One‐Electron Oxidation of [M(P(t)Bu(3))(2)] (M=Pd, Pt): Isolation of Monomeric [Pd(P(t)Bu(3))(2)](+) and Redox‐Promoted C−H Bond Cyclometalation

Oxidation of zero‐valent phosphine complexes [M(P(t)Bu(3))(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...

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Autores principales: Troadec, Thibault, Tan, Sze‐yin, Wedge, Christopher J., Rourke, Jonathan P., Unwin, Patrick R., Chaplin, Adrian B.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2016
Materias:
Communications
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4797707/
https://www.ncbi.nlm.nih.gov/pubmed/26879233
http://dx.doi.org/10.1002/anie.201511467
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author Troadec, Thibault
Tan, Sze‐yin
Wedge, Christopher J.
Rourke, Jonathan P.
Unwin, Patrick R.
Chaplin, Adrian B.
author_facet Troadec, Thibault
Tan, Sze‐yin
Wedge, Christopher J.
Rourke, Jonathan P.
Unwin, Patrick R.
Chaplin, Adrian B.
author_sort Troadec, Thibault
collection PubMed
description Oxidation of zero‐valent phosphine complexes [M(P(t)Bu(3))(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(κ (2) (PC)‐P(t)Bu(2)CMe(2)CH(2))(P(t)Bu(3))](+) with concomitant formation of [Pt(P(t)Bu(3))(2)H](+).
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spelling pubmed-47977072016-03-21 One‐Electron Oxidation of [M(P(t)Bu(3))(2)] (M=Pd, Pt): Isolation of Monomeric [Pd(P(t)Bu(3))(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. Angew Chem Int Ed Engl Communications Oxidation of zero‐valent phosphine complexes [M(P(t)Bu(3))(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(κ (2) (PC)‐P(t)Bu(2)CMe(2)CH(2))(P(t)Bu(3))](+) with concomitant formation of [Pt(P(t)Bu(3))(2)H](+). John Wiley and Sons Inc. 2016-02-16 2016-03-07 /pmc/articles/PMC4797707/ /pubmed/26879233 http://dx.doi.org/10.1002/anie.201511467 Text en © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution (http://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Communications
Troadec, Thibault
Tan, Sze‐yin
Wedge, Christopher J.
Rourke, Jonathan P.
Unwin, Patrick R.
Chaplin, Adrian B.
One‐Electron Oxidation of [M(P(t)Bu(3))(2)] (M=Pd, Pt): Isolation of Monomeric [Pd(P(t)Bu(3))(2)](+) and Redox‐Promoted C−H Bond Cyclometalation
title One‐Electron Oxidation of [M(P(t)Bu(3))(2)] (M=Pd, Pt): Isolation of Monomeric [Pd(P(t)Bu(3))(2)](+) and Redox‐Promoted C−H Bond Cyclometalation
title_full One‐Electron Oxidation of [M(P(t)Bu(3))(2)] (M=Pd, Pt): Isolation of Monomeric [Pd(P(t)Bu(3))(2)](+) and Redox‐Promoted C−H Bond Cyclometalation
title_fullStr One‐Electron Oxidation of [M(P(t)Bu(3))(2)] (M=Pd, Pt): Isolation of Monomeric [Pd(P(t)Bu(3))(2)](+) and Redox‐Promoted C−H Bond Cyclometalation
title_full_unstemmed One‐Electron Oxidation of [M(P(t)Bu(3))(2)] (M=Pd, Pt): Isolation of Monomeric [Pd(P(t)Bu(3))(2)](+) and Redox‐Promoted C−H Bond Cyclometalation
title_short One‐Electron Oxidation of [M(P(t)Bu(3))(2)] (M=Pd, Pt): Isolation of Monomeric [Pd(P(t)Bu(3))(2)](+) and Redox‐Promoted C−H Bond Cyclometalation
title_sort one‐electron oxidation of [m(p(t)bu(3))(2)] (m=pd, pt): isolation of monomeric [pd(p(t)bu(3))(2)](+) and redox‐promoted c−h bond cyclometalation
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4797707/
https://www.ncbi.nlm.nih.gov/pubmed/26879233
http://dx.doi.org/10.1002/anie.201511467
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