Kinetics and mechanism of the redox reaction of N,N′-phenylenebis-(salicylideneiminato)iron(III) with oxalic acid in mixed aqueous medium

  • I. IbrahimEmail author
  • S. O. Idris
  • I. Abdulkadir
  • A. D. Onu


The kinetics of electron transfer between N,N′-phenylenebis-(salicylideneiminato)iron(III), hereafter referred to as [Fe(Salphen)]+, and oxalic acid was studied in mixed aqueous medium (DMSO:H2O; 1:4 v/v) under pseudo-first-order conditions at 26 ± 1 °C, I = 0.2 coulomb2 mol dm−3 (NaCl) and λmax = 435 nm. The reaction was found to be second order overall and acid independent, and displayed zero Brønsted–Debye salt effect. There was no evidence for the formation of an intermediate complex or free radicals during the reaction. Overall, the kinetic data suggest an inner-sphere mechanism for the reaction, which is first order in both reactants. A plausible reaction mechanism is proposed.


  1. 1.
    Jacobsen EN, Zhang W, Guler ML (1991) Electronic tuning of asymmetric catalysts. J Am Chem Soc 113:6703–6704CrossRefGoogle Scholar
  2. 2.
    Bhattacharya S, Mandal SS (1996) DNA cleavage by intercalatable cobalt bispicolylamine complexes activated by visible light. Chem Commun 13:1515–1516CrossRefGoogle Scholar
  3. 3.
    Routier S, Bernier JL, Waring MJ, Colson P, Houssier C, Bailly C (1996) Synthesis of a functionalized salen copper complex and its interaction with DNA. J Org Chem 61:2326–2331CrossRefGoogle Scholar
  4. 4.
    Muller JG, Kayser LA, Paikoff SJ, Duarte V, Tang N, Perez RJ et al (1999) Formation of DNA adducts using nickel(II) complexes of redox-active ligands: a comparison of salen and peptide complexes. Coord Chem Rev 186:761–774CrossRefGoogle Scholar
  5. 5.
    Czlapinski JL, Sheppard TL (2001) Nucleic acid template-directed assembly of metallosalen DNA conjugates. J Am Chem Soc 123:8618–8619CrossRefPubMedGoogle Scholar
  6. 6.
    Doctrow SR, Huffman K, Marcus CB, Tocco G, Malfroy E, Adinolfi CA et al (2002) Salen-manganese complexes as catalytic scavengers of hydrogen peroxide and cytoprotective agents: structure-activity relationship studies. J Med Chem 45:4549–4558CrossRefPubMedGoogle Scholar
  7. 7.
    Komiyama M, Takeda N, Shigekawa H (1999) Hydrolysis of DNA and RNA by lanthanide ions: mechanistic studies leading to new applications. Chem Commun 16:1443–1451CrossRefGoogle Scholar
  8. 8.
    Cohen SM, Lippard SJ (2001) Cisplatin: from DNA damage to cancer chemotherapy. Prog Nucleic Acid Res Mol Biol 67:93–130CrossRefPubMedGoogle Scholar
  9. 9.
    Barnes KR, Lippard SJ (2004) Cisplatin and related anticancer drugs: recent advances and insights. Met Ions Biol Syst 42:143PubMedGoogle Scholar
  10. 10.
    Ott I, Gust R (2007) Non platinum metal complexes as anticancer drugs. Archiv der Pharmazie (Weinheim) 340(3):117–126CrossRefGoogle Scholar
  11. 11.
    Zaheer K, Athar AH, Lateef A, Haq MM (1998) Kinetics and mechanism of chromic acid oxidation of oxalic acid in absence and presence of different acid media. A kinetic study. Int J Chem Kinet 30:335–340CrossRefGoogle Scholar
  12. 12.
