Stable Mononuclear Organometallic Pd(III) Complexes and Their C−C Bond Formation Reactivity

Organometallic Pd(III) complexes have been implicated as intermediates in a number of catalytic and stoichiometric transformations. While a few dinuclear organometallic Pd(III) complexes have been characterized, no mononuclear organometallic Pd(III) complexes have been isolated to date. Reported herein is the synthesis and characterization of a series of Pd(III) complexes supported by the tetradentate ligand N,N'-di-tert-butyl-2,11-diaza[3.3](2,6)pyridinophane (N4). Chemical or electrochemical oxidation of the Pd(II) complexes (N4)Pd(II)(R)(X) (R = Me, X = Cl: 1; R = Ph, X = Cl: 2; R = X = Me: 3) generates [(N4)Pd(III)MeCl](+) (1(+)), [(N4)Pd(III)PhCl](+) (2(+)), and [(N4)Pd(III)Me(2)](+) (3(+)). These stable Pd(III) complexes were isolated and characterized by X-ray diffraction, cyclic voltammetry, UV-vis, EPR, magnetic moment measurements, and DFT to confirm the presence of paramagnetic d(7) Pd(III) centers. Moreover, these Pd(III) complexes undergo light-induced C-C bond formation to give the corresponding homocoupled products ethane or biphenyl. Particularly remarkable is the observation for the first time of ethane formation from monomethyl Pd complexes.