Advertisement

Journal of Solution Chemistry

, Volume 42, Issue 2, pp 441–458 | Cite as

Kinetic Studies on Interaction of Platinum(II) Complexes with an ‘S’ Containing Ligand in Aqueous Medium

  • Parnajyoti Karmakar
  • Sumon Ray
  • Debabrata Nandi
  • Arup Mandal
  • Subala Mondal
  • Subhasis Mallick
  • Biplab K. Bera
  • Alak K. GhoshEmail author
Article

Abstract

The kinetics of the substitution reactions of [Pt(dach)(H2O)2]2+ and [Pt(en)(H2O)2]2+ (where ‘dach’ and ‘en’ are cis-1,2-diaminocyclohexane and ethylenediamine, respectively) with excess N,N′-diethylthiourea have been studied in aqueous solution by UV–Vis spectrophotometry. The effect of different N–N spectator ligands on the reactivity of platinum(II) complexes was investigated by studying the water lability of the reactant complexes. The kinetic study has been substantiated by product isolation, IR, NMR and ESI-MS spectral analysis and DFT calculations. The reactions follow normal square-planar substitution mainly in an associative way. Rate parameters have been evaluated under different conditions. The substitution rates of the complexes studied can be tuned through the nature of the N–N chelates, which is important in the development of new active compounds for cancer therapy.

