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 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](+).