Skip to main content
SpringerLink
Log in

The outer-sphere association of p-sulfonatothiacalix[4]arene with some Co(III) complexes: the effect on their redox activity in aqueous solutions

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

Abstract

The effect of the ion-pairing of Co(III) complexes with p-sulfonatothiacalix[4]arene (STCA) on Fe(II)–Co(III) electron transfer rate was evaluated from the analysis and comparison of kinetic data in double Co(III)–Fe(II) and triple Co(III)–Fe(II)—STCA systems at various concentration conditions. Complexes [Co(en)3]3+(1), [Co(en)2ox]+(2), [Co(dipy)3]3+ (3), [Co(His)2]+(4) and [Fe(CN)6]4− were chosen as Co(III) and Fe(II) compounds. The effect of STCA was found to correlate with the association mode. The outer-sphere association with STCA was found to exhibit the insignificant effect on Fe(II)–Co(III) electron transfer k et constants for complexes 3 and 4 with bulky and rigid chelate rings, while more sufficient inclusion of flexible ethylendiaminate rings of 1 and 2 into the cavity of STCA results in the unusual increase of k et.

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

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Babich, O.A., Gould, E.S.: Reactions of corrin-bound cobalt (III) with s2 metal-ion reducing centers. Inorg. Chim. Acta. 336, 80–86 (2002)

    Article  CAS  Google Scholar 

  2. Hopfield, J.J., Onuchic, J.N., Beratan, D.N.: Electronic shift register memory based on molecular electron-transfer reactions. J. Phys. Chem. 93, 6350–6357 (1989)

    Article  CAS  Google Scholar 

  3. Szacilowski, K.: Molecular logic gates based on pentacyanoferrate complex. Chem. Eur. J. 10, 2520–2528 (2004)

    Article  CAS  Google Scholar 

  4. Andersson, M., Linke, M., Chambron, J.-C., Davidsson, J., Heitz, V., Hammarstrom, L., Sauvage, J.-P.: Long-range electron transfer in porphyrin-containing [2]-Rotaxanes: tuning the rate by metal cation coordination. J. Am. Chem. Soc. 124, 4347 (2002)

    Article  CAS  Google Scholar 

  5. Gutmann, V., Schmid, R.: Empirical approach to ligand effects on the kinetics of substitution and redox reactions. Coord. Chem. Rev. 12, 263–293 (1974)

    Article  CAS  Google Scholar 

  6. Neto-Ponce, P., Sanchez, F., Perez, F., Garcia-Santana, A., Perez-Tejeda, P.: Salt, solvent, and micellar effects on the intervalence transition within the binuclear complex pentaammineruthenium(III)(μ-cyano)pentacyanoironII). An estimation of rate constant from static (optical and electrochemical) data. Langmuir 17, 980–987 (2001)

    Article  CAS  Google Scholar 

  7. Morillo, M., Denk, C., Perez, P., Lopez, M., Sanchez, A., Prado, R., Sanchez, F.: Electron transfer reactions in solvent mixtures: the excess component of solvent reorganization free energy. Coord. Chem. Rev. 204, 173–198 (2000)

    Article  CAS  Google Scholar 

  8. Pferffer, J., Kirchner, K., Wherland, S.: Extensive inhibition by ion-pairing in a bimolecular outer-sphere electron transfer reaction, reduction of a cobalt chlatrochelate by ferrocene in methylene chloride. Inorg. Chim. Acta. 313, 37–42 (2001)

    Article  Google Scholar 

  9. Prado-Gotor, R., Jimenez, R., Lopez, P., Perez, P., Gomes-Herrera, C., Sanchez, F.: Micellar effects upon the reaction between acetonitrile pentacyanoferrate (II) and bis(ethylendiamine)(2-pyrazinecarboxylato)cobalt(III). Langmuir 14, 1539–1543 (1998)

    Article  CAS  Google Scholar 

  10. Prado-Gotor, R., Jimenez, R., Perez-Tejeda, P., Lopez-Lopez, M., Sanchez, F.: Electron transfer reactions in micellar systems: separation of the true (unimolecular) electron transfer rate constant in its components. Chem. Phys. 263, 139–148 (2001)

    Article  CAS  Google Scholar 

  11. Lopez-Cornejo, P., Prado-Gotor, R., Gomez-Herrera, C., Jimenez, R., Sanchez, F.: nfluence of the charge and concentration of coreactants on the apparent binding constant of the reactant to micelles. Langmiur 19, 5991–5995 (2003)

    Article  CAS  Google Scholar 

  12. de la Vega, R., Perez-Tejeda, P., Lopez-Cornejo, P., Sanchez, F.: Kinetic study of the oxidation of [Ru(NH3)5pz]2+ by [Co(C2O4)3]3- in AOT-oil-water microemulsions and in CTACl micellar solutions. Langmiur 20, 1598–1563 (2004)