Keywords

Pt(II) Interaction N,N′-diethylthiourea Aqueous medium 

References

  1. 1.
    Lipert, B. (ed.): Cisplatin—Chemistry and Biochemistry of Leading Anticancer Drug. Wiley VCH, Weinheim (1999)Google Scholar
  2. 2.
    Hindmarsh, K., House, D.A., Turnbull, M.M.: The hydrolysis products of cis-diamminedichloroplatinum(II) 9. Chloride and bromide anation kinetics for some [PtII(N)2(OH2)2]2+ complexes and the structures of [PtIVBr4(N)2] ((N)2 = en, tn). Inorg. Chim. Acta 257, 11–18 (1997)CrossRefGoogle Scholar
  3. 3.
    Baird, C.L., Griftitus, A.E., Baffic, S.P., Bryant, P., Wolf, B., Lutton, J., Beradini, M., Arvanitis, G.M.: Synthesis, characterization and antitumor activity of platinum triamine complexes containing imidazothiazole ligands. Inorg. Chim. Acta 256, 253–262 (1997)CrossRefGoogle Scholar
  4. 4.
    Jamieson, E.R., Lippard, S.J.: Structure, recognition, and processing of cisplatin–dna adducts. Chem. Rev. 99, 2467–2498 (1999)CrossRefGoogle Scholar
  5. 5.
    Arpalahti, J., Lippert, B.: Coordination of aquated cis-platinum(II) diamines to purine nucleosides. Kinetics of complex formation. Inorg. Chem. 29, 104–110 (1990)CrossRefGoogle Scholar
  6. 6.
    Rosenberg, B., Van Camp, L., Trosko, J.E., Mansour, V.H.: Platinum compounds: A new class of potent antitumour agents. Nature 222, 385–386 (1969)CrossRefGoogle Scholar
  7. 7.
    Kostova, I.: Platinum complexes as anticancer agents. Recent Pat. Anti Cancer Drug Discov. 1, 1–22 (2006)CrossRefGoogle Scholar
  8. 8.
    Umapathy, P.: The chemical and biochemical consequences of the binding of the antitumour drug cisplatin and other platinum group metal complexes to DNA. Coord. Chem. Rev. 95, 129–181 (1989)CrossRefGoogle Scholar
  9. 9.
    Wong, E., Giandomenico, C.M.: Current status of platinum-based antitumor drugs. Chem. Rev. 99, 2451–2466 (1999)CrossRefGoogle Scholar
  10. 10.
    Reedijk, J.: Why does cisplatin reach guanine-N7 with competing S-donor ligands available in the cell? Chem. Rev. 99, 2499–2510 (1999)CrossRefGoogle Scholar
  11. 11.
    Takahara, P.M., Frederick, C.A., Lippard, S.J.: Crystal structure of the anticancer drug cisplatin bound to duplex DNA. J. Am. Chem. Soc. 118, 12309–12321 (1996)CrossRefGoogle Scholar
  12. 12.
    Wang, X., Guo, Z.: The role of sulfur in platinum anticancer chemotherapy. Anti Cancer Agents Med. Chem. 7, 19–34 (2007)CrossRefGoogle Scholar
  13. 13.
    Cvitkovic, E.: Cumulative toxicities from cisplatin therapy and current cytoprotective measures. Cancer Treat. Rev. 24, 265–281 (1998)CrossRefGoogle Scholar
  14. 14.
    Saeed, S., Rashid, N., Ali, M., Hussain, R., Jones, P.: Synthesis, spectroscopic characterization, crystal structure and pharmacological properties of some novel thiophene–thiourea core derivatives. Eur. J. Chem. 1, 221–227 (2010)CrossRefGoogle Scholar
  15. 15.
    Khokhar, A.R., Krakoff, I.H., Hacker, M.P., McCormack, J.J.: The synthesis and antitumor properties of a series of water soluble carboxylato-(1,2-diaminocyclohexane) platinum(II) complexes. Inorg. Chim. Acta 108, 63–66 (1985)CrossRefGoogle Scholar
  16. 16.
    Lim, M.C., Martin, R.B.: The nature of cis amine Pd(II) and antitumor cis amine Pt(II) complexes in aqueous solutions. J. Inorg. Nucl. Chem. 38, 1911–1914 (1976)CrossRefGoogle Scholar
  17. 17.
    Coley, R.F., Martin Jr., D.S.: Kinetics and equilibria for the acid hydrolysis of dichloro(ethylenediamine)platinum(II). Inorg. Chim. Acta 7, 573–577 (1973)CrossRefGoogle Scholar
  18. 18.
    Bailey, R.A., Peterson, T.R.: Complexes of nickel(II) with substituted thioureas. Can. J. Chem. 46, 3119–3128 (1968)CrossRefGoogle Scholar
  19. 19.
    Lane, T.J., Yamaguchi, A., Quagliano, J.V., Ryan, J.A., Mizushima, S.: Infrared absorption spectra of inorganic coördination complexes. XXII. Infrared studies of methylthiourea and its metal complexes. J. Am. Chem. Soc. 81, 3824–3826 (1959)CrossRefGoogle Scholar
  20. 20.
    Miao, R., Yang, G., Miao, Y., Mei, Y., Hong, J., Zhao, C., Zhu, L.: Interactions of platinum(II) complexes with sulfur-containing peptides studied by electrospray ionization mass spectrometry and tandem mass spectrometry. Rapid Commun. Mass Spectrosc. 19, 1031–1040 (2005)CrossRefGoogle Scholar
  21. 21.
    Summa, N., Schiessl, W., Puchta, R., Hommes, N.V.E., Eldik, R.V.: Thermodynamic and kinetic studies on reactions of Pt(II) complexes with biologically relevant nucleophiles. Inorg. Chem. 45, 2948–2959 (2006)CrossRefGoogle Scholar
  22. 22.
    Banerjee, S., Sengupta, P.S., Mukherjee, A.K.: A detailed theoretical study of the interaction of thiourea with cis-diaqua(ethylenediamine) platinum(II). J. Mol. Struct. (Thoechem) 913, 97–106 (2009)CrossRefGoogle Scholar
  23. 23.
    Bachechi, F., Zambonelli, L.: Crystal and molecular structure of tetrakis(N-ethylthiourea)platinum(II) iodide. Inorg. Chim. Acta 17, 225–228 (1976)CrossRefGoogle Scholar
  24. 24.
    Walter, J.L., Walter, C.S.C., Ryan, J.A., Lane, T.J., Lane, C.C.S.: A study of thiourea and substituted thiourea analogs by the Bjerrum titration method. J. Am. Chem. Soc. 78, 5560–5562 (1956)CrossRefGoogle Scholar
  25. 25.
    Irving, H.M., Rossotti, H.S.: The stabilities of some metal complexes of 8-hydroxyquinoline and related substances. J. Chem. Soc. 2904–2910 (1954)Google Scholar
  26. 26.
    Weyh, J.A., Hamm, R.E.: Aquation of the cis-bis(iminodiacetato)chromate(III) and trans(fac)-bis(methyliminodiacetato)chromate(III) ions in acidic aqueous medium. Inorg. Chem. 8, 2298–2302 (1969)CrossRefGoogle Scholar
  27. 27.
    Sengupta, P.S., Sinha, R., De, G.S.: Kinetics and mechanism of the interaction of pyridine-2-thiol with cis-diaqua(ethylenediamine)platinum(II) perchlorate in aqueous medium. Indian J. Chem. 39A, 928–931 (2000)Google Scholar
  28. 28.
    Ghosh, S., Sengupta, P.S., De, G.S.: Kinetic and mechanistic studies of the interaction of thiosemicarbazide with cis-diaqua(ethylenediamine)platinum(II) ion. Indian J. Chem. 38A, 453–457 (2000)Google Scholar
  29. 29.
    Sinha, R., Choudhury, A.K., De, G.S.: Kinetics of substitution of aqua ligands from cis-diaqua(cis-1,2-diaminocyclohexane)platinum(II) perchlorate by glutathione in aqueous medium. Indian J. Chem. 42A, 473–477 (2003)Google Scholar
  30. 30.
    Mukhopadhyay, S.K.: Kinetics and mechanism of aqua ligand substitution from cis-diaqua(cis-1,2-diaminocyclohexane)platinum(II)perchlorate by diethyldithiocarbamate anion in aqueous medium. Transition Met. Chem. 33, 739–743 (2008)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2013

Authors and Affiliations

  • Parnajyoti Karmakar
    • 1
  • Sumon Ray
    • 1
  • Debabrata Nandi
    • 1
  • Arup Mandal
    • 1
  • Subala Mondal
    • 1
  • Subhasis Mallick
    • 1
  • Biplab K. Bera
    • 1
  • Alak K. Ghosh
    • 1
    Email author
  1. 1.Department of ChemistryThe University of BurdwanBurdwanIndia

Personalised recommendations