Skip to main content
SpringerLink
Log in

Proton NMR study of the stoichiometry, stability and thermodynamics of complexation of Rb+ ion with 18-crown-6 in binary dimethylsulfoxide–nitrobenzene mixtures

  • Original Article
  • Published:
Journal of Inclusion Phenomena and Macrocyclic Chemistry Aims and scope Submit manuscript

Abstract

Proton NMR was used to study the complexation reaction of Rb+ ion with 18-crown-6 (18C6) in a number of binary dimethylsulfoxide (DMSO)–nitrobenzene (NB) mixtures at different temperatures. In all cases, the exchange between free and complexed 18C6 was fast on the NMR time scale and only a single population average 1H signal was observed. The 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 DMSO in the solvent mixtures. The enthalpy and entropy values for the complexation reaction were evaluated from the temperature dependence of formation constants. In all solvent mixtures studied, the resulting complex is enthalpy stabilized but entropy destabilized. The ∆H° versus T∆S° plot of all thermodynamic data obtained shows a fairly good linear correlation indicating the existence of enthalpy–entropy compensation in the complexation reaction.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Pedersen, C.J.: Cyclic polyethers and their complexes with metal salts. J. Am. Chem. Soc. 89, 2495–2496 (1967)

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    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 and anions. Chem. Rev. 91, 1721–2085 (1991)

    Article  CAS  Google Scholar 

  5. 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 

  6. Shamsipur, M., Irandoust, M., Alizadeh, K., Lippolis, V.: Proton NMR study of the stoichiometry, stability and thermodynamics of complexation of Ag+ ion with octathia-24-crown-8 in binary dimethylsulfoxide–nitrobenzene mixtures. J. Incl. Phenom. Macrocycl. Chem. 59, 203–209 (2007)

    Article  CAS  Google Scholar 

  7. Shamsipur, M., Madrakian, T.: Competitive lithium-7 NMR study of the complexation of some alkaline earth and transition metal ions with 18-crown-6 in acetonitrile and its 50:50 mixtures with nitrobenzene and nitroethane. Polyhedron 19, 1681–1685 (2000)

    Article  CAS  Google Scholar 

  8. Armentrout, P.B.: Cation–ether complexes in the gas phase: thermodynamic insight into molecular recognition. Int. J. Mass Spectrom. 193, 227–240 (1999)

    Article  CAS  Google Scholar 

  9. Ziemer, S.P., Niederhauser, T.L., Woolley, E.M.: Thermodynamics of complexation of aqueous 18-crown-6 with rubidium and cesium ions: apparent molar volumes and apparent molar heat capacities of aqueous (18-crown-6 + rubidium chloride) and (18-crown-6 + cesium chloride) at temperatures (278.15 to 393.15) K, at molalities (0.02 to 0.33) mol.kg−1, and at the pressure 0.35 MPa. J. Chem. Thermodyn. 38, 323–336 (2006)

    Article  CAS  Google Scholar 

  10. Ghasemi, J., Saaidpour, S.: QSPR modeling of stability constants of diverse 15-crown-5 ethers complexes using best multiple linear regression. J. Incl. Phenom. Macrocycl. Chem. 60, 339–351 (2008)

    Article  CAS  Google Scholar 

  11. Lee, M., Oh, S.Y., Pathak, T.S., Paeng, I.R., Cho, B.Y., Paeng, K.J.: Selective solid-phase extraction of catecholamines by the chemically modified polymeric adsorbents with crown ether. J. Chromatogr. 1160, 340–344 (2007)

    Article  CAS  Google Scholar 

  12. Costero, A.M., Sanchis, J., Peransi, S., Gil, S., Sanz, V.: Bis(crown ethers) derived from biphenyl: extraction and electrochemical properties. Tetrahedron 60, 4683–4691 (2004)

    Article  CAS  Google Scholar 

  13. Kijak, A.M., James, A.: Self-assembled monolayers of crown ethers for solid phase extraction in flow-injection analysis. Anal. Chim. Acta 489, 13–19 (2003)

