One-Electron Oxidation of [M(P(t) Bu3 )2 ] (M=Pd, Pt): Isolation of Monomeric [Pd(P(t) Bu3 )2 ](+) and Redox-Promoted C-H Bond Cyclometalation

Angewandte Chemie
Thibault TroadecAdrian B Chaplin

Abstract

Oxidation of zero-valent phosphine complexes [M(P(t) Bu3 )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) Bu2 CMe2 CH2 )(P(t) Bu3 )](+) with concomitant formation of [Pt(P(t) Bu3 )2 H](+) .

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Citations

Mar 18, 2017·Chemical Communications : Chem Comm·Sebastian D PikeAdrian B Chaplin
Jul 12, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Anna MonfrediniMax Malacria
Oct 18, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·S JamaliH R Shahsavari
May 16, 2018·Angewandte Chemie·Yosi KratishYitzhak Apeloig
May 24, 2019·Chemical Communications : Chem Comm·Nereida HidalgoJesús Campos
May 7, 2020·Chemical Communications : Chem Comm·Pablo RíosSalvador Conejero
Nov 21, 2017·Chemistry : a European Journal·Miriam Mareen SchwabIngo Krossing
Oct 16, 2020·Angewandte Chemie·Christoph FrickeFranziska Schoenebeck
Jul 8, 2021·Journal of the American Chemical Society·Jian LiuLiang Deng
Sep 8, 2018·Organic Letters·Quillon SimpsonJoel F Hooper
Nov 12, 2019·Inorganic Chemistry·Andrew W CookTrevor W Hayton

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Methods Mentioned

BETA
NMR

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