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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
Author(s) -
Troadec Thibault,
Tan Szeyin,
Wedge Christopher J.,
Rourke Jonathan P.,
Unwin Patrick R.,
Chaplin Adrian B.
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201511467
Subject(s) - chemistry , electron paramagnetic resonance , palladium , cyclic voltammetry , valence (chemistry) , phosphine , electrochemistry , redox , crystallography , stereochemistry , medicinal chemistry , inorganic chemistry , nuclear magnetic resonance , catalysis , electrode , biochemistry , physics , organic chemistry
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] + .