    Article  CAS  Google Scholar 

  14. Yun, L.: High extraction efficiency solid-phase microextraction fibers coated with open crown ether stationary phase using sol–gel technique. Anal. Chim. Acta 486, 63–72 (2003)

    Article  CAS  Google Scholar 

  15. Gherrou, A., Kerdjoudj, H.: Specific membrane transport of silver and copper as Ag(CN) 2−3 and Cu(CN) 3−4 ions through a supported liquid membrane using K+-crown ether as a carrier. Desalination 151, 87–94 (2002)

    Article  Google Scholar 

  16. Chauhan, B.S., Boudjouk, P.: New neutral carrier-type ion sensors. Crown ether derivatives of poly(methylhydrosiloxane). Tetrahedron Lett. 40, 4123–4126 (1999)

    Article  CAS  Google Scholar 

  17. Aghaie, H., Giahi, M., Monajjemi, M., Arvand, M., Nafissi, G.H., Aghaie, M.: Tin (II)-selective membrane potentiometric sensor using a crown ether as neutral carrier. Sens. Actuators 107, 756–761 (2005)

    Article  CAS  Google Scholar 

  18. Mahajan, R.K., Kumar, M., Sharma, V.: Cesium ion selective electrode based on calyx [4] crown ether-ester. Talanta 58, 445–450 (2002)

    Article  CAS  Google Scholar 

  19. Su, C.C., Chang, M.C., Liu, L.K.: New Ag+ and Pb2+ selective electrodes with lariat crown ethers as ionophores. Anal. Chim. Acta 432, 261–267 (2001)

    Article  CAS  Google Scholar 

  20. Gupta, V.K., Pal, M.K., Singh, A.K.: Comparative study of Ag(I) selective poly(vinyl chloride) membrane sensors based on newly developed Schiff-base lariat ethers derived from 4, 13-diaza-18-crown-6. Anal. Chim. Acta 631, 161–169 (2009)

    Article  CAS  Google Scholar 

  21. Gromov, S., Alfimov, M.: Supramolecular organic photochemistry of crown ether styryl dyes (review). Russ. Chem. Bull. 46, 641–665 (1997)

    Article  Google Scholar 

  22. Takeshita, M., Soong, C., Irie, M.: Alkali metal ion effect on the photochromism of 1,2-bis(2,4-dimethylthien-3-yl)-perfluorocyclopentene having benzo-15-crown-5 moieties. Tetrahedron Lett. 39, 7717–7720 (1998)

    Article  CAS  Google Scholar 

  23. Kawai, S.: Photochromic bis(monoaza-crown ether)s. Alkali-metal cation complexing properties of novel diarylethenes. Tetrahedron Lett. 39, 4445–4448 (1998)

    Article  CAS  Google Scholar 

  24. Lamb, J.D., Izatt, R.M., Christensen, J.J., Eatough, D.J.: In: Melson, G.A. (ed.) Coordination Chemistry of Macrocyclic Compounds, Chap. 3. Plenum, New York (1979)

  25. Popov, A.I., Lehn, J.M.: In: Melson, G.A. (ed.) Coordination Chemistry of Macrocyclic Compounds, Chap. 1. Plenum, New York (1979)

  26. Lifson, S., Felder, C.E., Shanzer, A., Libman, J.: Synthesis of macrocycles. In: Izatt, R.M., Christensen, J.J. (eds.) The Design of Selective Complexing Agents, Chap. 4, pp. 241–307. Wiley-Interscience, New York (1987)

  27. Dietrich, B., Viout, P., Lehn, J.M.: Aspects de la Chimie des Compose′s Macrocycliques. Inter Editions, Paris (1991)

    Google Scholar 

  28. Arenaz, P., Bitticks, I., Pannell, K., Garcia, S.: Genotoxic potential of crown ethers in mammalian cells: induction of sister-chromatid exchanges. Mutat. Res. 280, 109–115 (1992)

    Article  CAS  Google Scholar 

  29. Liou, C.C., Brodbelt, J.S.: Determination of orders of relative alkali metal ion affinities of crown ethers and acyclic analogs by the kinetic method. J. Am. Soc. Mass Spectrom. 3, 543–548 (1992)

