Cisplatin (cis-diamminedichloroplatinum(II), cis-[PtCl2(NH3)2]), widely used drug in cancer treatment, has been allowed to react with simple molecular targets (L) mimicking biological functional groups. The selected molecules (L = acetamide, dimethylacetamide, urea and thiourea) react by ligand exchange leading to cis-[PtCl(NH3)2(L)]+ complexes that have been assayed by ESI-MS, IRMPD spectroscopy and computations in order to characterize their structure and platination site. Formal five-coordinate complexes are also delivered by ESI, [(PtCl(NH3)2(H2O)(L)]+, notably absent only when L is thiourea. IRMPD spectroscopy combined with computational analysis has revealed non-covalent adducts of the reactant aqua complex with an external ligand L corresponding to {cis-[PtCl(NH3)2(H2O)]+ · L}, reminiscent of the Eigen-Wilkins encounter complex invoked in the ligand displacement path in solution. The complex, successfully isolated in the gas phase, undergoes ligand exchange yielding cis-[PtCl(NH3)2(L)]+ + H2O when activated by multiple IR photons, testifying at the same time both structure and reactivity.

Short-lived intermediates (encounter complexes) in cisplatin ligand exchange elucidated by infrared ion spectroscopy / Corinti, Davide; Cecilia, Coletti; Nazzareno, Re; Roberto, Paciotti; Philippe, Maître; Chiavarino, Barbara; Crestoni, Maria Elisa; Fornarini, Simonetta. - In: INTERNATIONAL JOURNAL OF MASS SPECTROMETRY. - ISSN 1387-3806. - 435(2019), pp. 7-17. [10.1016/j.ijms.2018.10.012]

Short-lived intermediates (encounter complexes) in cisplatin ligand exchange elucidated by infrared ion spectroscopy

CORINTI, DAVIDE;Barbara Chiavarino;Maria Elisa Crestoni;Simonetta Fornarini
2019

Abstract

Cisplatin (cis-diamminedichloroplatinum(II), cis-[PtCl2(NH3)2]), widely used drug in cancer treatment, has been allowed to react with simple molecular targets (L) mimicking biological functional groups. The selected molecules (L = acetamide, dimethylacetamide, urea and thiourea) react by ligand exchange leading to cis-[PtCl(NH3)2(L)]+ complexes that have been assayed by ESI-MS, IRMPD spectroscopy and computations in order to characterize their structure and platination site. Formal five-coordinate complexes are also delivered by ESI, [(PtCl(NH3)2(H2O)(L)]+, notably absent only when L is thiourea. IRMPD spectroscopy combined with computational analysis has revealed non-covalent adducts of the reactant aqua complex with an external ligand L corresponding to {cis-[PtCl(NH3)2(H2O)]+ · L}, reminiscent of the Eigen-Wilkins encounter complex invoked in the ligand displacement path in solution. The complex, successfully isolated in the gas phase, undergoes ligand exchange yielding cis-[PtCl(NH3)2(L)]+ + H2O when activated by multiple IR photons, testifying at the same time both structure and reactivity.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11573/1279839
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