Skip to main content
Log in

Solution properties of iron(III) complexes with 5-fluorosalicylic acid — spectra, speciation, and redox stability

  • Original Paper
  • Published:
Chemical Papers Aims and scope Submit manuscript

Abstract

Iron(III)-5-fluorosalicylic acid systems were investigated in water by pH potentiometry combined with UV-VIS spectrophotometry. The data revealed that stable aquated mono-, bis-, and tris(5-fluorosalicylato) iron(III) complexes are formed together with their monohydroxo and dihydroxo analogues. The stability constants of all present iron(III) species were calculated. Based on pH and the metal: ligand ratio dependent distribution of the species, electronic absorption spectra of the complexes in the visible region were obtained. Redox stability was monitored as an ability to undergo both spontaneous and photoinduced reduction of iron(III) to iron(II). Complexes do not undergo any redox changes when in dark neither in methanol nor in water. While aqueous solutions of complexes are stable under the influence of incident visible radiation, steady-state irradiation of the methanolic systems by visible light led to photoreduction of iron(III) to iron(II), the quantum yield of iron(II) photoformation was determined.

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

  • Albertus, F., Cladera, A., & Cerda V. (2000). A robust multisyringe system for process flow analysis. Part II. A multi-commuted injection system applied to the photometric determination of free acidity and iron (III) in metallurgical solutions. Analyst, 125, 2364–2371. DOI: 10.1039/b0042501.

    Article  CAS  Google Scholar 

  • Beck, M., & Nagypal, I. (1989). Chemistry of complex equilibria. Budapest: Akademiai Kiado.

    Google Scholar 

  • Bonneville, S., Behrends, T., Haese, R., & Van Cappellen, P. (2003). Thermodynamic constraints on microbial iron oxide reduction. In Geophysical Research Abstracts, Vol. 5, April 6–11, 2003 (pp. 12591). Nice: EGS-AGU-EUG Joint Assembly. http://www.cosis.net/abstracts/EAE03/12591/EAE03J-12591.pdf.

    Google Scholar 

  • Corigli, R., Secco, F., & Venturini, M. (1982). Equilibriums and kinetics of complex formation at gallium(III). Evidence for an associative mode of activation. Inorganic Chemistry, 21, 2992–2998. DOI: 10.1021/ic00138a016.

    Article  CAS  Google Scholar 

  • Deacon, G. B., Forsyth, C. M., Behrsing, T., Konstas, K., & Forsyth, M. (2002). Heterometallic CeIII-FeIII-salicylate networks: models for corrosion mitigation of steel surfaces by the ‘Green’ inhibitor, Ce(salicylate)3. Chemical Communication, 2820–2821. DOI: 10.1039/b207722a.

  • Demougeot, C., Marie, C., & Beley, A. (2000). Importance of iron location in iron-induced hydroxyl radical production by brain slices. Life Science, 67, 399–410. DOI: 10.1016/S0024-3205(00)00638-X.

    Article  CAS  Google Scholar 

  • Ernst, Z. L., & Menashi, J. (1963). Complex formation between the Fe3+ ion and some substituted phenols. Part 1. Spectrophotometric determination of the stability constant of ferric salicylate. Transactions of the Faraday Society, 59, 1794–1802. DOI: 10.1039/TF9635901794.

    Article  CAS  Google Scholar 

  • Grenthe, I. (1992). Chemical thermodynamics of uranium. Amsterdam: NEA, North-Holland.

    Google Scholar 

  • Gupta, V. P., Shtapak, J. K., & Sharma, D. D. (1981). Stability constants for copper complexes of substituted salicylic acids. Journal of Inorganic and Nuclear Chemistry, 43, 3019–3022. DOI: 10.1016/0022-1902(81)80671-9.

    Article  CAS  Google Scholar 

  • Hartley, F. R., Burgess, C., & Alcock, R. M. (1980). Solution equilibria. New York: Ellis Horwood.

    Google Scholar 

  • Harvey, D. (1999). Modern analytical chemistry, pp. 278–350. New York: McGraw-Hill Science.

    Google Scholar 

  • Hooper, D. C. and Rubinstein, E. (2003). Quinolone antimicrobial agents (3rd ed.). Washington, DC: ASM Press.