    Article  CAS  Google Scholar 

  30. Sherman, C.L., Brodbelt, J.S.: Electrospray ionization mass spectrometric detection of self-assembly of a crown ether complex directed by p-stacking interactions. J. Am. Soc. Mass Spectrom. 16, 1162–1171 (2005)

    Article  CAS  Google Scholar 

  31. Agnihotri, P., Suresh, E., Ganguly, B., Paul, P., Ghosh, P.K.: Study of the competitive binding of mixed alkali and alkaline earth metal ions with dibenzo-30-crown-10. Polyhedron 24, 1023–1032 (2005)

    Article  CAS  Google Scholar 

  32. Zhan, D., Yuan, Y., Xiao, Y., Wua, B., Shao, Y.: Alkali metal ions transfer across a water/1,2-dichloroethane interface facilitated by a novel monoaza-B15C5 derivative. Electrochim. Acta 47, 4477–4483 (2002)

    Article  CAS  Google Scholar 

  33. Buschmann, H.J., Schollmeyer, E.: A test reaction from macrocyclic chemistry for calorimetric titrations. Thermochim. Acta 333, 49–53 (1999)

    Article  CAS  Google Scholar 

  34. Alizadeh, N., Shamsipur, M.: Nuclear magnetic resonance 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 

  35. Alizadeh, N., Shamsipur, M.: Nuclear magnetic resonance study of the ligand interchange of Ba2+-18-crown-6 complex in methanol solution. J. Solut. Chem. 25, 1029–1039 (1996)

    Article  CAS  Google Scholar 

  36. Fakhari, A.R., 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 

  37. 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 

  38. Fakhari, A.R., Shamsipur, M.: Proton NMR study of the ligand interchange of the Ba2+-18-crown-6 complex in binary acetonitrile-water mixtures. J. Incl. Phenom. 32, 405–414 (1998)

    Article  CAS  Google Scholar 

  39. Shamsipur, M., Talebpour, Z., Alizadeh, N.: NMR study of the stoichiometry, stability and ligand interchange of silver ionhexathia-18-crown-6 complex in binary dimethylsulfoxide-acetonitrile and dimethylsulfoxide-methanol solvent mixtures at 300 K. J. Solut. Chem. 32, 227–238 (2003)

    Article  CAS  Google Scholar 

  40. Talebpour, Z., Alizadeh, N., Bijanzadeh, H.R., Shamsipur, M.: Cadmium-113 NMR and theoretical studies of complexation of 15-crowns-5 and benzo-15-crown-5 in acetonitrile and its binary mixtures with water and nitromethane. J. Incl. Phenom. 49, 101–106 (2004)

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  42. Bordbar, M., Shamsipur, M., Alizadeh, N.: 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 

  43. Gajewski, M., Tuszynski, J., Mori, H., Miyoshi, E., Klobukowski, M.: DFT studies of the electronic structure and geometry of 18-crown-6, hexaaza[18]annulene, and their complexes with cations of the heavier alkali and alkaline earth metals. Inorg. Chim. Acta 361, 2166–2171 (2008)

    Article  CAS  Google Scholar 

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

    Article  Google Scholar 

  45. Cahen, Y.M., Dye, J.L., Popov, A.I.: Lithium-7 nuclear magnetic resonance study of lithium cryptates in various solvents. J. Phys. Chem. 79, 1289–1291 (1975)

    Article  CAS  Google Scholar 

  46. Chantooni Jr., M.K., Roland, G., Kolthoff, I.M.: Transfer activity coefficients of crown ethers and their complexes with univalent metal ions between pairs of polar organic solvents. J. Solut. Chem. 17, 175–189 (1988)

    Article  CAS  Google Scholar 

  47. Lamb, J.D., Izatt, R.M., Christensen, J.J.: In: Izatt, R.M., Christensen, J.J. (eds.) Progress in Macrocyclic Chemistry, Chap. 3, vol. 2. Wiley, New York (1981)

