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Kinetics and mechanism of the substitution reactions of [PtCl(bpma)]+, [PtCl(gly-met-S,N,N)] and their aqua analogues with l-methionine, glutathione and 5′-GMP

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Abstract

The substitution reactions of [PtCl(bpma)]+, [PtCl(gly-met-S,N,N)], [Pt(bpma)(H2O)]2+ and [Pt(gly-met-S,N,N)(H2O)]+ [where bpma is bis(2-pyridylmethyl)amine and gly-met-S,N,N is glycylmethionine] with l-methionine, glutathione and guanosine 5′-monophosphate (5′-GMP) were studied in aqueous solutions in 0.10 M NaClO4 under pseudo-first-order conditions as a function of concentration and temperature using UV–vis spectrophotometry. The reactions of the chloro complexes were followed in the presence of 10 mM NaCl and at pH ~ 5, whereas the reactions of the aqua complexes were studied at pH 2.5. The [PtCl(bpma)]+ complex is more reactive towards the chosen nucleophiles than [PtCl(gly-met-S,N,N)]. Also, the aqua complexes are more reactive than the corresponding chloro complexes. The activation parameters for all the reactions studied suggest an associative substitution mechanism. The reactions of [PtCl(bpma)]+ and [PtCl(gly-met-S,N,N)] with 5′-GMP were studied by using 1H NMR spectroscopy at 298 K. The pK a value of the [Pt(gly-met-S,N,N)(H2O)]+ complex is 5.95. Density functional theory calculations (B3LYP/LANL2DZp) show that in all cases guanine coordination to the L3Pt fragment (L3 is terpyridine, bpma, diethylenetriamine, gly-met-S,N,N) is much more favorable than the thioether-coordinated form. The calculations collectively support the experimentally observed substitution of thioethers from Pt(II) complexes by N7-GMP. This study throws more light on the mechanistic behavior of platinum antitumor complexes.

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Notes

  1. The performance of the computational level employed in this study is well documented; for example, see [40–46].

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Acknowledgements

The authors gratefully acknowledge financial support from the Ministry of Science and Technology, Republic of Serbia (project no. 142008) and the Deutsche Forschungsgemeinschaft (SFB 583 “Redox-active metal complexes”). We thank Tim Clark for hosting this work at the CCC and the Regionales Rechenzentrum Erlangen (RRZE) for a generous allotment of computer time.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, University of Kragujevac, R. Domanovića 12, P.O. Box 60, 34000, Kragujevac, Serbia

    Živadin D. Bugarčić, Jovana Rosić & Biljana Petrović

  2. Institute for Inorganic Chemistry, University of Erlangen-Nürnberg, Egerlandstrasse 1, 91058, Erlangen, Germany

    Živadin D. Bugarčić, Nadine Summa, Raph Puchta & Rudi van Eldik

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  1. Živadin D. Bugarčić
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Correspondence to Rudi van Eldik.

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Bugarčić, Ž.D., Rosić, J., Petrović, B. et al. Kinetics and mechanism of the substitution reactions of [PtCl(bpma)]+, [PtCl(gly-met-S,N,N)] and their aqua analogues with l-methionine, glutathione and 5′-GMP. J Biol Inorg Chem 12, 1141–1150 (2007). https://doi.org/10.1007/s00775-007-0283-1

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