 78, 1763–1772 (2005)

    Article  CAS  Google Scholar 

  36. Kayne, F.J., Reuben, J.: Tallium-205 nuclear magnetic resonance as a probe for studying metal ion binding to biological macromolecules. Estimate of the distance between monovalent and divalent activators of pyruvate kinase. J. Am. Chem. Soc. 92, 220–222 (1970)

    Article  CAS  Google Scholar 

  37. Williams, R.J.F.: Tilden Lecture. The biochemistry of sodium, potassium, magnesium, and calcium. Q. Rev. Chem. Soc. 24, 331–365 (1970)

    Article  CAS  Google Scholar 

  38. Britten, J.S., Blank, M.: Thallium activation of the (Na+–K+)-activated ATPase of rabbit kidney. Biochim. Biophys. Acta 92, 160–166 (1968)

    Google Scholar 

  39. Kayne, F.J.: Thallium(I) activation of pyruvate kinase. Arch. Biochem. Biophys. 143, 232–239 (1971)

    Article  CAS  Google Scholar 

  40. Gokel, G.W., Cram, D.J., Liotta, C.L., Harris, H.P., Cook, F.L.: 18-Crown-6. Org. Synth. 56, 30–33 (1977)

    Google Scholar 

  41. Pedersen, C.J., Frensdorff, H.K.: Macrocyclic polyethers and their complexes. Angew. Chem. Int. Ed. Engl. 11, 16–25 (1972)

    Article  CAS  Google Scholar 

  42. Pedersen, C.J.: Crystalline salt complexes of macrocyclic polyethers. J. Am. Chem. Soc. 92, 386–391 (1970)

    Article  CAS  Google Scholar 

  43. Shannon, R.D.: Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr. 32A, 751–767 (1976)

    Google Scholar 

  44. Roach, E.T., Handy, P.R., Popov, A.I.: Study of the interaction of lithium ion with pentamethylenetetrazole by lithium-7 NMR. Inorg. Nucl. Chem. Lett. 9, 359–363 (1973)

    Article  CAS  Google Scholar 

  45. Dye, J.L., Nicely, V.A.: A general purpose curve fitting program for class and research use. J. Chem. Educ. 48, 443–447 (1971)

    Article  CAS  Google Scholar 

  46. Lamb, J.D., Izatt, R.M., Christensen, J.J.: In: Izatt, R.M., Christensen, J.J. (eds.) Progress in Macrocyclic Chemistry, vol. 2. Wiley, New York (1981)

    Google Scholar 

  47. Guttmann, V., Wychera, E.: Coordination reactions in non aqueous solutions—the role of the donor strength. Inorg. Nucl. Chem. Lett. 2, 257–260 (1966)

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Mojtaba Shamsipur.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Shamsipur, M., Irandoust, M. A Proton NMR Study of the Stoichiometry and Stability of 18-Crown-6 Complexes with K+, Rb+ and Tl+ Ions in Binary Dimethyl Sulfoxide-Nitrobenzene Mixtures. J Solution Chem 37, 657–664 (2008). https://doi.org/10.1007/s10953-008-9261-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10953-008-9261-7

Keywords

Navigation