Reversible Single-Electron-Transfer to Oxygen in a Stable N‑Heterocyclic Carbene Palladium(I) Metalloradical

The chemical and electrochemical one-electron oxidation of [Pd­(IPr)2] (1) leads to the formation of mononuclear palladium­(I) complex [Pd­(IPr)2]­[PF6] (2). This bench-stable metalloradical has been fully characterized and its structure confirmed by X-ray diffraction analysis. EPR and DFT studies c...

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Bibliographic Details
Published in:Inorganic chemistry 2023-12, Vol.62 (49), p.19838-19842
Main Authors: Maties, Georgiana, Gómez-Sal, Pilar, Yebra, Cristina G., Andrés, Román, de Jesús, Ernesto
Format: Article
Language:English
Subjects:
Communication
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Summary:The chemical and electrochemical one-electron oxidation of [Pd­(IPr)2] (1) leads to the formation of mononuclear palladium­(I) complex [Pd­(IPr)2]­[PF6] (2). This bench-stable metalloradical has been fully characterized and its structure confirmed by X-ray diffraction analysis. EPR and DFT studies confirm the localization of the unpaired electron onto the metal center. Low temperature NMR and EPR measurements reveal the ability of complex 2 to reversibly coordinate and reduce the dioxygen molecule, leading to the formation of a three-coordinate complex, [PdII(IPr)2(η1-O2)]+ (4), in which the unpaired electron has been transferred to the superoxido ligand.
ISSN:0020-1669
1520-510X
DOI:10.1021/acs.inorgchem.3c02878