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

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Abstract

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.

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References

  1. Jacobsen EN, Zhang W, Guler ML (1991) Electronic tuning of asymmetric catalysts. J Am Chem Soc 113:6703–6704

    Article  CAS  Google Scholar 

  2. Bhattacharya S, Mandal SS (1996) DNA cleavage by intercalatable cobalt bispicolylamine complexes activated by visible light. Chem Commun 13:1515–1516

    Article  Google Scholar 

  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 61:2326–2331

    Article  CAS  Google Scholar 

  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 186:761–774

    Article  Google Scholar 

  5. Czlapinski JL, Sheppard TL (2001) Nucleic acid template-directed assembly of metallosalen DNA conjugates. J Am Chem Soc 123:8618–8619

    Article  CAS  PubMed  Google Scholar 

  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 45:4549–4558

    Article  CAS  PubMed  Google Scholar 

  7. Komiyama M, Takeda N, Shigekawa H (1999) Hydrolysis of DNA and RNA by lanthanide ions: mechanistic studies leading to new applications. Chem Commun 16:1443–1451

    Article  Google Scholar 

  8. Cohen SM, Lippard SJ (2001) Cisplatin: from DNA damage to cancer chemotherapy. Prog Nucleic Acid Res Mol Biol 67:93–130

    Article  CAS  Google Scholar 

  9. Barnes KR, Lippard SJ (2004) Cisplatin and related anticancer drugs: recent advances and insights. Met Ions Biol Syst 42:143

    CAS  PubMed  Google Scholar 

  10. Ott I, Gust R (2007) Non platinum metal complexes as anticancer drugs. Archiv der Pharmazie (Weinheim) 340(3):117–126

    Article  CAS  Google Scholar 

  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 30:335–340

    Article  Google Scholar 

  12. Ehrsson H, Wallin I, Yachnin J (2002) Pharmacokinetics of oxaliplatin in humans. Med Oncol 19(4):261–265

    Article  CAS  PubMed  Google Scholar 

  13. Kovacs KA, Grof P, Burai L, Riedel M (2004) Revising the mechanism of the permanganate/oxalate reaction. J Phys Chem A 108(50):11026–11031

    Article  CAS  Google Scholar 

  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 31:805–810

    Article  CAS  Google Scholar 

  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 30:239–342

    Google Scholar 

  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 16:26–35

    Article  CAS  PubMed  Google Scholar 

  17. Liou YW, Wang CM (2000) Peroxidase mimicking: Fe(Salen)Cl modified electrodes, fundamental properties and applications for biosensing. J Electroanal Chem 481(1):102–109

    Article  CAS  Google Scholar 

  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):211–217

    CAS  Google Scholar 

  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 44:8156–8166

    Article  CAS  PubMed  Google Scholar 

  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):10–18

    CAS  Google Scholar 

  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):185–193

    Article  CAS  Google Scholar 

  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):1159–1163

    CAS  Google Scholar 

  23. Benson D (1969) Mechanism of inorganic reactions in solution, 2nd edn. Mc Graw-Hill, New York City, p 153

    Google Scholar 

  24. Atkins PW, de Paula J (2002) Physical chemistry, 7th edn. Oxford University Press, Oxford, p 962

    Google Scholar 

  25. Steven Mifsud (2018) MarZ Kreations Malta. http://www.marz-kreations.com/Chemistry/Cation-ID/162k-Iron.html. Accessed 31 Aug 2018

  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 

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Authors and Affiliations

  1. Department of Chemistry, Ahmadu Bello University, Zaria, Nigeria

    I. Ibrahim, S. O. Idris & I. Abdulkadir

  2. Department of Chemistry, Federal College of Education, Zaria, Nigeria

    A. D. Onu

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  1. I. Ibrahim
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  2. S. O. Idris
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  3. I. Abdulkadir
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  4. A. D. Onu
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Correspondence to I. Ibrahim.

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Ibrahim, I., Idris, S.O., Abdulkadir, I. et al. Kinetics and mechanism of the redox reaction of N,N′-phenylenebis-(salicylideneiminato)iron(III) with oxalic acid in mixed aqueous medium. Transit Met Chem 44, 269–273 (2019). https://doi.org/10.1007/s11243-018-0291-8

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