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

doi:10.1002/anie.201511467

One-Electron Oxidation of [M(P^tBu₃)₂] (M=Pd, Pt): Isolation of Monomeric [Pd(P^tBu₃)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 journal › Article › peer-review

35 Citations (Scopus)

Abstract

Oxidation of zero-valent phosphine complexes [M(P^tBu₃)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 Pd^I 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 Pt^II complex [Pt(κ² _PC-P^tBu₂CMe₂CH₂)(P^tBu₃)]⁺ with concomitant formation of [Pt(P^tBu₃)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(P^tBu₃)₂] (M=Pd, Pt) using [Fc][PF₆].

Original language	English
Pages (from-to)	3754-3757
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	55
Issue number	11
Early online date	16 Feb 2016
DOIs	https://doi.org/10.1002/anie.201511467
Publication status	Published - 7 Mar 2016
Externally published	Yes

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

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].",

keywords = "C-H activation, oxidation, palladium, phosphane ligands, platinum",

author = "Thibault Troadec and Tan, {Sze Yin} and Wedge, {Christopher J.} and Rourke, {Jonathan P.} and Unwin, {Patrick R.} and Chaplin, {Adrian B.}",

year = "2016",

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doi = "10.1002/anie.201511467",

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T2 - Isolation of Monomeric [Pd(PtBu3)2]+ and Redox-Promoted C-H Bond Cyclometalation

AU - Troadec, Thibault

AU - Tan, Sze Yin

AU - Wedge, Christopher J.

AU - Rourke, Jonathan P.

AU - Unwin, Patrick R.

AU - Chaplin, Adrian B.

PY - 2016/3/7

Y1 - 2016/3/7

N2 - 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].

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].

KW - C-H activation

KW - oxidation

KW - palladium

KW - phosphane ligands

KW - platinum

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DO - 10.1002/anie.201511467

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One-Electron Oxidation of [M(P^tBu₃)₂] (M=Pd, Pt): Isolation of Monomeric [Pd(P^tBu₃)₂]⁺ and Redox-Promoted C-H Bond Cyclometalation

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