Short-lived intermediates (encounter complexes) in cisplatin ligand exchange elucidated by infrared ion spectroscopy
| Autor: | Roberto Paciotti, Nazzareno Re, Maria Elisa Crestoni, Simonetta Fornarini, Davide Corinti, Philippe Maître, Barbara Chiavarino, Cecilia Coletti |
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| Přispěvatelé: | Dipartimento di Chimica e Tecnologie del Farmaco, Università degli Studi di Roma 'La Sapienza' = Sapienza University [Rome], Università degli studi 'G. d'Annunzio' Chieti-Pescara [Chieti-Pescara] (Ud'A), Laboratoire de Chimie Physique D'Orsay (LCPO), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Dipartimento di Studi di Chimica e Tecnologia delle Sostanze Biologicamente Attive |
| Rok vydání: | 2019 |
| Předmět: |
inorganic chemicals
IRMPD spectroscopy non-covalent complexes DFT calculations 010402 general chemistry 01 natural sciences Medicinal chemistry Dimethylacetamide Adduct chemistry.chemical_compound [CHIM.ANAL]Chemical Sciences/Analytical chemistry [CHIM]Chemical Sciences Molecule [CHIM.COOR]Chemical Sciences/Coordination chemistry Reactivity (chemistry) Infrared multiphoton dissociation Physical and Theoretical Chemistry Spectroscopy Instrumentation ComputingMilieux_MISCELLANEOUS platinum(II) complexes photodissociation reaction mechanisms Ligand 010401 analytical chemistry Condensed Matter Physics 0104 chemical sciences chemistry Thiourea |
| Zdroj: | International Journal of Mass Spectrometry International Journal of Mass Spectrometry, Elsevier, 2019, 435, pp.7-17. ⟨10.1016/j.ijms.2018.10.012⟩ |
| ISSN: | 1387-3806 |
| DOI: | 10.1016/j.ijms.2018.10.012 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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