Can an Elusive Platinum(III) Oxidation State be Exposed in an Isolated Complex?
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim..
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.
| Errataetall: |
ErratumIn: Angew Chem Int Ed Engl. 2022 May 2;61(19):e202202822. - PMID 35466534 |
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| Medienart: |
E-Artikel |
| Erscheinungsjahr: |
2020 |
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| Erschienen: |
2020 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:59 |
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| Enthalten in: |
Angewandte Chemie (International ed. in English) - 59(2020), 36 vom: 01. Sept., Seite 15595-15598 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Corinti, Davide [VerfasserIn] |
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| Links: |
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| Themen: |
Ab initio calculations |
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| Anmerkungen: |
Date Completed 11.12.2020 Date Revised 25.04.2022 published: Print-Electronic ErratumIn: Angew Chem Int Ed Engl. 2022 May 2;61(19):e202202822. - PMID 35466534 Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1002/anie.202007597 |
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NLM311860966 |
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| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. | ||
| 520 | |a 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 | ||
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| 650 | 4 | |a Research Support, Non-U.S. Gov't | |
| 650 | 4 | |a IRMPD spectroscopy | |
| 650 | 4 | |a ab initio calculations | |
| 650 | 4 | |a non-innocent ligands | |
| 650 | 4 | |a radical ions | |
| 650 | 4 | |a reactive intermediates | |
| 700 | 1 | |a Frison, Gilles |e verfasserin |4 aut | |
| 700 | 1 | |a Chiavarino, Barbara |e verfasserin |4 aut | |
| 700 | 1 | |a Gabano, Elisabetta |e verfasserin |4 aut | |
| 700 | 1 | |a Osella, Domenico |e verfasserin |4 aut | |
| 700 | 1 | |a Crestoni, Maria Elisa |e verfasserin |4 aut | |
| 700 | 1 | |a Fornarini, Simonetta |e verfasserin |4 aut | |
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