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Can an Elusive Platinum(III) Oxidation State be Exposed in an Isolated Complex?
Author(s) -
Corinti Davide,
Frison Gilles,
Chiavarino Barbara,
Gabano Elisabetta,
Osella Domenico,
Crestoni Maria Elisa,
Fornarini Simonetta
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202007597
Subject(s) - platinum , chemistry , deprotonation , prodrug , dissociation (chemistry) , oxidation state , ligand (biochemistry) , combinatorial chemistry , stereochemistry , photochemistry , catalysis , organic chemistry , receptor , ion , biochemistry
Platinum(IV) complexes are extensively studied for their activity against cancer cells as potential substitutes for the widely used platinum(II) drugs. Pt IV complexes are kinetically inert and need to be reduced to Pt II 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 d xz orbital of platinum and the p z of nitrogen on the amino group, the latter acting as a non‐innocent ligand.