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

Thibault Troadec, Sze Yin Tan, Christopher J. Wedge, Jonathan P. Rourke, Patrick R. Unwin, Adrian B. Chaplin

Research output: Contribution to journalArticle

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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(κ2 PC-PtBu2CMe2CH2)(PtBu3)]+ with concomitant formation of [Pt(PtBu3)2H]+. Uncharted territory: The reaction chemistry of palladium and platinum complexes bearing a +I formal oxidation state has been accessed through one-electron oxidation of [M0(PtBu3)2] (M=Pd, Pt) using [Fc][PF6].

LanguageEnglish
Pages3754-3757
Number of pages4
JournalAngewandte Chemie - International Edition
Volume55
Issue number11
Early online date16 Feb 2016
DOIs
Publication statusPublished - 7 Mar 2016
Externally publishedYes

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Oxidation
phosphine
Electrons
Palladium
Bearings (structural)
X ray crystallography
Platinum
Cyclic voltammetry
Paramagnetic resonance
Cations
Positive ions
Derivatives
Oxidation-Reduction
1,2-difluorobenzene
ferrocenium

Cite this

Troadec, Thibault ; Tan, Sze Yin ; Wedge, Christopher J. ; Rourke, Jonathan P. ; Unwin, Patrick R. ; Chaplin, Adrian B. / One-Electron Oxidation of [M(PtBu3)2] (M=Pd, Pt) : Isolation of Monomeric [Pd(PtBu3)2]+ and Redox-Promoted C-H Bond Cyclometalation. In: Angewandte Chemie - International Edition. 2016 ; Vol. 55, No. 11. pp. 3754-3757.
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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.; Chaplin, Adrian B.

In: Angewandte Chemie - International Edition, Vol. 55, No. 11, 07.03.2016, p. 3754-3757.

Research output: Contribution to journalArticle

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AB - 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(κ2 PC-PtBu2CMe2CH2)(PtBu3)]+ with concomitant formation of [Pt(PtBu3)2H]+. Uncharted territory: The reaction chemistry of palladium and platinum complexes bearing a +I formal oxidation state has been accessed through one-electron oxidation of [M0(PtBu3)2] (M=Pd, Pt) using [Fc][PF6].

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