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One-electron oxidation of [M(Pt Bu3 )2 ] (M=Pd, Pt): isolation of monomeric [Pd(Pt Bu3 )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(Pt Bu3 )2 ] (M=Pd, Pt): isolation of monomeric [Pd(Pt Bu3 )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: Chemistry
Publisher: Wiley
ISSN: 1433-7851
Date of First Compliant Deposit: 16 January 2019
Date of Acceptance: 16 February 2016
Last Modified: 21 Jan 2019 12:45
URI: http://orca-mwe.cf.ac.uk/id/eprint/118453

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