    Article  CAS  Google Scholar 

  13. Lopez-Cornejo, P., Perez, P., Garcia, F., de la Vega, R., Sanchez, F.: Use of the pseudo-phase model in the interpretation of reactivity under restricted geometry conditions. J. Amer. Chem. Soc. 124, 5154–5164 (2002)

    Article  CAS  Google Scholar 

  14. Lopez-Cornejo, P., Predo-Gotor, R., Garcia-Santana, A., Perez, F., Sanchez, F.: Comparative study of micellar and DNA effects on the reaction [Ru(NH3)5py]2+ + S2O8 2-. Langmiur 19, 3185–3189 (2003)

    Article  CAS  Google Scholar 

  15. Chevanieu, A., Guichou, J.F., Prado-Gotor, R., Perez-Tejeda, P., Jimenez, R., Lopez-Cornejo, P., Sanchez, F.: Strength and character of peptide/anion interactions. J. Phys. Chem. B. 109, 19676–19680 (2005)

    Article  CAS  Google Scholar 

  16. Macartney, D.H., Roszak, A.W., Smith, K.C.: Effects of β-cyclodextrin inclusion on the kinetics of the oxidation of bisferrocenyl cations by bis(pyridine-2,6-dicarboxylato)cobaltate(III) in aqueous solution: Crystal structure of dimethyldi-(1-methylferrocene)ammonium bromid. Inorg. Chim. Acta. 291, 365–371 (1999)

    Article  CAS  Google Scholar 

  17. Takusagawa, F., Shaw, J., Everett, G.W.: Hexaamminecobalt(3+) lasalocid A. A second-sphere complex involving a natural carboxylic ionophore. Inorg. Chem. 27, 3107–3112 (1988)

    Article  CAS  Google Scholar 

  18. Nichols, P.J., Raston, C.L., Steed, J.W.: Engineering of porous p-stacked solids using mechanochemistry. Chem. Commun. 1062–1063 (2001)

  19. Mitkina, T.V., Sokolov, M.N., Naumov, D.Y., Kuratieva, N.V., Gerasko, O.A., Fedin, V.P.: orgensen complex within a molecular container: selective encapsulation of trans-[Co(en)2Cl2]+ into cucurbit[8]uril and influence of inclusion on guest's properties. Inorg. Chem. 45, 6950–6955 (2006)

    Article  CAS  Google Scholar 

  20. Pina, F., Parola, A.J.: Photochemistry of supramolecular species involving anionic coordination compounds and polyammonium macrocyclic receptors. Coord. Chem. Rev. 185–186, 149–165 (1999)

    Article  Google Scholar 

  21. Mandolini, L., Ungaro, R. (eds.): Calixarenes in Action; Imperial College Press, London (2000)

  22. Liu, Y., Han, B.-H., Chen, Y.-T.: Molecular recognition and complexation thermodynamics of dye guest molecules by modified cyclodextrins and calixarenesulfonates. J. Phys. Chem. B. 106, 4678 (2002)

    Article  CAS  Google Scholar 

  23. Tao, W., Barra, M.J.: Inhibition of quinine–imine dye deamination by complexation with para-sulfonated calixarenes. Org. Chem. 66, 2158–2160 (2001)

    Article  CAS  Google Scholar 

  24. Alvares, J., Wang, Y., Gomes-Kaifer, M., Kaifer, A.: Importance of intramolecular hydrogen bonding for preorganization and binding of molecular guests by water-soluble calix[6]arene hosts. Chem. Commun. 1455–1456 (1998)

  25. Wang, Y., Alvares, J., Kaifer, A.: Redox control of host-guest recognition: a case of host selection determined by the oxidation state of the guest. Chem. Commun. 1457–1458 (1998)

  26. Mustafina, A.R., Skripacheva, V.V., Gubskaya, V.P., Gruner, M., Solov’yeva, S.E., Antipin, I.S., Konovalov, A.I., Habicher, W.: Outer-sphere interaction between octahedral chiral cobalt(III) complexes and water-soluble calixarenes. Russ. Chem. Bull. Int. Ed. 53, 1453–1519 (2004)

    Article  Google Scholar 

  27. Mustafina, A.R., Skripacheva, V.V., Gubaidullin, A.T., Latipov, Sh.K., Toropchina, A.V., Yanilkin, V.V., Solovieva, S.E., Antipin, I.S., Konovalov, A.I.: The outer-sphere association of p-sulfonatothiacalix[4]arene and tetrasulfonatomethylated calix[4]resorcinarene with cobalt (III) tris(dipyridyl): the effect on the spectral and electrochemical properties of the latter. Inorg. Chem. 44, 4017–4023 (2005)

    Article  CAS  Google Scholar 

  28. Iki, N., Fujimoto, T., Miyano, S.: A new water-soluble host molecule derived from thiacalixarene. Chem. Lett. 625–626 (1998)

