Oxidative ring expansion of a low-coordinate palladacycle: Synthesis of a robust T-shaped alkylpalladium(II) complex

[Display omitted] •Novel low-coordinate palladacycles have been isolated and full characterised.•Oxidation of cyclometalated tri-tert-butylphosphine using PhIO.•Oxygen-atom transfer is proposed to proceed by formation of a palladium oxo species.•Hemi-labile coordination of cyclometalated tri-tert-bu...

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Bibliographic Details
Published in:Inorganica Chimica Acta 2020-12, Vol.513, p.119948, Article 119948
Main Authors: Sinclair, Matthew J.G., Chaplin, Adrian B.
Format: Article
Language:English
Subjects:
Agostic interactions
Cyclometallation reactions
Low-coordinate complexes
Oxidation
Palladium
Synthesis
T shape
Terminal oxo complexes
Transition metals
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Summary:[Display omitted] •Novel low-coordinate palladacycles have been isolated and full characterised.•Oxidation of cyclometalated tri-tert-butylphosphine using PhIO.•Oxygen-atom transfer is proposed to proceed by formation of a palladium oxo species.•Hemi-labile coordination of cyclometalated tri-tert-butylphosphine. The synthesis of an unusual T-shaped alkylpalladium(II) complex featuring a cyclometalated tri-tert-butylphosphineoxide ligand by oxidation of the corresponding cyclometalated tri-tert-butylphosphine complex with PhIO is reported. We speculate that this reaction proceeds by formation of a transient palladium oxo intermediate and there are structural similarities with a late transition metal exemplar: Milstein’s seminal pincer ligated Pt(IV) oxo (Nature2008, 455, 1093–1096).
ISSN:0020-1693
1873-3255
DOI:10.1016/j.ica.2020.119948