  48. Gutmann, V.: Coordination Chemistry in Nonaqueous Solvents. Springer, Vienna (1968)

    Google Scholar 

  49. Baerends, E., Ellis, D., Ros, P.: Self-consistent molecular Hartree-Fock-Slater calculations I. The computational procedure. Chem. Phys. 2, 41–51 (1973)

    Article  CAS  Google Scholar 

  50. Baerends, E., Ros, P.: Self-consistent molecular Hartree–Fock–Slater calculations II. The effect of exchange scaling in some small molecules. Chem. Phys. 2, 52–59 (1973)

    Article  CAS  Google Scholar 

  51. Baerends, E., Ros, P.: Self-consistent molecular Hartree-Fock-Slater calculations: III. The influence of non-spherical contributions to the electron density and potentials. Chem. Phys. 8, 412–418 (1975)

    Article  CAS  Google Scholar 

  52. Boerrigter, P., Velde, G., Baerends, E.: Three-dimensional numerical integration for electronic structure calculations. Int. J. Quantum Chem. 33, 87–113 (1988)

    Article  CAS  Google Scholar 

  53. Velde, G., Baerends, E.: Numerical integration for polyatomic systems. J. Comput. Phys. 99, 84–98 (1992)

    Article  Google Scholar 

  54. Dunitz, J.D., Dobler, M., Seiler, P., Phizackerley, R.P.: Crystal structure analyses of 1,4,7,10,13,16-hexaoxacyclooctadecane and its complexes with alkali thiocyanates. Acta Crystallogr. 30, 2733–2738 (1974)

    Article  Google Scholar 

  55. Maverick, E., Seiler, P., Schweizer, W.B., Dunitz, J.D.: 1,4,7,10,13,16-Hexaoxacyclooctadecane: crystal structure at 100 K. Acta Crystallogr. 36, 615–620 (1980)

    Google Scholar 

  56. Shamsipur, M., Pouretedal, H.R.: Conductance study of complexation of lead ions with several 18-membered crown ethers in binary acetonitrile-dimethylsulfoxide mixtures between 25 and 55 °C. J. Solut. Chem. 28, 1187–1205 (1999)

    Article  CAS  Google Scholar 

  57. 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 

  58. Ghasemi, J., Shamsipur, M.: Conductance study of some transition and heavy metal complexes with 1,10-diaza-18-crown-6 in binary acetonitrile-dimethylsulfoxide mixtures. J. Solut. Chem. 25, 485–504 (1996)

    Article  CAS  Google Scholar 

  59. Inoue, Y., Takushi, T., Liu, Y., Tong, L.-H., Lin, D.S.: Thermodynamics of molecular recognition by cyclodextrins. 1. Calorimetric titration of inclusion complexation of naphthalenesulfonates with alpha-cyclodextrin, beta-cyclodextrin, and gamma-cyclodextrin—enthalpy entropy compensation. J. Am. Chem. Soc. 115, 475–481 (1993)

    Article  CAS  Google Scholar 

  60. Visser, H.C., Reinhoudt, D.N., de Jong, F.: Carrier-mediated transport through liquid membranes. Chem. Soc. Rev. 23, 75–81 (1994)

    Article  CAS  Google Scholar 

  61. Grunwald, E., Steel, C.: Solvent reorganization and thermodynamic enthalpy-entropy compensation. J. Am. Chem. Soc. 117, 5687–5692 (1995)

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

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

    Mohsen Irandoust, Mojtaba Shamsipur & Hiua Daraei

Authors
  1. Mohsen Irandoust
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mojtaba Shamsipur
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Hiua Daraei
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Mohsen Irandoust.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Irandoust, M., Shamsipur, M. & Daraei, H. Proton NMR study of the stoichiometry, stability and thermodynamics of complexation of Rb+ ion with 18-crown-6 in binary dimethylsulfoxide–nitrobenzene mixtures. J Incl Phenom Macrocycl Chem 66, 365–370 (2010). https://doi.org/10.1007/s10847-009-9654-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10847-009-9654-2

Keywords

Search

Navigation