Advertisement

Chemical Papers

, Volume 72, Issue 4, pp 883–893 | Cite as

Thermodynamic aspect: kinetics of the reduction of dicyanobis(phen)iron(III) by acetylferrocene and methylferrocenemethanol

  • Rozina Khattak
  • Misbah Nazir
  • Shazia Summer
  • Murtaza Sayed
  • Aaliya Minhaz
  • Iftikhar I. Naqvi
Original Paper

Abstract

Protonation plays an important role in the redox reactions. We observed this leading role during the reduction of [FeIII(phen)2(CN)2]+ by FcCOMe and FcCHOHMe. The kinetic data showed that the reaction(s) followed a complex kinetics due to the formation of protonated acetylferrocene (FcC+OHMe), and or, protonated α-methylferrocenemethanol (FcCHO+H2Me) in aqueous dioxane (80% v/v). Our results helped us to conclude that the reactions were completed in three phases. An overall zeroth order was observed in the first phase of the reactions. In the second phase, the kinetic data showed an overall second order reaction. The third phase was a complex phase where the rate of redox reactions and the insolubility of the neutral product ([FeII(phen)2(CN)2]) competed with each other. We studied the effect of different factors to identify the reacting entities, which take part in the rate-determining step of each reaction in the second phase. Consequently, we determined the effects of selected factors upon the observed pseudo-first order rate constant(s) (k′ obs) of each reaction. The value of k′ obs increased upon addition of protons in the reaction mixture in case of FcCOMe, and it decreased during the oxidation of FcCHOHMe. Meanwhile, upon enhancing the ionic strength, we observed an increase in k′ obs for FcCOMe, and no change in the value of k′ obs during the reaction of FcCHOHMe. However, a decrease in k′ obs was noticed upon increasing the dielectric constant of the reaction mixture when the reductant was FcCOMe, and no effect was observed in case of FcCHOHMe. Together, these results suggested oxidation of FcC+OHMe and FcCHOHMe in the slow-step, and FcCOMe and FcCHO+H2Me during the fast-step. We refined our results by estimating the thermodynamic parameters of activation. The low values of activation energy and enthalpy of activation confirmed that the reduction of [FeIII(phen)2(CN)2]+ hardly depends upon temperature when the reducing agent is FcCOMe. The outcomes justified that the rate of reaction depends upon the unsaturated FcC+OHMe. This intermediate species contain a ‘carbonium ion’, which is very reactive and energetic. We obtained comparatively high values of the activation energy and enthalpy of activation for the reaction between [FeIII(phen)2(CN)2]+ and FcCHOHMe. The results show that FcCHOHMe is a saturated and stable compound that leads the slow-step and controls the rate of reaction.

Keywords

Acetylferrocene α-Methylferrocenemethanol Dicyanobis(phen)iron(III) Outer-sphere mechanism 

Notes

Acknowledgements

The authors are indebted to the HEJ Research Institute of Chemistry, University of Karachi, Pakistan, for providing analytical services to carry out IR and microanalytical characterization of the synthesized compound(s).

Supplementary material

11696_2017_334_MOESM1_ESM.docx (240 kb)
Supplementary material 1 (DOCX 239 kb)