    Ehrsson H, Wallin I, Yachnin J (2002) Pharmacokinetics of oxaliplatin in humans. Med Oncol 19(4):261–265CrossRefPubMedGoogle Scholar
  13. 13.
    Kovacs KA, Grof P, Burai L, Riedel M (2004) Revising the mechanism of the permanganate/oxalate reaction. J Phys Chem A 108(50):11026–11031CrossRefGoogle Scholar
  14. 14.
    Bakore GV, Jian CL (1969) Chromic acid oxidation of oxalic acid: kinetic investigation of the uncatalyzed oxidation of oxalic acid by chromic acid. J Inorg Nucl Chem 31:805–810CrossRefGoogle Scholar
  15. 15.
    Subba-Rao PV, Krishna-Rao GSR, Ramakrishna K, Murthy PSN (1991) Kinetics of chromic acid–oxalic acid reaction catalyzed by manganese(II)—kinetic analysis of the consecutive pathway. Indian J Chem 30:239–342Google Scholar
  16. 16.
    Ansari IK, Sahba K, James DG, Mandal SS (2011) Fe(III) salen and salphen complexes induce caspase activation and apoptosis in human cells. J Biomol Screen 16:26–35CrossRefPubMedGoogle Scholar
  17. 17.
    Liou YW, Wang CM (2000) Peroxidase mimicking: Fe(Salen)Cl modified electrodes, fundamental properties and applications for biosensing. J Electroanal Chem 481(1):102–109CrossRefGoogle Scholar
  18. 18.
    Subramaniam P, Vanitha T, Kodispathi T, Sundari CRS (2014) Role of iron(III)-salen chloride as oxidizing agent with thiodiglycolic acid: the effect of axial ligands. J Mex Chem Soc 58(2):211–217Google Scholar
  19. 19.
    Kurahashi T, Kobayashi Y, Nagatomo S, Tosha T, Kitagawa T, Fujii H (2005) Oxidizing intermediates from the sterically hindered iron salen complexes related to the oxygen activation by nonheme iron enzymes. Inorg Chem 44:8156–8166CrossRefPubMedGoogle Scholar
  20. 20.
    Hamza SA, Iyun JF, Idris SO (2012) Kinetics and mechanism of the redox reaction of toluidine blue and nitrite ions in aqueous acidic medium. Arch Appl Sci Res 4(1):10–18Google Scholar
  21. 21.
    Idris SO, Tanimu A, Iyun JF, Mohammed Y (2015) Kinetics and mechanism of malachite green oxidation by hypochlorite ion in aqueous acidic medium. Am Chem Sci J 5(2):185–193CrossRefGoogle Scholar
  22. 22.
    Adetoro A, Iyun JF, Idris SO (2011) Kinetic approach to the mechanism of redox reaction of pyrocatechol violet and nitrite ion in aqueous hydrochloric acid. Res J Appl Sci Eng Technol 3(10):1159–1163Google Scholar
  23. 23.
    Benson D (1969) Mechanism of inorganic reactions in solution, 2nd edn. Mc Graw-Hill, New York City, p 153Google Scholar
  24. 24.
    Atkins PW, de Paula J (2002) Physical chemistry, 7th edn. Oxford University Press, Oxford, p 962Google Scholar
  25. 25.
    Steven Mifsud (2018) MarZ Kreations Malta. Accessed 31 Aug 2018
  26. 26.
    Vogel AI (1979) Vogel’s textbook of macro and semimicro qualitative inorganic analysis, 5th edn. Longman, London, p 298 (Svehla G revised edn.) Google Scholar

Copyright information

© Springer Nature Switzerland AG 2018

Authors and Affiliations

  • I. Ibrahim
    • 1
    Email author
  • S. O. Idris
    • 1
  • I. Abdulkadir
    • 1
  • A. D. Onu
    • 2
  1. 1.Department of ChemistryAhmadu Bello UniversityZariaNigeria
  2. 2.Department of ChemistryFederal College of EducationZariaNigeria

Personalised recommendations