Can an Elusive Platinum(III) Oxidation State be Exposed in an Isolated Complex?

Autor: Davide Corinti, Simonetta Fornarini, Gilles Frison, Elisabetta Gabano, Maria Elisa Crestoni, Barbara Chiavarino, Domenico Osella
Přispěvatelé: Dipartimento di Chimica e Tecnologie del Farmaco, Università degli Studi di Roma 'La Sapienza' = Sapienza University [Rome], Laboratoire de chimie moléculaire (LCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X), Dipartimento di Scienze e Innovazione Tecnologica [Alessandria] (DISIT), Università degli Studi del Piemonte Orientale - Amedeo Avogadro (UPO)
Rok vydání: 2020
Předmět:
Zdroj: Angewandte Chemie International Edition
Angewandte Chemie International Edition, Wiley-VCH Verlag, 2020, 59 (15595-15598), ⟨10.1002/anie.202007597⟩
ISSN: 1521-3773
1433-7851
DOI: 10.1002/anie.202007597⟩
Popis: International audience; Platinum(IV) complexes are extensively studied for their activity against cancer cells as potential substitutes for the widely used platinum(II) drugs. PtIV complexes are kinetically inert and need to be reduced to PtII species to play their pharmacological action, thus acting as prodrugs. The mechanism of the reduction step inside the cell is however still largely unknown. Gas-phase activation of deprotonated platinum(IV) prodrugs was found to generate products in which platinum has a formal +3 oxidation state. IR multiple photon dissociation spectroscopy is thus used to obtain structural information helping to define the nature of both the platinum atom and the ligands. In particular, comparison of calculations at DFT, MP2 and CCSD levels with experimental results demonstrates that the localization of the radical is about equally shared between the dxz orbital of platinum and the pz of nitrogen on the amino group, the latter acting as a non-innocent ligand.
Databáze: OpenAIRE
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