    Google Scholar 

  • Högfeldt, E. (1982). Stability constants of metal-ion complexes (2nd ed.), Part A. Inorganic ligands, p. 32. Oxford: Pergamon Press.

    Google Scholar 

  • Jahagirdar, D. V. (1974). Potentiometric studies of Fe(III) complexes of some substituted salicylic acids. Journal of Nuclear and Inorganic Chemistry, 36, 2388–2390. DOI: 10.1016/0022-1902(74)80290-3.

    Article  CAS  Google Scholar 

  • Karnik, B. S., Davies, S. H., Baumann, M. J., & Masten, S. J. (2007). Use of salicylic acid as a model compound to investigate hydroxyl radical reaction in an ozonation-membrane filtration hybrid process. Environmental Engineering Science, 24, 852–860. DOI: 10.1089/ees.2006.0156.

    Article  CAS  Google Scholar 

  • Kotrlý, S., & Šucha, L. (1988). Chemical equilibria in analytical chemistry. Praha: SNTL.

    Google Scholar 

  • Lajunen, L. H. J., Portanova, R., Piispanen J., & Tolazzi, M. (1997). Stability constants for alpha-hydroxycarboxylic acid complexes with protons and metal ions and the accompanying enthalpy changes — Part I: Aromatic ortho-hydroxycarboxylic acids. Pure & Applied Chemistry, 69, 329–381. DOI: 10.1351/pac199769020329.

    Article  CAS  Google Scholar 

  • Ma, J.-H. (2005). Reactions of hydroxyl radical with salicylic acid derivatives: A pulse radiolysis study. Chinese Journal of Chemistry, 23, 1273–1274. DOI: 10.1002/cjoc.200591273.

    Article  CAS  Google Scholar 

  • Martell, A. E. & Smith, R. M. (1989). Critical stability constants (4th ed.). New York: Plenum Press.

    Google Scholar 

  • Martelli, P. G., Reis, B. F., Kronka, E. A. M., Bergamin, H., Korn, M., Zagatto, E. A. E., Lima, J. L. F. C., & Araujo, A. N. (1995). Multicommutation in flow analysis. Part 2. Binary sampling for spectrophotometric determination of nickel, iron and chromium in steel alloys. Analytica Chimica Acta, 308, 397–405. DOI: 10.1016/0003-2670(94)00281-P.

    Article  CAS  Google Scholar 

  • Meloun, M., & Havel, J. (1985). Computation of solution equilibria. 1. Spectrophotometry. Brno: J. E. Purkyně University Press.

    Google Scholar 

  • Mentasti, E., Secco, F., & Venturini, M. (1980). Complex formation between nickel(II) and cobalt(II) with salicylic acids. Equilibriums and reaction mechanisms. Inorganic Chemistry, 19, 3528–3531. DOI: 10.1021/ic50213a064.

    Article  CAS  Google Scholar 

  • Momoki, K., Sekino, J., Sato, H., & Yamaguchi, N. (1969). Theory of curved molar ratio plots and a new linear plotting method. Analytical Chemistry, 41, 1286–1299. DOI: 10.1021/ac60279a008.

    Article  CAS  Google Scholar 

  • Obata, T. (2006). Effect of desferrioxamine, a strong iron (III) chelator, on 1-methyl-4-phenylpyridinium ion (MPP+)-induced hydroxyl radical generation in the rat striatum. European Journal of Pharmacology, 539, 34–38. DOI: 10.1016/j.ejphar.2006.03.071.

    Article  CAS  Google Scholar 

  • Obata, T., & Yamanaka, Y. (2002). Iron (III) attenuates hydroxyl radical generation accompanying non-enzymatic oxidation of noradrenaline in the rat heart. Naunyn Schmiedeberg’s Archives of Pharmacology, 365, 158–163. DOI: 10.1007/s002100000249.

    Article  CAS  Google Scholar 

  • Palanisami, N., Prabusankar, G., & Murugavel, R. (2006). A novel dimeric copper salicylate with an undissociated COOH group: Synthesis and crystal structure of [Cu2(HSal)(Sal)(2,2′-bpy)2](ClO4). Inorganic Chemistry Communications, 9, 1002–1006. DOI: 10.1016/j.inoche.2006.05.025.