  29. Broomhead, J.A., Dwyer, F.D., Hogarth, J.W.: Inorg. Synth. 6, 183 (1960)

    Google Scholar 

  30. Bagger, S., Jensen, H.P.: Optical properties of bis(histidinato) cobalt (III) complexes. Acta Chem. Scand. A. 32, 659–662 (1978)

    Google Scholar 

  31. Ferguson, J., Hawkins, C.J., Kane-Maguire, N.A.P., Lip, H.: Absolute configurations of 1,10-phenanthroline and 2, 2'-bipyridine metal complexes. Inorg. Chem. 8, 771–779 (1969)

    Article  CAS  Google Scholar 

  32. Dwyer, F.P., Reid, I.K., Garvan, F.L.: Oxalato- and malanato-ethylenediaminecobalt(III)-complexes. J. Amer. Chem. Soc. 83, 1285–1287 (1961)

    Article  CAS  Google Scholar 

  33. Wolsey, W.C.: Perchlorate salts, their uses and alternatives. J. Chem. Educ. 50, A335–A345 (1973)

    Article  CAS  Google Scholar 

  34. Holder, A.A., Dasgupta, T.P.: Kinetics and mechanism of the reduction of the molybdatopentaamminecobalt (III) ion by aqueous sulfite and aqueous potassium hexacyanoferrate (II). Inorg. Chem. 331, 279–289 (2002)

    CAS  Google Scholar 

  35. Lever, A.B.P.: Inorganic Electronic Spectroscopy, 2nd edn. Elsevier, Amsterdam (1984)

    Google Scholar 

  36. Matsumiya, H., Terazono, Y., Iki, N., Miyano, S.: Acid–base properties of sulfur-bridged calix[4]arenas. J. Chem. Soc. Perkin Trans. 2, 1166–1172 (2002)

    Google Scholar 

  37. Schneider, Y.-J., Yatsimirsky, A.K.: Principles and methods in supramolecular chemistry, John Wiley & Sons, New York (2000), p. 349

    Google Scholar 

  38. Bodek, I., Davies, G.: Studies of ammineaquacobalt (III) chemistry. Kinetics and mechanism of some electron transfer reactions of cis-diamminecobalt (III) in acid perchlorate solution. Inorg. Chem. 15, 922–926 (1976)

    Article  CAS  Google Scholar 

  39. Martinez, M., Pitarque, M.-A., van Edlik, R.: Outer-sphere redox reactions of (N)5- macrocyclic cobalt(III) complexes. A temperature and pressure dependence kinetic study on the influence of size and geometry of different macrocycles. Inorg. Chim. Acta. 256, 51–59 (1997)

    Article  CAS  Google Scholar 

  40. Miralles, A.J., Szecsy, A.P., Haim, A.: Electron-transfer reactions of ion pairs: reductions of various substituted pyridinepentaamminecobalt(III) complexes by hexacyanoferrate(II). Inorg. Chem. 21, 697–699 (1982)

    Article  CAS  Google Scholar 

  41. Larsson, R.: Studies on cobaltammines. X. Some reactions of the (+)-trisethylenediamine cobalt(III) ion with the hexacyanoferrate(II) ion. Acta Chem. Scand. 21, 257–270 (1967)

    Article  CAS  Google Scholar 

  42. Langford, C.H., Sasseville, R.L.P.: The photochemical reaction of the tris(ethylenediamine) cobalt(III) ion with ferrocyanide. Can. J. Chem. 59, 647–651 (1981)

    Article  CAS  Google Scholar 

Download references

Acknowledgments

We thank RFBR (grant N 04-03-32909) and BRHE (Y3-C-07-15) for financial support.

Author information

Authors and Affiliations

  1. A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center of the Russian Academy of Sciences, Arbuzov str. 8, Kazan, 420088, Russia

    A. R. Mustafina, L. Ya Zakharova, V. V. Skripacheva, S. E. Solov’eva, I. S. Antipin & A. I. Konovalov

  2. A.M. Butlerov Chemistry Institute, Kazan State University, Kremlyovskaya Str., 18, 420008, Kazan, Russia

    V. G. Shtyrlin, R. R. Zairov, I. S. Antipin & A. I. Konovalov

Authors
  1. A. R. Mustafina
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. V. G. Shtyrlin
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. L. Ya Zakharova
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. V. V. Skripacheva
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. R. R. Zairov
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. S. E. Solov’eva
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. I. S. Antipin
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. A. I. Konovalov
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to A. R. Mustafina.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Mustafina, A.R., Shtyrlin, V.G., Zakharova, L.Y. et al. The outer-sphere association of p-sulfonatothiacalix[4]arene with some Co(III) complexes: the effect on their redox activity in aqueous solutions. J Incl Phenom Macrocycl Chem 59, 25–32 (2007). https://doi.org/10.1007/s10847-007-9290-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10847-007-9290-7

Keywords

Search

Navigation