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One-Electron Oxidation of [M(PtBu3)2] (M=Pd, Pt): Isolation of Monomeric [Pd(PtBu3)2]+and Redox-Promoted C−H Bond Cyclometalation

Troadec, Thibault, Tan, Sze-yin, Wedge, Christopher J., Rourke, Jonathan P., Unwin, Patrick R. and Chaplin, Adrian B. (2016) One-Electron Oxidation of [M(PtBu3)2] (M=Pd, Pt): Isolation of Monomeric [Pd(PtBu3)2]+and Redox-Promoted C−H Bond Cyclometalation. Angewandte Chemie International Edition, 55 (11). pp. 3754-3757. ISSN 1433-7851

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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
Subjects: Q Science > QD Chemistry
Schools: School of Applied Sciences
Related URLs:
Depositing User: Christopher Wedge
Date Deposited: 27 Mar 2017 13:37
Last Modified: 15 Nov 2017 17:32
URI: http://eprints.hud.ac.uk/id/eprint/30047

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