References

  1. Arnett EM, Bushick RD (1962) Quantitative estimates of the strong electron donor properties of metallocenyl nuclei. J Org Chem 27(1):111–115.  https://doi.org/10.1021/jo01048a028 CrossRefGoogle Scholar
  2. Baciocchi E, Floris B, Muraglia E (1993) Reactions of ferrocene and acetylferrocene with carbon-centered free radicals. J Org Chem 58(8):2013–2016.  https://doi.org/10.1021/jo00060a011 CrossRefGoogle Scholar
  3. Blake R, White KJ, Shute EA (1991) Mixed ligand complexes of iron with cyanide and phenanthroline as new probes of metalloprotein electron transfer reactivity. Analysis of reactions involving rusticyanin from Thiobacillus ferrooxidans. J Biol Chem 266(29):19203–19211. http://www.jbc.org/content/266/29/19203.full.pdf
  4. Casas JS, Castaño MV, Cifuentes MC, García-Monteagudo JC, Sánchez A, Sordo J, Touceda A (2007) Interaction of organolead(iv) derivatives with formyl- and acetylferrocene thiosemicarbazones: coordination versus dephenylation or reductive elimination processes. J. Organometal Chem 692(11):2234–2244.  https://doi.org/10.1016/j.jorganchem.2007.01.049 CrossRefGoogle Scholar
  5. Connelly NG, Geiger WE (1996) Chemical redox agents for organometallic chemistry. Chem Rev 96(2):877–910.  https://doi.org/10.1021/cr940053x CrossRefGoogle Scholar
  6. Floris B (2015) Ferrocene in agriculture: from agrochemicals and soil remediation to selective chemosensors. Chem Biol Technol Agric 2(1):15.  https://doi.org/10.1186/s40538-015-0038-0 CrossRefGoogle Scholar
  7. Gao Z-N, Ma J-F, Liu W-Y (2005a) Electrocatalytic oxidation of sulfite by acetylferrocene at glassy carbon electrode. Appl Organometal Chem 19(11):1149–1154.  https://doi.org/10.1002/aoc.975 CrossRefGoogle Scholar
  8. Gao Z-N, Zhang J, Liu W-Y (2005) Electrocatalytic oxidation of n-acetyl-l-cysteine by acetylferrocene at glassy carbon electrode. J Electroanal Chem 580(1):9–16. http://www.sciencedirect.com/science/article/B6TGB-4FXV79B-6/2/31261f9ef9b2fb7ce46753ffbffd8415
  9. Jong S-J, Fang J-M, Lin C-H (1999) The reactions of acylferrocenes with samarium diiodide: reduction, deoxygenation, reductive coupling and rearrangement. J Organometal Chem 590(1):42–45.  https://doi.org/10.1016/S0022-328X(99)00411-8 CrossRefGoogle Scholar
  10. Khattak R (2011) Comparative kinetic study for the electron transfer reactions of some iron complexes. In: Department of Chemistry. University of Karachi, Karachi, p 501Google Scholar
  11. Khattak R, Naqvi II, Farrukh MA (2008) Kinetics and mechanism of the oxidation of a ferrous complex with an α, α′-diimine chelate ligand by ceric sulfate in aqueous acidic medium by UV-Vis absorption spectroscopy. J Iran Chem Soc 5(4):631–640.  https://doi.org/10.1007/BF03246144 CrossRefGoogle Scholar
  12. Khattak R, Naqvi II, Summer S, Sayed M (2016) Mechanism of the oxidation of 1-(ferrocenyl)-ethanone/ethanol by dicyanobis(phenanthroline)iron(iii). Arab J Chem.  https://doi.org/10.1016/j.arabjc.2016.05.007
  13. Matsumoto M, Tarumi T, Sugimoto K-I, Kagayama N, Funahashi S, Takagi HD (1997) Oxidation reaction of l-ascorbic acid by dicyanobis(1,10-phenanthroline)iron(iii) in dimethyl sulfoxide at elevated pressure: evidence for adiabatic electron transfer. Inorg Chim Acta 255:81–85.  https://doi.org/10.1016/S0020-1693(96)05342-X CrossRefGoogle Scholar
  14. Osella D, Ferrali M, Zanello P, Laschi F, Fontani M, Nervi C, Cavigiolio G (2000) On the mechanism of the antitumour activity of ferrocenium derivatives. Inorg Chim Acta 306:42–48.  https://doi.org/10.1016/S0020-1693(00)00147-X CrossRefGoogle Scholar
