One-electron oxidation of [M((PBu3)-Bu-t)(2)] (M=Pd, Pt): isolation of monomeric [Pd((PBu3)-Bu-t)(2)](+) and redox-promoted C-H bond cyclometalation

Troadec, Thibault, Tan, Sze-yin, Wedge, Christopher J., Rourke, Jonathan P. ORCID: https://orcid.org/0000-0002-8961-1021, Unwin, Patrick R. and Chaplin, Adrian B. 2016. One-electron oxidation of [M((PBu3)-Bu-t)(2)] (M=Pd, Pt): isolation of monomeric [Pd((PBu3)-Bu-t)(2)](+) and redox-promoted C-H bond cyclometalation. Angewandte Chemie International Edition 55 (11) , pp. 3754-3757. 10.1002/anie.201511467

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Abstract

Oxidation of zero-valent phosphine complexes [M(PtBu3)2] (M=Pd, Pt) has been investigated in 1,2-difluorobenzene solution using cyclic voltammetry and subsequently using the ferrocenium cation as a chemical redox agent. In the case of palladium, a mononuclear paramagnetic PdI derivative was readily isolated from solution and fully characterized (EPR, X-ray crystallography). While in situ electrochemical measurements are consistent with initial one-electron oxidation, the heavier congener undergoes C−H bond cyclometalation and ultimately affords the 14 valence-electron PtII complex [Pt(κ2PC-PtBu2CMe2CH2)(PtBu3)]+ with concomitant formation of [Pt(PtBu3)2H]+.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Schools > Chemistry
Publisher:	Wiley
ISSN:	1433-7851
Date of First Compliant Deposit:	3 April 2023
Last Modified:	12 May 2023 15:21
URI:	https://orca.cardiff.ac.uk/id/eprint/155223

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