    Article  CAS  Google Scholar 

  • Poulias, G., Papadopoulos, N., & Jannakoudakis, D. (1986). Dissociation of 5-fluoro-and 3,5-dinitrosalicyclic acids in water-methanol mixtures at 25°. Talanta, 33, 461–462. DOI: 10.1016/0039-9140(86)80118-7.

    Article  CAS  Google Scholar 

  • Renz, F., Linert, W., Fleischauer, P., Klement, R., Mazúr, M., Šima, J., & Boča, R. (1995). Iron(II) spin crossover system: [Fe(bzimpy)2](ClO4)2. In Current Trends in Coordination Chemistry, June 5–9, 1995 (pp. 303–308). Bratislava: STU Press.

    Google Scholar 

  • Rose, A. L. & Waite, T. D. (2005). Reduction of organically complexed ferric iron by superoxide in a simulated natural water. Environmental Science and Technology, 39, 2645–2650. DOI: 10.1021/es048765k.

    Article  CAS  Google Scholar 

  • Rossotti, F. J. C. & Rossotti, H. (1961). The determination of stability constants, and other equilibrium constants in solution, pp. 149–150. New York: McGraw-Hill.

    Google Scholar 

  • Szabó-Plánka, T., Gyurcsik, B., Nagy, N. V., Rockenbauer, A., Šipoš, R., Šima, J., & Melník, M. (2008). Complexation of 5-fluorosalicylic acid with copper(II): A pH-potentiometric, UV-vis spectroscopic, and electron spin resonance study by the two-dimensional simulation of spectra. Journal of Inorganic Biochemistry, 102, 101–109. DOI: 10.1016/j.jinorgbio.2007.07.019.

    Article  CAS  Google Scholar 

  • Šima, J. & Makáňová, J. (1997). Photochemistry of iron(III) complexes. Coordination Chemistry Reviews, 160, 161–189. DOI: 10.1016/S0010-8545(96)01321-5.

    Article  Google Scholar 

  • Šima, J., Mrázová, J., & Kotočová, A. (1999). Photoredox properties of iron (III) fluoro complexes containing tetradentate open-chain N2O2-ligands. Journal of the Chinese Chemical Society, 46, 993–997.

    Google Scholar 

  • Šima, J., Šípoš, R., Izakovič, M., Valigura, D., & Tarapčík, P. (2006). Speciation and spectra of bromokojatoiron(III) complexes in aqueous solutions. Polish Journal of Chemistry, 80, 1991–1999.

    Google Scholar 

  • Udnan, Y., Jakmunee, J., Jayasavati, S., Christian, G. D., Synovec, R. E., & Grudpan, K. (2004). Cost-effective flow injection spectrophotometric assay of iron content in pharmaceutical preparations using salicylate reagent. Talanta, 64, 1237–1240. DOI: 10.1016/j.talanta.2004.03.067.

    Article  CAS  Google Scholar 

  • Zarembowitch, J., Kahn, O., Jaud, J., & Galy, J. (1982). Versatility of iron(III) upon coordination with the binucleating ligand N,N′-bis-(2-hydroxy, 3-carboxybenzilidene)1,2-diaminoethane. Inorganica Chimica Acta, 65, L35–L36. DOI: 10.1016/S0020-1693(00)93485-6.

    Article  CAS  Google Scholar 

  • Zékány, L., Nagypál, I., & Peintler, G. (1991). PSEQUAD for chemical equilibria [computer software]. Baltimore, MD: Technical Software Distributors.

    Google Scholar 

  • Zhang, C., Wang, L., Wu, F., & Deng, N. (2006). Quantitation of hydroxyl radicals from photolysis of Fe(III)-citrate complexes in aerobic water. Environmental Science and Pollution Research — International, 13, 156–160. DOI: 10.1065/espr2005.10.287.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Rastislav Šípoš.

Additional information

Dedicated to Professor Milan Melník on the occasion of his 70th birthday

Rights and permissions

Reprints and permissions

About this article

Cite this article

Šípoš, R., Šima, J., Tarapčík, P. et al. Solution properties of iron(III) complexes with 5-fluorosalicylic acid — spectra, speciation, and redox stability. Chem. Pap. 62, 496–503 (2008). https://doi.org/10.2478/s11696-008-0061-8

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.2478/s11696-008-0061-8

Keywords

Navigation