  15. Patra M, Gasser G (2017) The medicinal chemistry of ferrocene and its derivatives. Nat Rev Chem 1:0066.  https://doi.org/10.1038/s41570-017-0066 CrossRefGoogle Scholar
  16. Pelizzetti E, Mentasti E, Pramauro E (1978) Outer-sphere oxidation of ascorbic acid. Inorg Chem 17(5):1181–1186.  https://doi.org/10.1021/ic50183a018 CrossRefGoogle Scholar
  17. Pladziewicz JR, Espenson JH (1973) Kinetics and mechanisms of some electron transfer reactions of ferrocenes. J Am Chem Soc 95(1):56–63.  https://doi.org/10.1021/ja00782a011 CrossRefGoogle Scholar
  18. Quirk PF, Kratochvil B (1970) Determination of ferrocene derivatives by oxidation with copper(ii) in acetonitrile. Anal Chem 42(4):535–536.  https://doi.org/10.1021/ac60286a035 CrossRefGoogle Scholar
  19. Realista S, Quintal S, Martinho PN, Melato AI, Gil A, Esteves T, Carvalho MD, Ferreira LP, Vaz PD, Calhorda MJ (2017) Electrochemical studies and potential anticancer activity in ferrocene derivatives. J Coord Chem 70(2):314–327.  https://doi.org/10.1080/00958972.2016.1257125 CrossRefGoogle Scholar
  20. Rubalcava HE, Thomson JB (1963) A spectroscopic study of the protonation of acetylferrocenes. Hydrogen-deuterium exchange in the conjugate acids. J Phys Chem 67(2):310–313.  https://doi.org/10.1021/j100796a023 CrossRefGoogle Scholar
  21. Saleem M, Yu H, Wang L, Zain ul A, Khalid H, Akram M, Abbasi NM, Huang J (2015) Review on synthesis of ferrocene-based redox polymers and derivatives and their application in glucose sensing. Analyt Chim Acta 876(Supplement C):9–25.  https://doi.org/10.1016/j.aca.2015.01.012 CrossRefGoogle Scholar
  22. Sasaki Y, Pittman CU (1973) Acid-catalyzed reaction of acetylferrocene with triethyl orthoformate. J Org Chem 38(21):3723–3726.  https://doi.org/10.1021/jo00961a014 CrossRefGoogle Scholar
  23. Schilt AA (1960) Mixed ligand complexes of iron(ii) and (iii) with cyanide and aromatic di-imines. J Am Chem Soc 82(12):3000–3005.  https://doi.org/10.1021/ja01497a007 CrossRefGoogle Scholar
  24. Shago RF, Swarts JC, Kreft E, Rensburg CEJV (2007) Antineoplastic activity of a series of ferrocene-containing alcohols. Anticancer Res 27:3431–3434. http://citeseerx.ist.psu.edu/viewdoc/download?doi=10.1.1.1022.7131&rep=rep1&type=pdf
  25. Summer S, Naqvi II, Khattak R, Gulzar S, Reyaz F (2016) Kinetics and mechanism of [fe (bipy)3]2+ and [bro3] system in aqueous acidic medium. J Chem Soc Pak 38(03):384–389. http://www.jcsp.org.pk/ViewByVolume.aspx?v=1209&i=VOLUME%2038,%20NO3,%20JUNE-2016
  26. Takagi HD, Kagayama N, Matsumoto M, Tarumi T, Funahashi S (1995) Mechanistic study of oxidation reactions of hydroquinone, catechol and l-ascorbic acid by dicyanobis(1,10-phenanthroline)iron(iii) in dimethyl sulfoxide. J Mol Liq 65–66:277–280.  https://doi.org/10.1016/0167-7322(95)00827-0 CrossRefGoogle Scholar
  27. Xu X, Nolan SP, Cole RB (1994) Electrochemical oxidation and nucleophilic addition reactions of metallocenes in electrospray mass spectrometry. Anal Chem 66(1):119–125.  https://doi.org/10.1021/ac00073a021 CrossRefGoogle Scholar

Copyright information

© Institute of Chemistry, Slovak Academy of Sciences 2017

Authors and Affiliations

  • Rozina Khattak
    • 1
    • 2
  • Misbah Nazir
    • 2
  • Shazia Summer
    • 3
  • Murtaza Sayed
    • 4
  • Aaliya Minhaz
    • 1
  • Iftikhar I. Naqvi
    • 2
  1. 1.Department of ChemistryShaheed Benazir Bhutto Women UniversityPeshawarPakistan
  2. 2.Department of ChemistryUniversity of KarachiKarachiPakistan
  3. 3.Department of ChemistryJinnah University for WomenKarachiPakistan
  4. 4.National Center of Excellence in Physical ChemistryUniversity of PeshawarPeshawarPakistan

Personalised recommendations